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31st Annual

International Symposium on Polymer Analysis and Characterization

Book of Abstracts

June 3-6, 2018

North Bethesda, Maryland, USA

ISPAC 2018

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ISPAC 2018

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Major Exhibitor Sponsor

ISPAC 2018

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ISPAC 2018

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What is ISPAC?

ISPAC stands for International Symposium on Polymer Analysis and Characterization. It is a non-profit scientific organization formed to provide an international forum for the presentation of recent advances in the field of polymer analysis and characterization methodologies. This unique Symposium brings together analytical chemists and polymers scientists involved in the analysis and characterization of polymeric materials. Meetings are held annually, rotating to venues in the USA, Europe and Asia.

ISPAC sessions comprise a two and a half day program with invited lectures, submitted lectures, poster sessions, discussions and information exchange on polymer analysis and characterization approaches, techniques and applications. Invited talks include state-of-the art developments. Each session features lectures and a 30 minute open discussion period. The participants typically come from academic, industrial, and government settings and work with different aspects of polymer analysis and characterization approaches, techniques and applications. It will be useful to network with one another, exchanging information and tips about different techniques, and learning about the latest developments.

Lecturers are urged to include introductory material in their presentation to bring participants "up to speed", and are allotted the time to accomplish this. The discussion periods allow for extended interaction among the lecturers and the conference participants.

If your work involves any aspect of polymer characterization, physical testing, materials analysis, or polymers in general, please consider attending this conference. You are welcome to submit a contributed oral paper or a poster.

ISPAC 2018

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Save the Date : ISPAC 2019

Date: June 2nd (SUN) to 5th (WED) Location: Miyagi Zao Royal Hotel

(http://www.daiwaresort.jp.e.zr.hp.transer.com/zaou/index.html/)

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ISPAC 2018

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ISPAC Governing Board

Wayne F. Reed, Tulane University, USA; [email protected], ISPAC GB Chair for the Americas, ISPAC-2013 Chair

G. Julius Vancso, University of Twente, The Netherlands; [email protected], ISPAC GB Chair for Europe and Asia, ISPAC-2012 Chair

Taihyun Chang, Pohang University of Science and Technology, Republic of Korea; [email protected]

H.N. Cheng, USDA Southern Regional Research Center, USA; [email protected]

A. Willem deGroot, Dow Chemical Co., USA; [email protected], ISPAC-2015 Chair

Nikos Hadjichristidis, KAUST, King Abdullah University of Science and Technology, Saudi Arabia; [email protected]

Josef Janca, Institute of Scientific Instruments, Academy of Sciences of the Czech Republic, Brno, Czech Republic; [email protected]

Yeng Ming Lam, NTU-MSE, Singapore, [email protected], ISPAC 2016 Symposium Chair

Harald Pasch, University of Stellenbosch, South Africa; [email protected]

Clemens Schwarzinger, Johannes Kepler University, Linz, Austria; [email protected], ISPAC 2017 Symposium Chair

Associate Member of the Governing Board

Hiroshi Jinnai, Tohoku University, Japan, [email protected]

Emeritus Members of the Governing Board

Howard Barth, DuPont Co., USA, ISPAC Founding Chair Emeritus

Guy Berry, Carnegie Mellon University, USA; [email protected], ISPAC GB Honorary Chair Emeritus

Stephen T. Balke, University of Toronto, Canada

Oscar Chiantore, University of Torino, Italy, [email protected]

John V. Dawkins, Loughborough University, UK

Marguerite Rinaudo, CERMAV-CNRS, France, [email protected], ISPAC-2014 Chait

Pavel Kratochvil, Institute of Macromolecular Chemistry, Czech Republic

Sadao Mori, Mie University, Japan

Petr Munk, University of Texas at Austin, USA

ISPAC 2018

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ISPAC 2018 Organizing Committee

Ronald Jones (Symposium Chair) – NIST, [email protected]

Kathryn Beers - NIST, [email protected]

Willem deGroot – DowDupont, [email protected]

Alexander Norman – ExxonMobil, [email protected]

Peter Olmsted – Georgetown University, [email protected]

Lawrence Sita – University of Maryland, [email protected]

Andre Striegel – NIST, [email protected]

ISPAC 2018 – Sunday, June 3, 2018

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ISPAC Short Courses Emerging Trends in Polymer Characterization 7:45 AM Breakfast – Linden Oak 8:00 Registration, All Day – Brookside Foyer

Neutron and X-ray Techniques

Brookside A

Advances in Polymer Characterization Brookside B

9:00 Elastic Scattering Methods for Characterizing Structure Michael Hore, Case Western Reserve University

Introduction to interaction-based separations: IC, LCCC and 2D-LC Taihyun Chang, Pohang University

10:30 Break

10:45 Inelastic scattering methods for characterizing mobility Yun Liu, NIST

Introduction to size-based separations: SEC, HDC, FFF, and detection methods Andre Striegel, NIST

12:15 PM Lunch (Linden Oak)

1:00 Imaging Soft Materials with X-rays and Neutrons Daniel Hussey, NIST

Emerging Trends in Rheology Anthony Kotula, NIST

2:30 Break

2:45 Rheology and Small Angle Scattering Kathleen Weigandt, NIST

Polymer Science and Advanced Solid State NMR Ryan Nieuwendaal, NIST

6:00 Reception – Forest Glen

ISPAC 2018 – Monday, June 4, 2018

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7:00 AM Registration, All Day – Grand Foyer

Vendor Exhibition, All Day – Grand Foyer 7:00 AM Breakfast – Salon H

8:00 AM Opening Remarks – Dr. Ronald Jones and Prof. Wayne Reed (Salon F/G) 8:15 AM Materials Science at NIST – Dr. Eric Lin, Director, Material Measurement

Laboratory, NIST (Salon F/G)

Advances in Polymer and Soft Materials Rheology Plenary Lectures – Salon F/G 8:30 AM M.01 - DowDuPont Lecture

Polyethylene topology and rheology control for recycling applications Jaap den Doelder, DowDuPont

9:00 AM M.02 - Predicting the Linear and Non-Linear Rheology of Polydisperse Linear Polymers Daniel Read, University of Leeds

9:30 AM M.03 - Toward in situ morphology characterization of polymeric fluids under arbitrary processing flows Matthew Helgeson, University of California Santa Barbara

10:00 AM Rheology Discussion Panel

10:30 AM Refreshments

Deformation of Soft Materials Salon F

Characterization with Chromatography Salon G

11:00 AM M.11 – Rheo-Raman microscopy for polymer crystallization characterization – A. Kotula

M.15 – Comparison of fast SEC and UHP SEC for the second dimension in two-dimensional liquid chromatography of polymers – E. Uliyanchenko

11:20 AM M.12 – Effects of Orientation and Deformation Mode in Dynamic Mechanical Analysis of Engineered Materials – S. Cotts

M.16 – Understanding Polymer Structure by Interaction Polymer Chromatography - C.J.Rasmussen


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11:40 AM M.13 – Selective Cell Adhesion on Peptide-Polymer Nano-Fiber Mats - G. Kaur

M.17 – Light Scattering without Refractive Index Increment: A New Approach to Calibrate SEC-Light Scattering Setups – D. Lohmann

12:00 PM M.14 – Viscoelastic behavior of polyelectrolyte complexes across coacervate-precipitate transition regime – S. Ali

M.18 – Fast Separations of Synthetic Polymers Using Advanced Polymer Chromatography (APC) - Janco, M.

12:20 PM Buffet Lunch - Salon H

12:30 PM

Poster Setup

V.1 – Ondax (sponsored presentation) Salon G

12:50 PM V.2 – Tosoh (sponsored presentation) Salon G

1:10 PM V.3 – Waters (sponsored presentation) Salon G

Advancing Materials Science with Big Data Plenary Lectures - Salon F/G

2:00 PM M.04 – Scoping the Polymer Genome: A Roadmap for Rational Polymer Dielectrics Design and Beyond Rampi Ramprasad, Georgia Institute of Technology

2:30 PM M.05 – Towards Polymer Informatics: Databases, Infrastructure and Beyond Debra Audus, NIST

3:00 PM M.06 – Materials-Specific Considerations for Machine Learning Bryce Meredig, Citrine Informatics

3:30 PM Big Data Discussion Panel 4:00 PM Refreshments


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Computation and Characterization Salon F

Molecular Control and Characterization Salon G

4:30 M.21 – From Data Science to Data Stories: Automating advanced analytics for R&D and manufacturing – G. Smits

M.24 – Perfect Polystyrene Sulfonate: Synthesis, Characterization and Self Diffusion in Ternary Solutions – P. Balding

4:50 PM M.22 – typyPRISM: A Computational Tool for Liquid-State Theory Calculations of Macromolecular Materials – T. Martin

M.25 – Conformational control of tethered functionalized mPEO on anatase nanocrystals surface – R. Simonutti

5:10 PM M.23 – TBA - F. Vargas Lara M.26 – Preparation and Characterization of Polyurethanes from Carbohydrates – H. N. Cheng

Poster Exhibition

White Oak A Heavy hors d’ouevres and Open Bar

6:30 – 9:00

ISPAC 2018 – Tuesday, June 5, 2018

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7:00 AM Registration, All Day – Grand Foyer

Vendor Exhibition, All Day – Grand Foyer 7:00 AM Breakfast – Salon H

Advances in Chromatography and Spectroscopy Plenary Lectures - Salon F/G

8:00 AM T.01 – Correlated polymer characterization via SEC-IR Detection with a new QCL Laser Spectrometer and SEC-NMR with a new 60 MHz MR-NMR Spectrometer Jennifer Kubel, Karlsruhe Institute of Technology

8:30 AM T.02 – Characterization of Complex Synthetic Polymers by Advanced Separations and Detection Techniques David Meunier, DowDuPont

9:00 AM T.03 – HPLC Characterization of Block Copolymers Taihyun Chang, Pohang University of Science and Technology

9:30 AM Chromatography and Spectroscopy Discussion Panel

10:00 AM Refreshments

Condensed Phases Salon F

Macromolecular Architectures Salon G

10:30 AM T.11 – Two-Dimensional Terahertz (2D THz) Raman Correlation Spectroscopy Study of the Crystallization of Bioplastics – I. Noda

T.15 – Synthesis and Characterization of Polyolefins with Precise Control of Branch Frequency and Branch Length – S. V. Orski

10:50 AM T.12 – Imaging Orientation Angles and Order Parameters of Semicrystalline Polymers by Polarization IR and Raman – Y. Lee

T.16 – Functional electrospun membranes featuring grafted polymer brushes: The characterization challenge – Y. Liu

11:10 AM T.13 – Multiple Order-to-Order Transitions within Ultrathin Films of Sugar-Polyolefin Amphiphilic Conjugates – S. R. Nowak

T.17 – Characterization of the chemical composition distribution of 1-octene based POP/POE by HPLC – J. H. Arndt


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11:30 PM T.14 – Liquid-solid transitions of a repulsive system with also a short-range attractive potential – G. Yuan

T.18 – Striving for Perfection: “Defect”-Free Polymer Networks for Improved Metrology – J. Sarapas

11:50 PM

Buffet Lunch – Salon H

ISPAC Leaders of R&D Panel Discussion

“The Next Generation of Characterization Needs in Polymer Science” Salon F/G 1:15 PM Pat Brant (ExxonMobil), Naryan Ramesh (DowDuPont), Raj Krishnaswamy

(Braskem North America), Peter Maziarz (Pfizer Consumer Health) Discussion Leader: Eric Lin, NIST

Macromolecular Architectures Plenary Lectures - Salon F/G

2:30 PM T.04 – ExxonMobil Lecture Molecular Engineering with Anionic Polymerization Lian Hutchings, Durham University

3:00 PM T.05 – New Opportunities for Precision Polyolefins: Design, Characterization and Dynamic Behavior of Nanostructured Polyolefin Block Copolymers Lawrence Sita, University of Maryland

3:30 PM T.06 - Polyhomologation: A Powerful Tool Towards Well-Defined Polyethylene-Based Polymeric Materials Nikos Hadjichristidis, KAUST

4:00 PM Architectures Discussion Panel

4:30 PM Break


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Condensed Phase Spectroscopy Salon F

Advances in Chromatography Salon G

5:00 PM T.21 – Bulk heterojunction interfacial structure from REDOR NMR – R. Nieuwendaal

T.25 – Characterization of branched polycarbonate by comprehensive two-dimensional liquid chromatography with multi-detector setup and correlation with Monte-Carlo simulations – N. Appel

5:20 PM T.22 – Characterization of modified silicas with industrial interest – A. M. Netto

T.26 – Valorisation of multi-dimensional analytical approaches to unlock complex products characterization. The particular case of apolar commercial synthetic polymers – J. Desport

5:40 PM T.23 – Relating Post Yield Mechanical Behavior in Polyethylenes to Spatially-varying Molecular Deformation Using Infrared Spectroscopic Imaging: Homopolymers – P. Mukherjee

T.27 – Size Exclusion Chromatography Characterization of Poly(Ester Urethane) Degradation Products – D. Yang

6:00 PM T.24 - Influencing liquid crystalline gel formation in cellulose ionic liquid solutions by adding water and nanoparticles – A. Rajeev

T.28 – Polymer separation beyond SEC – expanding the range from molecules to particles – R. Reed

6:30 PM ISPAC Social Hour Grand Ballroom Veranda Hors d’Ouevres and Open Bar

7:30 PM 2018 ISPAC Banquet Ballroom E

ISPAC 2018 – Wednesday, June 6, 2018

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7:00 AM Registration, All Day 7:00 AM Breakfast

Emerging Methods in Scattering Plenary Lectures - Salon F/G

8:00 AM W.01 - Wyatt Technology Lecture Structure and Dynamics in Polymer Grafted Nanoparticle Systems Michael Hore, Case Western Reserve University

8:30 AM W.02 – Recent Advances in X-ray Scattering Methods for Soft Materials Kevin Yager, Brookhaven National Laboratory

9:00 AM W.03 – Pfizer Consumer Healthcare Lecture Soft matter structure measurement by Polarized Resonant Soft X-ray Scattering Dean DeLongchamp, NIST

9:30 AM Scattering Discussion Panel 10:00 AM Refreshment Pause/Lunch Pickup

Tour of the National Institute of Standards and Technology (NIST) Participants must register for tour through ISPAC website prior to meeting to meet security requirements.

10:30 AM Bus pickup at Marriot Main Lobby 11:15 AM NIST Integrating Sphere Laboratory 12:00 PM Lunch at NIST Cafeteria (not included in registration)

Walk thru NIST Museum 1:15 PM Trace Contraband Detection Laboratory 2:00 PM NIST Center for Neutron Research 3:00 PM Arrive at Marriot

End of 2018 ISPAC meeting, see you in Japan!!

ISPAC 2018 – Plenary : Advances in Polymer and Soft Materials Rheology

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DowDuPont Lecture

M.1 - Polyethylene topology and rheology control for recycling applications

Jaap den Doelder

Performance Plastics R&D, Dow Benelux BV, Terneuzen, The Netherlands. [email protected]

Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, The

Netherlands. [email protected]

Transforming polymer pellets into desired products like films and bottles requires tailored

viscoelastic polymer properties. The base rheology can be predicted from molecular structure,

including features such as molar mass distributions coupled to long-chain branching topology

distributions. This can be connected back to the chemistry and processes used to manufacture

the pellets. Examples of this process-to-product connectivity will be given in this talk for

industrial solution and high-pressure ethylene polymerization.

Thermoplastic polymers like polyethylene can be remolten and extruded multiple times. As

such, they are very suitable to feature in mechanical recycling applications, which is an area of

strongly growing society interest. Current applications however are limited due to lack of

knowledge and control of recycled polymer grade performance. We will present two scenarios

where the molecular rheology framework, as used before for virgin polymers, is applied to

predict the processability performance of recycled material. The first case deals with post-

consumer HDPE blend viscosity predictions. The second example quantifies the rheological

implications of structural modification and degradation during high-temperature extrusion of

LDPE. This methodology brings added control to mechanical recycling and thus opens up a

growing spectrum of applications for recycled polymers.


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M.2 - Predicting the Linear and Non-Linear Rheology of Polydisperse

Linear Polymers

Daniel J. Read, Chinmay Das, Victor A.H. Boudara

School of Mathematics, University of Leeds, Leeds, LS2 9JT, U.K. [email protected]

The last fifty (yes, fifty!) years have seen an enormous amount of progress in predicting the

flow behavior of entangled polymeric materials. Building on the pioneering work of de

Gennes, Edwards and Doi, the dynamics of polymers are understood in terms of the “tube

model” (or related theories), which predict relaxation processes such as reptation, contour

length fluctuations, and constraint release; and, for rapid non-linear deformations, stretch

relaxation of the polymer chains. Academic studies have typically (and successfully) focused

on idealized polymeric systems: nearly monodisperse polymers, or mixtures of two or three

molecular weights. However, industrial polymer resins are almost always polydisperse, often

strongly so. This drives the question: for a given, known, distribution of molecular weight,

can we predict the linear, and non-linear, rheology?

Most schemes for predicting linear rheology of polydisperse polymers have built on the

“double reptation” formalism (see [1] for a summary). This predicts the relaxation of the

mixture from the relaxation profiles of the individual components, but crucially assumes that

the relaxation spectrum of one polymer is not affected by being mixed with the others. This

assumption is certainly wrong for the simplest “polydisperse” polymer, a bidisperse mixture

of just two molecular weights (but broad polydispersity often masks these errors).

We will present two developments from our group: (i) a computational algorithm for

predicting the linear rheology of arbitrary mixtures of linear polymers, which builds upon

our recent work on bidisperse polymers, and (ii) a simple “toy” constitutive equation which

can be used to predict non-linear flow behavior in shear and extension of bidisperse, and

polydisperse, polymers.

[1] Dealy, J. M., D. J. Read, and R. G. Larson, “Structure and rheology of molten polymers:

from structure to flow behavior and back again” (Carl Hanser Verlag GmbH & Co. KG,

Munchen, 2018).


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M.3 - Toward in situ morphology characterization of polymeric fluids

under arbitrary processing flows

Matthew E. Helgeson

Department of Chemical Engineering, University of California Santa Barbara, Santa Barbara, CA USA.

[email protected]

In situ small angle neutron scattering under flow (flow-SANS) has become a critical tool for

measuring and formulating processing-structure-property relationships of polymeric fluids.

However, sample environments and associated measurement methods for flow-

SANS/SAXS have largely limited these measurements to steady state flows and simple

rheometric deformations (pure shearing or elongation) that fail to capture the complex

nonlinear and time-varying deformations encountered during polymer processing. Recently,

significant advances in neutron detection as well as the design of new fluidic devices have

opened up new capabilities for probing complex, time-varying deformations that more

reliably emulate real processing flows. Here, we will summarize the key advances leading

to these capabilities, and illustrate their usefulness with two examples involving the flow-

induced structuring in polymer nanocomposites. In the first example, we use time-resolved

rheo-SANS, involving simultaneous flow-SANS and rheological measurement, to explore

the kinetics and mechanics of shear-induced aggregation of nanoparticle suspensions in

associative polymers during startup and cessation. The results show that, over a wide range

of conditions, clustering is dominated by competition of hydrodynamic interactions and

Brownian motion of the dispersed nanoparticles, rather than by polymer normal stresses as

originally proposed. In the second, we use a newly developed fluidic four-roll mill (FFoRM)

in order to probe how the flow-induced alignment of rodlike nanoparticles in polymer

solutions depends on the type of applied deformation.

Figure 1: Schematic illustrating the fluidic four roll mill (FFoRM) and its use in flow visualization and SANS

measurements on polymeric fluids during complex flows.

FFoRM Flow visualization SANS

ISPAC 2018 - Session: Deformation of Soft Materials

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M.11 - Rheo-Raman microscopy for polymer crystallization

characterization

A.P. Kotula

Materials Science and Engineering Division, NIST, Gaithersburg, MD; [email protected]

Polymer processing requires a deep understanding of the connection between

viscoelastic polymer flow and the mechanical properties of the final product. Therefore,

instrumentation that can simultaneously measure flow properties and physicochemical

changes in materials is crucial to explaining structure-process-property relationships in

polymers. Chemical information such as composition, bond formation or scission, and

molecular conformation affect the rheological properties of polymers; this critical chemical

information can be obtained via vibrational spectroscopic techniques such as infrared (IR)

or Raman spectroscopy. Attenuated total reflection IR measurements on a rheometer are

limited by a short penetration depth into the sample (order 1 μm) and water absorption.

Because Raman spectroscopy does not have these limitations, techniques for coupling

Raman spectroscopy and rheology are desirable.

Given this need, we have developed an instrument for simultaneous measurements

of rheology, Raman spectroscopy, and polarized optical microscopy which we call the rheo-

Raman microscope.[1] The instrument combines a stress-controlled rheometer with a Raman

spectrometer and optical microscope via a transparent glass base. Features in the Raman

spectra can be quantitatively correlated with crystallinity via comparison with differential

scanning calorimetry measurements, and epi-illumination imaging using crossed-polarizers

reveals the size and orientation of birefringent structures in the sample.

The rheo-Raman microscope is especially useful in characterizing the relationship

between crystallinity and rheology during polymer crystallization. We demonstrate this

capability by measuring the isothermal crystallization of polycaprolactone (PCL), an

aliphatic polyester commonly used in the additive manufacturing of biomedical implants.

Our measurements allow us to critically assess the various models currently used to relate

crystallinity to rheology as well as develop novel phenomenological models that can be used

to explain crystallization via percolation-type phenomena.[2] We find that a general effective

medium equation can be used to characterize the relationship between viscoelasticity and

crystallinity.

We further apply our simultaneous measurement technique to characterize the

crystallization of high-density polyethylene. Quiescent crystallization measurements

indicate differences in the sensitivity of Raman spectra compared to the appearance of

birefringent structures in optical microscopy, as well as the sensitivity of the viscoelastic

shear modulus to small increases in the degree of crystallinity during crystallization. We

apply the effective medium model to determine the crystalline fractions where mechanical

percolation occurs.

References

[1] – A.Kotula, M.Meyer, F.de Vito, J.Plog, A.Hight-Walker, and K.Migler, Rev.Sci.Inst. 87, 105105 (2016).

[2] – A.Kotula and K.Migler, J. Rheol. 62, 343 (2018).


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M.12 - Effects of Orientation and Deformation Mode in Dynamic Mechanical

Analysis of Engineered Materials

Sarah Cotts

TA Instruments

Dynamic Mechanical Analysis (DMA) is widely used to characterize glass transition behavior of

polymeric materials. By monitoring changes in viscoelastic properties as a function of

temperature, DMA is more sensitive to glass transition than any other technique. In addition, it

provides insights into microstructure and bulk physical properties. Therefore, DMA is especially

valuable in characterizing engineered materials with complex morphologies created by their

processing. The testing shown here includes traditional thermoplastics and polymer composites

with varying degrees of molecular orientation and macro orientation, and examines the effects of

the orientation on the DMA measurements through the glass transition, using varying

deformation modes to either highlight or minimize those effects. Samples generated using

additive manufacturing (3D printing) are also studied using DMA. 3D printing is becoming a

popular technique for rapid prototyping or generating parts quickly and inexpensively. The

material can have significant orientation on the micro scale or macro scale, depending on the

process and the material. Mechanical measurements like tensile stress detect the effect on the

bulk properties, but Dynamic Mechanical Analysis adds further understanding into the

morphologies of 3D printed materials by the observing the changes in viscoelasticity, damping,

and glass transition temperature range with varying orientation.


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M.13 - Selective Cell Adhesion on Peptide-Polymer Nano-Fiber Mats

G. Kaur#, S. Kumari, P. Saha, S. Patil, S. Ganesh, S. Verma*

#Department of Pharmaceutical Sciences, College of Pharmacy, Texas A&M University, Reynolds Medical

Building, TAMU Mailstop 1114, College Station, Texas 77843, United States

*Department of Chemistry, Indian Institute of Technology, Kanpur, India-208016

Email: [email protected]

The electrospun nanofibers are valuable for a number of applications ranging from

catalysis to drug delivery. At times, the lack of biocompatibility, biodegradability and

hydrophobicity presents hindrance in their use in biological applications. Aromatic amino acids

are veritable precursors for biocompatible nanofibers, which could also be chemically modified

with suitable addressable recognition tags to invoke specific binding events. This study presents

an attractive strategy for constructing electrospun fibrous nanomats from dityrosine based folic

acid conjugate and polycaprolactone (PCL) to afford a new hybrid material displaying excellent

tensile properties, biocompatibility and cell adhesion. We demonstrate that appropriate choice of

peptide-to-polymer ratio gave mats with sufficient hydrophilic, better mechanical properties and

allowed favorable interaction of folate receptor presenting cells with nanomats, while the ones

lacking folate receptor did not exhibit binding. Such selectivity could be possibly invoked for

separation and also for custom synthesis of nanomats for healthcare applications.

Figure 1: A working model for peptide-polymer mats

References

[1] - G. Kaur, A. Shukla, S. Sivakumar and S. Verma, J. Pept. Sci. 21, 248 (2015).

[2] - J. J. Castillo, W., E. Svendsen, N. Rozlosnik, P. Escobar, F. Martínez and J. Castillo-León, Analyst 138, 1026

(2013).


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M.14 - Viscoelastic behavior of polyelectrolyte complexes across

coacervate-precipitate transition regime

S. Ali and V.M Prabhu

Material Measurement Laboratory, National Institute of Standards and Technology, 100

Bureau Drive, Gaithersburg, Maryland 20899, United States


Complexation between anionic and cationic polyelectrolytes results in solid-like

precipitates or liquid-like coacervate depending on the added salt in the aqueous medium

[1]. Understanding the boundary between these polymer-rich phases and the associated

changes in the polymer relaxation in the complexes across the phase transition regime is

fundamentally important for their various technological applications including surgical wet

adhesives, tissue engineering, food processing and packaging. This presentation will

describe the relaxation dynamics probed over a wide timescale by measuring viscoelastic

spectra and zero-shear viscosities at varying temperatures and salt concentrations of

complexes from coacervate to near-precipitate. The complexes exhibit time-temperature

superposition (TTS) at all salt concentrations, which is further supported by small angle

neutron scattering measurements. Moreover, the range of overlapped-frequencies for time-

temperature-salt superposition (TTSS) strongly depends on the salt concentration (Cs) and

gradually shifts to higher frequencies as Cs is decreased. These observations are further

analyzed using the main results of the sticky-Rouse model [2].

References [1] Q. Wang and J. B. Schlenoff, Macromolecules 47, 3108 (2014)

[2] S. Ali and V. M. Prabhu, Gels 4(1), 11 (2018)

ISPAC 2018 - Session: Characterization with Chromatography

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M.15 - Comparison of fast SEC and UHP SEC for the second dimension in

two-dimensional liquid chromatography of polymers

Elena Uliyanchenko, Stijn Rommens

SABIC, Plasticslaan 1, 4612 PX Bergen op Zoom, the Netherlands, [email protected]

Two-dimensional liquid chromatography (2D LC) is an important characterization technique for

polymers. 2D LC can provide information on two macromolecular distributions and their mutual

dependence that allows for deeper understanding of structure-properties relationships of the

polymers. This, in turn, accelerates the development of new materials with specific set of

properties meeting the needs of the modern society.

The most common comprehensive 2D LC approach combines chemical-composition based

separation by gradient-elution liquid chromatography as a first dimension (D1) and a size-based

separation by size-exclusion chromatography (SEC) as a second dimension (D2). This setup

requires a labour-intensive method development and optimization of multiple experimental

parameters. The main limiting factor is the D2 analysis speed, which needs to be very fast in order

to maintain the quality of the D1 separation. However, the separation speed in D2 is restricted in

practice by the column material stability and by the minimum acceptable efficiency in D2.

Typically, wide-bore short SEC columns are used at a very high flow rates and a satisfactory D2

separations can be achieved within 2.5 – 3 min. At these conditions, the solvent consumption is

very high and the total 2D analysis time can reach 3-4 hours. An alternative could be the use of

ultra-high pressure size-exclusion chromatography (UHP SEC) in D2. UHP SEC columns are

made of smaller (sub 3-m) silica-organic hybrid particles that can withstand higher pressures and

therefore they can be run at higher linear velocities without significant efficiency loss. This allows

for smaller column dimensions, lower flow rates, and therefore, for reduction of solvent

consumption, higher environmental sustainability and reduced costs. The separation time in D2

can be shortened to approximately 1 min and the total analysis time can be decreased to about 1

hour. Thus, applications of such columns in 2D LC setup seem to be beneficial. However, different

stationary phase chemistry and smaller dimensions of such columns may cause some additional

practical challenges.

In this study, we compare the performance of fast SEC and UHP SEC for rapid polymer analysis

and address challenges associated with the use of both types of columns. The influence of

parameters such as polymer molecular weight and injection volume on the separation efficiency is

studied. Based on the theoretical considerations and practical data we highlight potential and

drawbacks of both fast SEC and UHP SEC for the applications in 2D LC. Finally, we provide a

guideline for the use of these columns in 2D LC of polymers.


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M.16 - Understanding Polymer Structure by Interaction Polymer

Chromatography

Christopher J. Rasmussen1, Yefim Brun2

1. DuPont Science & Innovation 2. DuPont Industrial Bioscience, Wilmington, DE.

[email protected]

A defining characteristic of polymers is the polydispersity of chain lengths. Revealing the

molecular weight distribution enables a full understanding of how molecular properties can

affect end-use and material properties. Size Exclusion Chromatography (SEC) is an

analytical technique capable of resolving a polymer’s molecular weight distribution, and as

such, in an indispensable tool for polymer chemists. However, molecular weight is only one

distributed property that can characterize a given polymer. Additional complexities such as

functional end groups, substituted side groups, and comonomer composition, all exist as

distributed properties. SEC is, at best, not sensitive to these properties, and at worst,

invalidated by them. And while other spectrometric techniques such as NMR, FTIR, and MS

provide invaluable averages, a separation technique is required to quantify any distributed

property.

In this talk, a simple theoretical framework for Interaction Polymer Chromatography (IPC)

will be introduced. IPC is a collection of chromatographic methods that rely on the

interaction of polymer analyte and a stationary phase by enthalpic adsorption forces, rather

than steric exclusion as is the case for SEC. Separations can thus be designed to minimize or

eliminate retention by molecular weight, and reveal the underlying molecular properties that

define a polymer’s structure. Cases covered include end group characterization of

functionalized poly(ethylene glycol) stars, distribution of comonomer in acrylate

copolymers, and determination of structure parameters such the blockiness “B-value” for

transesterified polyesters.


27

M.17 - Light Scattering without Refractive Index Increment

A New Approach to Calibrate SEC-Light Scattering Setups

D. Lohmann1 , W. Radke2, J. Preis2, S. Lavric3

1PSS USA Inc, Amherst, MA, 2PSS GmbH, Mainz, Germany, 3 Melamin d.d., Kocevje, Slovenia

[email protected]

Size exclusion chromatography (SEC) with light scattering detection (SEC-LS) has

become a popular method for polymer characterization. In contrast to conventional SEC,

which yields molar masses only relative to a calibration curve, SEC-LS can provide absolute

molar masses at each elution volume. This allows determining true molar mass distributions

and molar mass averages. SEC-LS requires use of a light scattering instrument in conjunction

with a concentration detector, typically a RI detector. The primary information obtained by

the detectors are voltages, which have to be converted to the respective physical property

measured.

At present, calibration of SEC-light scattering detectors is either achieved by

calibration using a reference liquid of known Rayleigh ratio, e.g. toluene, or by using well-

characterized polymer standards for calibration. It needs to be understood that true molar

masses are obtained by SEC-light scattering, even if the standards used to calibrate the SEC-

light scattering setup are not of identical chemical structure as the analyte. This in in contrast

to conventional SEC. If calibration is performed using a polymer standard, the molar mass

and the specific refractive index increment, dn/dc, of the standard needs to be known. For

molar mass determination of unknown analytes, knowledge of their refractive index

increment, dn/dc is also required

Unfortunately, the correct refractive increment is often unknown in the solvent

applied, or its determination is difficult, e.g. in mixed solvents or in solvents containing salts

or additives. The present contribution will describe an alternative approach to calibrate an

SEC-LS setup and to determine the molar mass of a unknown analytes, requiring neither the

refractive index increment of the sample, nor of the polymer used for calibration. Only the

molar mass of the calibrant and the concentrations of the calibrant and the unknown samples

are required. The new calibration approach does not require any refractive index increment,

Consequently, experimental difficulties arising from preferential solvation as they are

present in ternary systems (mixed solvent, salt containing eluents) are eliminated.

Besides the theoretical approach, the contribution will provide experimental results, in

organic as well as aqueous solvent, proving the suitability of the new approach.


28

M.18 - Fast Separations of Synthetic Polymers Using Advanced Polymer

Chromatography (APC)

M. Jančo

Dow Chemical, 400 Arcola Road, Collegeville, PA 19426, e-mail: [email protected]

Size Exclusion Chromatography (SEC) is the preferred method for the determination

of the molecular weight parameters of synthetic polymers as a result of its universality,

reliability, reproducibility and low sample consumption. To achieve sufficient resolution of

separated species, the column sets are composed of at least two, and more often, three

analytical columns (300 x 7.5-10 mm ID). Typical flow rates are 1 - 2 mL/min in order not

to damage the column packing by exceeding its back pressure limit. Therefore, resulting

SEC separation run times are often in range of 30 to 60 min.

Substantial acceleration of SEC separations remains difficult to achieve due to

column packing pressure limitations. Short and wide diameter SEC columns (50 x 25 mm

ID) that allow high eluent flow rates (typically 5 to 10 mL/min) while still running at

moderate backpressure are the only present solution to speed up SEC separations [1]. A

limitation to this approach is lower resolution of the separation.

Advanced Polymer Chromatography (APC) is a newly developed disruptive

technology allowing separation of synthetic polymers with very short analysis times and

improved resolution [2]. Using a Waters ACQUITY APC system and BEH APC columns

packed with 1.7-2.5 μm particles with pore size ranging from 45 to 900 Å, size based

separations of 16 component mixture of narrow PS standards can be achieved in less than 6

minutes (Figure 1). Power of APC in speed, resolution, precision and sustainability will be

compared to conventional SEC. APC of polymers soluble in aqueous buffers will be also

presented.

Figure 1: APC chromatogram of 16 component mixture of PS standards obtained on three BEH XT columns

(150x4.6 mm id) packed with 2.5 m BEH particles in THF using RI detection. Flow rate: 1ml/min.

References

[1] http://www.polymer.de/products/columns-forgpcsecgfc/gpcsec-highspeed-columns.html

[2] M. Janco, J. Alexander, E. Bouvier, D. Morrison, J. Sep. Sci., 2012, 36, p. 2718-2727

http://www.polymer.de/products/columns-forgpcsecgfc/gpcsec-highspeed-columns.html

ISPAC 2018 – Vendor Presentation : Waters

29

V.1 -Utilization of Advanced Polymer Chromatography coupled with Light

Scattering Detectors for the Advancement of Material Science

Jennifer Gough, Robert Birdsall, Isabelle François, Michael Jones, Michael O’Leary, Jean-

Michel Plankeele, Ben MacCreath, and Damian Morrison

Scientific Operations, Waters Corporation, USA, [email protected]

The need for comprehensive characterization in materials science usually involves a vast

array of techniques such as spectroscopy, thermal analysis, and chromatography. The novel

design of the Waters ACQUITY Advanced Polymer Chromatography (APC) system has been

shown to efficiently yield both high resolution and high speed size exclusion chromatography

(SEC). This separation technique, coupled to a variety of low dispersion detectors, enables the

technique to become more widely used in academic research and material science to solve the

most challenging problems. In this presentation, we will show the expansion of the Waters

APC technique to hyphenation with light scattering (LS) detection. In addition to the LS

detection, the newest applications will be presented from academic researchers and include

work such as the analysis of lignins, polymer microstructures, and highly functional polymers.

Case studies will further be presented that focus the use of this technique for the analysis of

synthetic polymers and biopolymers.

[1] - Provder, Theodore; Urban, Marek W.; Barth, Howard G., Hyphenated Techniques in Polymer

Characterization, American Chemical Society, 1994.

ISPAC 2018 – Plenary: Advancing Materials Science with Big Data

30

M.04 - Scoping the Polymer Genome: A Roadmap for Rational Polymer

Dielectrics Design and Beyond

Rampi Ramprasad

Georgia Institute of Technology

[email protected]

http://ramprasad.mse.gatech.edu

The Materials Genome Initiative (MGI) has heralded a sea change in the philosophy of materials

design. In an increasing number of applications, the successful deployment of novel materials has

benefited from the use of computational methodologies, data descriptors, and machine learning.

Extensive efforts over the last few years have seen the fruitful application of MGI principles toward

the accelerated discovery of attractive polymer dielectrics for capacitive energy storage [1]. Here, we

review these efforts, highlighting the importance of computational data generation and screening,

targeted synthesis and characterization, polymer fingerprinting and machine-learning prediction

models, and the creation of an online Polymer Informatics platform

(https://www.polymergenome.org) to guide ongoing and future polymer discovery and design. We

lay special emphasis on the fingerprinting of polymers in terms of their genome or constituent atomic

and molecular fragments [2], an idea that pays homage to the pioneers of the human genome project

who identified the basic building blocks of the human DNA. By scoping the polymer genome, we

present an essential roadmap for the design of polymer dielectrics, and provide future perspectives

and directions for expansions to other polymer subclasses and properties.

[1] A. Mannodi-Kanakkithodi, A. Chandrasekaran, C. Kim, T. D. Huan, G. Pilania, V. Botu, R.

Ramprasad, “Scoping the Polymer Genome: A Roadmap for Rational Polymer Dielectrics Design

and Beyond”, Materials Today, in press (2017).

[2] R. Ramprasad, R. Batra, G. Pilania, A. Mannodi-Kanakkithodi, C. Kim, “Machine Learning and

Materials Informatics: Recent Applications and Prospects”, npj Computational Materials 3, 54

(2017).

mailto:[email protected]

http://ramprasad.mse.gatech.edu/

https://www.polymergenome.org/


31

Braskem Lecture

M.05 -Towards Polymer Informatics: Databases, Infrastructure and

Beyond

Debra Audus,6 Roselyne Tchoua,1,2 Kyle Chard,1 Logan Ward,1 Jian Qin,3 Joshua

Lequieu,4 Juan de Pablo,5 Ian Foster1,2 1Computation Institute, University of Chicago, Chicago, Illinois, USA.

2Department of Computer Science, University of Chicago, Chicago, Illinois, USA. 3Department of Chemical Engineering, Stanford University, Stanford, California, USA.

4Materials Research Laboratory, University of California, Santa Barbara, Santa Barbara, California, USA. 5Institute for Molecular Engineering, University of Chicago, Chicago, Illinois, USA.

6Materials Science and Engineering Divison, National Institute of Standards and Technology, Gaithersburg,

Maryland, USA. [email protected]

Polymer informatics has the potential to revolutionize material discovery by reducing both

the development time and cost [1]. However, in order to achieve such a goal, significant

barriers still remain---a lack of large, accessible datasets, a lack of infrastructure to support

the sharing of data and code, among others. We aim to reduce and eliminate such barriers.

Regarding the lack of datasets, we have developed information extraction pipelines to

harness the vast quantities of valuable experimental polymer data trapped in the literature.

Initially, we developed the largest Flory-Huggins parameter database using

crowdsourcing. Through this process, we determined that the use of human effort was

suboptimal as over half of the reviewed journal articles contained no relevant data. Turning

to machine learning, we found that we could significantly reduce this burden by having the

computer identify the most promising articles. After these initial promising results, we opted

to further reduce human input, which although necessary, is a limitation for collecting the

data for polymer informatics. Specifically, we used natural language processing software

coupled with specially designed software modules to extract grass transition temperatures

with minimal human input; ultimately, we extracted over 250 glass transition temperatures.

In line with the goals of polymer informatics, all of the resulting data is freely available at

http://pppdb.uchicago.edu. Finally, I will highlight some of the other efforts at NIST that

aim to reduce the barriers to polymer informatics including the development of a more

efficient code for computing hydrodynamics properties of polymers called ZENO [2] and a

pilot project under the NIST center for excellence, CHiMaD [3], in collaboration with ACS

and RSC to release virtual issues in multiple journals where the polymer data is published

along with the journal article.

References [1] D.J. Audus, J.J. de Pablo. ACS Macro Lett. 2017 6: p. 1078-1082.

[2] D. Juba, D.J. Audus, J.F. Douglas, M. Mascagni, W. Keyrouz. J. Res. NIST 2017 122.

[3] http://chimad.northwestern.edu/

http://pppdb.uchicago.edu/


32

M.06 -Materials-Specific Considerations for Machine Learning

Bryce Meredig

Citrine Informatics, San Francisco, CA

The use of of machine learning (ML) is rapidly expanding within materials science, to the

point that “vanilla” applications of ML are becoming commoditized—much like what has

happened with simple density functional theory calculations. If a few lines of python, using

open-source libraries, are sufficient to train a reasonable model for superconducting Tc, it

is worth asking a provocative question: What is missing for ML to unlock a Nobel-caliber

discovery?

In this talk, we will outline a set of key considerations for applying ML to materials design

problems. We will begin with an introduction of how materials are, across many

dimensions, fundamentally different from more common application areas for ML. We

then explore the question above, focusing on these underlying issues: (1) data

infrastructure and access to training data; (2) representations of materials for input to

machine learning; (3) how ML models may be used to guide materials discovery; (4)

quantifying the predictive accuracy of materials property models; and (5) treating

inherently hierarchical, multiscale materials phenomena with ML.

ISPAC 2018 – Session: Computation and Characterization

33

M.21 - From Data Science to Data Stories: Automating advanced

analytics for R&D and manufacturing.

Guido F. Smits

Ph. D., Chief Scientific Officer at DataStories Int. NV, [email protected]

Advanced Predictive analytics is gaining importance and proven impact in many areas

despite some of the hype. Surprisingly, the data science universe and the business universe

keep co-existing without too much overlap. We claim that data-driven solutions will see a

greater success in business and industry only when they are understood and internalized by

domain experts (not just data scientists), and when domain experts can generate and take

ownership of the solutions themselves with minimal effort. This also requires that

predictive analytics outcomes are communicated to domain experts in human language

with a narrative; otherwise they have little chance to be sustainably deployed.

We willl show some specific examples of what is possible both in new product design and

in manufacturing.


34

M.22 – typyPRISM: A Computational Tool for

Liquid-State Theory Calculations of Macromolecular Materials

Tyler B. Martin1, Thomas E. Gartner III2, Ronald L. Jones1, Chad R. Snyder1, Arthi

Jayaraman2

National Institute of Standards and Technology, Gaithersburg, MD

Chemical and Biological Engineering, University of Delaware, DE

Polymer Reference Interaction Site Model (PRISM) theory describes the equilibrium spatial-

correlations of liquid-like polymer systems including melts, blends, solutions, block

copolymers, ionomers, polyelectrolytes, liquid crystal forming polymers and

nanocomposites. Using PRISM theory, one can calculate thermodynamic (second virial

coefficient, χ interaction parameters, potential of mean force) and structural (pair correlation

functions, structure factor) information for these macromolecular materials. Here, we present

a Python-based, open-source framework, typyPRISM, for conducting PRISM theory

calculations. This framework aims to simplify PRISM-based studies by providing a user-

friendly scripting interface for setting up and numerically solving the PRISM equations.

typyPRISM also provides data structures, functions, and classes that streamline PRISM

calculations, allowing typyPRISM to be extended for use in other tasks such as the coarse-

graining of atomistic simulation force-fields or the modeling of experimental scattering data.

The goal of providing this framework is to reduce the barrier to correctly and appropriately

using PRISM theory and to provide a platform for rapid calculations of the structure and

thermodynamics of polymeric fluids and nanocomposites.


35

M.23 – Abstract TBA

L. Fernando Vargas Lara

Georgetown University, Georgetown, DC

ISPAC 2018 – Session: Molecular Control and Characterization

36

M. 24 - Perfect Polystyrene Sulfonate: Synthesis, Characterization and

Self Diffusion in Ternary Solutions

P. Balding1, R. Cueto2, P.S. Russo1,3

1School of Chemistry and Biochemistry, Georgia Institute of Technology

2Department of Chemistry and Macromolecular Studies Group, Louisiana State 3School of Materials Science and Engineering, Georgia Institute of Technology

[email protected]

Sodium Polystyrene Sulfonate (NaPSS) is a model polyelectrolyte that is widely studied both

experimentally and theoretically. The traditional synthesis of NaPSS by the sulfonation of

polystyrene results in an imperfect material that is still commonly used to experimentally

understand polyelectrolyte systems. The need for better polyelectrolytes has driven our

research to synthesize perfectly sulfonated NaPSS by aqueous ATRP. Reaction control,

synthetic repeatability, desired molecular weight and low polydispersity are obtained

through an interplay of reaction variables such as pH, methanol cosolvent content, added

NaCl as a deactivator species, Cu(I)/L to initiator ratio, type of ligand and deactivator. The

monomer to initiator ratio was held fixed in order to understand how various ATRP side

reactions effect the final polymer properties.

Characterization of reaction progress by 1H NMR showed that monomer conversion and

reaction kinetics were heavily dictated by adjustments in certain reaction variables. Kinetics

and conversion both increased significantly by varying reaction pH from 6-7 to 12-13.

Increasing the methanol solvent composition showed a decrease in kinetics and conversion

while added deactivator in the form of NaCl showed a maximum in conversion and kinetics

at concentrations equivalent to the Cu(I)/L used.

Characterization of polymer size and architecture was obtained by aqueous GPC-MALS-

DLS. Desired molecular weight from the fixed monomer to initiator ratio was obtained at a

reaction pH of 6-7 but an order of magnitude increase was found at a pH of 12-13. Similarly

increasing the methanol decreased the molecular weight over a given reaction period and

added salt again showed a maxima in molecular weight at equivalent Cu(I)/L concentrations.

Analysis of the dimensionless ratio between Rg and Rh along with conformation plots

confirmed the linear random coil nature of the NaPSS polymer in good solvent conditions.

Self-diffusion measurements of NaPSS was measured by fluorescence photobleaching

recovery. FITC-labelled NaPSS showed an increase in self-diffusion as a function of

increased NaCl concentration. Diffusion of FITC-labelled NaPSS through a matrix of

dissolved, unlabelled NaPSS proves to be a complex problem. As a function of matrix

concentration and molecular weight the diffusion of the labelled NaPSS did not scale

according to theoretical predictions [1], [2].

References

[1] – A.V. Dobrynin, R.H. Colby and M. Rubinstein, Macromolecules. 28, 6 (1995).

[2] – M. Muthukumar, J. Chem. Phys. 107, 2619 (1997).


37

M.25 - Conformational control of tethered functionalized mPEO on

anatase nanocrystals surface

M.Tawfilas, M. Mauri and R. Simonutti

aDepartment of Materials Science, University of Milano-Bicocca, via R. Cozzi 55, 20125 Milan, Italy

email: [email protected]

Improving nanocomposite materials performance it is strongly desired[1]. To reach this goal

it is necessary to work on the surface ligand engineering, an effective tool since it plays a

major role against the trickiest issue related to this kind of materials: the incompatibility of

the organic/inorganic phase. The introduction of a thin polymeric layer enables a good

dispersion of the inorganic nanocrystals (NCs) in solvents and matrixes in which bare

particles aggregate and precipitate. Thanks to the control over the graft density (σ) and the

grafted chains molecular weight (N) it is possible to control morphology of the dispersions

in matrix[2]. Defining the conformation of the grafted polymer, that can be brush or

mushroom, improves the solubility of the nanocomposite into polymer matrixes and gives

specific properties to the final material[3]. In our contribution we explored the grafting-to

approach (Fig.1) of polyethylene oxide monomethylether (mPEO) chains, of different

molecular weights (Mw, 102-104 gmol-1), functionalized with three anchoring groups:

alcoholic, carboxylic and phosphate end group. The grafting reactions have been made using

two different solvents (water and dichloromethane) in order to manage the environment in

which the polymer and the NCs surface react. Anatase NCs (<10nm) are synthesized via

solvothermal technique and fully characterized with transmission electron microscopy

(TEM), dynamic light scattering (DLS), X ray diffraction (XRD), Z-Potential and N2

adsorption. The functionalized mPEO samples are characterized with nuclear magnetic

resonance (NMR) and Furrier transform infra-red spectroscopy (FTIR), while the grafted

polymers are quantitatively defined through thermogravimetric analysis. It is observed the

effect of the anchoring group at low Mw on σ that is strictly related to the enthalpy gain due

to the bond formation at the NCs surface. At higher Mw the enthalpy gain is overwhelmed

by the entropic cost due to the disadvantaged chain stretching bringing low σ. In order to

describe the regime of the anchored polymers, we can assume that a single grafted chain acts

as a rigid sphere; calculating a theoretical mean distance between two chains as two times

the radius of gyration (2Rg) and an experimental mean distance (Dm), deducted by TGA and

BET analysis it is possible to define a brush regime when Dm<2Rg, vice versa when Dm ≥2Rg

the mushroom regime is described. Thus gives us a full control over σ and the polymer

conformation on spherical NCs.

Figure 1: Representation of the grafting-to approach applied in this work for mPEO on anatase NCs.

References

[1] - Li Y, Krentz TM, Wang L, Benicewicz BC, Schadler LS., ACS Appl. Mater. Interfaces 2014, 6,

6005−6021

[2] - Kumar SK, Jouault N, Benicewicz B, Neely T.. Macromolecules. 2013;46(9):3199-3214.

[3] - Brittain WJ, Minko S., J Polym. Sci. Part A Polym. Chem. 2007;45(16):3505-3512.


38

M. 26 - Preparation and Characterization of Polyurethanes from

Carbohydrates

H. N. Cheng1, Atanu Biswas2

1Southern Regional Research Center, USDA Agricultural Research Service,

1100 Robert E. Lee Blvd., New Orleans, LA 70124, USA 2National Center for Agricultural Utilization Research, USDA Agricultural Research Service,

1815 N. University St., Peoria, IL 61604, USA


Carbohydrates represent a useful platform for the generation of polymers from agro-based

sustainable and renewable resources. Indeed, many derivatives of carbohydrate polymers are

known and available as commercial products [1]. One of the ways to derivatize a

carbohydrate is convert it into a polyurethane, replacing a petroleum-based polyol and

thereby rendering the final product more biodegradable and sustainable [2-4].

Polyurethanes, of course, are well-known for their many commercial uses, e.g., foams,

elastomers, adhesives, surface coatings, and synthetic fibers [5].

In our efforts to develop green polymer technologies, we have coupled the use of

carbohydrates in polyurethane synthesis with microwave-assisted reactions [6-8]. In our

latest work [9], we have concentrated on sucrose, which is inexpensive and widely available.

Thus, we have synthesized polyurethanes from sucrose and toluene diisocyanate (TDI)

through microwave technology. As expected, the sucrose/TDI ratio has a large effect on the

degree of crosslinking of the product. Relative to conventional heat, microwave-assisted

synthesis has been found to significantly decrease the reaction time and save energy.

Through the incorporation of a second material in a semi-interpenetrating polymer networks,

appropriate modifications of the mechanical properties of the polyurethane can be achieved.

Characterization of the polymers has been conducted with 13C NMR, FT-IR, SEC, and

thermal analysis.

References

[1] J.N. BeMiller and R. L. Whistler. Industrial Gums, 3rd ed. Academic Press, San Diego, CA, 1993.

[2] Y. Li, X. Luo and S. Hu. Bio-based Polyols and Polyurethanes. Springer, Cham, CH, 2015.

[3] F. Zia, K. M. Zia, M. Zuber, S. Kamal, and N. Aslam. Starch based polyurethanes: A critical review

updating recent literature. Carbohydr. Polym. 134, 784 (2015).

[4] N. J. Sangeetha, A. M. Retna, Y. J. Joy, and A. Sophia. A review on advanced methods of polyurethane

synthesis based on natural resources. J. Chem. Pharm. Sci. 7, 242 (2014).

[5] M. Szycher, Szycher’s Handbook of Polyurethanes, 2nd ed. CRC Press, Boca Raton, FL, 2013.

[6] A. Biswas, S. Kim, Z. He, and H. N. Cheng. Microwave-assisted synthesis and characterization of

polyurethanes from TDI and starch. Int. J. Polym. Anal. Charac. 20, 1 (2015).

[7] A. Biswas, M. Appell, Z. Liu, and H. N. Cheng. Microwave-assisted synthesis of cyclodextrin

polyurethanes. Carbohydr. Polym. 133, 74 (2015).

[8] H. N. Cheng, R.F. Furtado, C.R. Alves, M.S.R. Bastos, S. Kim, and A. Biswas. Novel polyurethanes

from xylan and TDI: Preparation and characterization. Int. J. Polym. Anal. Charac. 22, 35 (2017).

[9] A. Biswas, S. Kim, A. Gómez, M. Buttrum, V. Boddu, and H.N. Cheng. Microwave-assisted synthesis

of sucrose polyurethanes and their semi-IPN’s with polycaprolactone and soybean oil. Ind. Eng. Chem.

Res., accepted; https://pubs.acs.org/doi/10.1021/acs.iecr.7b04059.

ISPAC 2018 - Plenary: Advances in Chromatography and Spectroscopy

39

T.01 - Correlated polymer characterization via SEC-IR Detection with a

new QCL Laser Spectrometer and SEC-NMR with a new 60 MHz MR-

NMR Spectrometer

Jennifer Kübel, Johannes Höpfner, Carlo Botha, Sascha Morlock, and Manfred Wilhelm

Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT),

Karlsruhe, Germany, [email protected]

Polymers have three important molecular characteristics: the molecular weight

distribution (MWD), the chemical composition and the topology. The MWD is usually

determined using size exclusion chromatography (SEC). SEC detectors commonly in use,

such as refractive index detectors, light scattering or viscometers, do not provide information

about the chemistry or topology. This information is normally gained separately using

spectroscopic methods.

Coupling IR or NMR spectroscopy with SEC is a promising approach to gain this

correlated information. [1] An inherent problem to this pairing is the normally very high

solvent signals, which arise from the low sample concentration necessary for SEC

separation. Previously, we developed an online SEC-FTIR coupling using a standard

research FTIR spectrometer, specially constructed flow cells and mathematical solvent

suppression of the solvent signals. [2] For an even higher sensitivity, different infrared light

sources are needed. We now present results from a SEC coupled with an IR spectrometer

using a tunable Quantum Cascade Laser (QCL) light source, which has a higher light

intensity, but a limited bandwidth. [3] A table-top 60 MHz MR-NMR spectrometer equipped

with a permanent magnet was also coupled with SEC to make online measurements. [4] The

resulting S/N ratio is sufficient for online MR-NMR-SEC measurements. The method

development for SEC-QCL-IR and MR-NMR-SEC including the general setup, flow cells

and solvent suppression will be presented. [3,4]

Figure 1. Comparison of online SEC-FTIR and SEC-QCL-IR measurements. [3] References

[1] H. Pasch, Hyphenated separation techniques for complex polymers, Polym. Chem. 2013, 4, 2628.

[2] T.F. Beskers, T. Hofe, M. Wilhelm, Macromol. Rapid Commun. 2012, 33, 1747-1752; T.F. Beskers, T.

Hofe, M. Wilhelm, Polym. Chem. 2015, 6, 128-142.

[3] S. Morlock, J. M. Kuebel, T.F. Beskers, B. Lendl, M. Wilhelm, Macromol. Rapid Commun. 2018,

1700307.

[4] J. Höpfner, K.-F. Ratzsch, C. Botha, M. Wilhelm, Macromol. Rapid Commun. 2018, 1700766.


40

T.02 - Characterization of Complex Synthetic Polymers by Advanced

Separations and Detection Techniques

David M. Meunier

The Dow Chemical Company, Core R&D, Analytical Sciences, Midland, MI

[email protected]

Polymer structure dictates properties, and ultimately performance, in the market place.

Elucidation of structural differences among polymer samples is therefore critical for defining

structure-property relationships and process-structure relationships. Although often simply

depicted as a structural repeat unit enclosed in parentheses with a subscripted “n”, synthetic

polymers are actually complex mixtures of similar species. For example, a polyethylene

sample, depicted simply as repeating ethylene units, as in –(CH2-CH2)n–, can include

overlapping distributions in molar mass, chemical composition, branching topology,

functionality type (e. g., end groups), block architecture and microstructure. In fact, virtually

all commercial synthetic polymers contain at least two overlapping distributions of structural

heterogeneity, while many, especially copolymers, exhibit more than two. Because they

comprise complex mixtures of overlapping distributions, gaining insight into the structural

diversity of polymer samples requires advanced separations and detection techniques.

Several approaches for elucidating structural heterogeneity in synthetic polymers will be

highlighted in this talk. Used alone or in combinations, separations techniques like size

exclusion chromatography, field flow fractionation and liquid adsorption chromatography

have been developed and applied to many industrial polymers. Combinations of detectors

including concentration, composition and molecular weight/size sensitive are utilized in

conjunction with single or multidimensional separations to provide even greater insight.

Several examples of application and development of these approaches for characterization

of synthetic polymers and particles will be presented and discussed.


41

T.03 - HPLC Characterization of Block Copolymers

Taihyun Chang Department of Chemistry and Division of Advanced Materials Science, POSTECH, Pohang, Korea

[email protected]

Block copolymers have been a subject of intensive research in the last few decades due to

their formation of ordered nanophases that can be used as templates for various applications

in nanotechnology. Block copolymers are also used in structural materials such as

thermoplastic elastomers or high impact polymers. They are usually prepared by controlled

polymerization methods such as anionic polymerization or controlled radical polymerization

to produce a well-defined block structure in the polymer chains. For the molecular

characterization of block copolymers, Size exclusion chromatography (SEC) has been used

routinely, but it often fails to elucidate the details due to their size dependent separation and

large band broadening. Other chromatographic methods can do a better job in the

characterization of block copolymers. For examples, liquid chromatography at the critical

condition (LCCC) successfully characterized individual block in block copolymers.[1]

Interaction chromatography (IC) is effective to fractionate homopolymer byproducts from

the block copolymers[2] and able to fractionate individual blocks into narrower fractions.[3]

In this talk, our efforts on the detailed characterization of block copolymers will be

presented.

References

[1] W. Lee, D. Cho, T. Chang, K.J. Hanley and T.P. Lodge, Macromolecules 34, 2353 (2001) [2] S. Park; I. Park, T. Chang, C.Y. Ryu, J. Am. Chem. Soc. 126, 8906 (2004)

[3] S. Park, D. Cho, J. Ryu, K. Kwon, W. Lee, T. Chang, Macromolecules 35, 5974 (2002)

[4] K. Im, H.-W. Park, Y. Kim, B. Chung, M. Ree, T. Chang, Anal. Chem. 79, 1067 (2007)

[5] S. Lee, H. Choi, T. Chang, B. Staal, Anal. Chem. Submitted

Figure 2. NP-TGIC x NP-LCCC 2D-LC

chromatogram of StyroluxTM [5] Figure 1. NP-TGIC x RPLC 2D-LC

chromatogram of low MW PS-b-PI [4]

ISPAC 2018 - Session: Condensed Phases

42

T.11 - Two-Dimensional Terahertz (2D THz) Raman Correlation

Spectroscopy Study of the Crystallization of Bioplastics

I. Noda1,2, A. Roy3, J. T. A. Carriere3 D. B. Chase1, J. F. Rabolt1

1Department of Materials Science and Engineering, University of Delaware, Newark, DE

19716, U.S.A. [email protected] 2Danimer Scientific, Bainbridge, GA 39817, U.S.A.

3Ondax, Monrovia, CA91016, GA 39817, U.S.A.

Raman spectroscopy was used to study the evolution of crystalline states of biodegradable

poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate] or PHBHx copolymer produced

by microbial biosynthesis [1]. The low-frequency Raman spectral region has become readily

accessible with the introduction of highly efficient optical notch filter technology, [2]. Thus,

Raman bands associated with the lattice mode vibrations of crystalline lamellae were

detected in the very low frequency/THz region, in addition to the conventional fingerprint

region bands [3].

Two-dimensional correlation analysis was applied to the time-dependent evolution of Raman

spectra during the isothermal crystallization of PHBHx. Simultaneous Raman measurement

of both carbonyl stretching and low-frequency crystalline lattice mode regions made it

possible to carry out the highly informative hetero-mode correlation analysis [4].

Coordinated dynamic variations in the spectral features were observed with the

crystallization process, and surprisingly detailed mechanisms for the development of

crystalline structures were revealed.

The crystallization process of PHBHx involves: i) the early nucleation stage, ii) the primary

growth of well-ordered crystals accompanied by the reduction of the amorphous component,

and finally iii) the secondary crystal growth most likely occurring in the inter-lamellar

region. Interestingly, the development of a fully formed lamellar structure comprised of 21

helices is detected not simultaneously but after the primary growth of crystals. In the later

stage, secondary inter lamellar space crystallization occurs after the full formation of packed

helices comprising the lamellae.

References

[1] – I. Noda, P.R. Green, M.M. Satkowski and L.A. Schechtman., Biomacromolecules. 6, 580 (2005).

[2] – J.T.A. Carrier, F. Havermeyer, R.A. Heyler, Proc. SPIE 9073, 90730K (2014).

[3] – I. Noda, A. Roy, J. Carriere, B.J. Sobieski, D.B. Chase, J.F. Rabolt, Appl, Spectrosc. 71, 1427 (2017).

[4] – I. Noda, Frontiers of Molecular Spectroscopy, 2nd ed, J. Laane, Ed. Pp.45-75, Elsevier, Amsterdam,

2018).



43

T.12 - Imaging Orientation Angles and Order Parameters of

Semicrystalline Polymers by Polarization IR and Raman

Young Jong Lee1, Jeremy Rowlette2

1NIST, [email protected], 2Daylight Solutions

Molecular alignment at the atomic level or the meso- and macroscopic levels can cause not

only directionality of a bulk property but also new unique properties of materials.

Understanding of the spatial heterogeneity and hierarchy in molecular orientation at each

level will help to find how the molecular orientation affects the resulting biological,

chemical, and mechanical properties of macromolecular materials. Therefore, accurate

measurement of molecular orientation with a spatial resolving power becomes critical to

understanding and optimization of the unique and directional properties of various complex

materials, such as bones, liquid crystals, silks, and polymers.

Figure 1: BCARS image of a high-density polyethylene film and 3D molecular orientations determined from

the polarization controlled BCARS hyperspectral images along the yellow dashed line. The red and green

colors represent the C-C and C-H stretching modes, respectively.

In this talk, I describe a new approach to non-iteratively determine the 3D angles and the

orientational order parameter without assuming a model function for an ODF. This method

is based on polarization-dependent IR and Raman signals of two non-parallel vibrational

modes. I will show how to determine the 3D angles and the second order parameter using

straightforward formula without iterative calculation. I demonstrate that this method can be

used to measure the 3D angles and order parameters at each image pixel of semicrystalline

polymers with a diffraction-limited spatial resolution.

References

[1] Y. J. Lee, Opt. Express, 23, 29279 (2015).

[2] Y. J. Lee, C. R. Snyder, A. M. Forster, M. T. Cicerone, W. -l. Wu, ACS Macro Lett., 1, 1347 (2012).


44

T.13 - Multiple Order-to-Order Transitions within Ultrathin Films of

Sugar-Polyolefin Amphiphilic Conjugates

S. R. Nowak1, K. Yager2, L. R. Sita1*

1 Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland

20742, United States 2 Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United

States

[email protected]

The development of nanostructured ‘smart’ materials that can respond to external stimuli on

practical time scales and moderate conditions remains a challenge and is a topic of great

academic and industrial interest. For thermoresponsive systems in the solid-state, the goal of

establishing extremely low kinetic barriers for order-to-order nanostructural transitions has

not yet been reached. This presentation will demonstrate the synthesis and characterization

of a new class of low molecular weight atactic sugar-polyolefin hybrid conjugates that can

meet this challenge. These amphiphilic hybrid conjugates consist of hydrophobic end-group-

functionalized poly(alpha-olefinate) (xPAO) “tails” chemically tethered to hydrophilic

saccharide “head” groups and display organized nanostructures within ultra-thin films with

sub-10 nm features. We previously reported that the conjugate consisting of the disaccharide

(D)-(+)-Cellobiose as the head group and atactic polypropylene (aPP) as the tail (CB-aPP)

undergoes a unique reorientation of self-assembled domains upon thermal annealing at

physiological temperatures. Herein we report that these conjugates display a rich and

dynamic self-assembly behavior in the form of multiple ‘order-to-order’ phase transitions

within ultrathin-films (< 100 nm), which were investigated by GISAXS with a synchrotron

x-ray source as a function of temperature. These results demonstrate the utility of sugar-

polyolefin conjugates as nanostructured smart materials for nanotechnological applications.

References

[1] –T. S. Thomas, W., Hwang, and L. R. Sita, Angew. Chem. Int. Ed. 55, 4683 (2016).

[2] – S. R. Nowak, W., Hwang, and L. R. Sita, J. Am. Chem. Soc. 139, 5281 (2017).



45

T.14 - Liquid-solid transitions of a repulsive system with also a short-

range attractive potential

G. Yuan1, 2, J. Luo,3 C. Zhao,4 C. C. Han5

1Georgetown university. 2NIST center for neutron research, [email protected]. 3Institute of

Chemistry, Chinese Academy of Sciences, [email protected] 4Ningbo University,

[email protected]. 5Shenzhen university, [email protected]

The liquid-solid transitions problem is approached from a very fundamental way---build a

model system with simple and tunable inter-particle potential, then investigate the effect of

the inter-particle potential (mainly the attractive part) on the transitions, which includes

gelation at low packing density and glass formation at high packing density. Inter-particle

attraction is tuned by mixed suspensions of large hard colloid and adsorptive small soft

microgel, in which small microgels can either serve as bridges to connect neighbouring large

particles thus to introduce the bridging attraction, or serve as stabilizers fully covered on the

surface of large particles. With neutron scattering and rheology techniques, we determined

the boundaries of various state-transitions (Figure 1) and describe the characters of these

transitions, from structural, dynamical, and thermodynamic point of views. Our results

indicate that the attraction force between the added small polymers and the large particles

(or the origin of effective inter-particle potentials, or maybe the very details of attractive

potentials) have a fundamental impact on the mechanism of liquid-solid transition [1, 2].

Figure 1: A framework of state transition and schematic illustration of PS microsphere and PNIPAM

microgel structures.

References

[1] G. Yuan, H. Cheng and C. C. Han, Polymer. 131, 272 (2017).

[2] J, Luo, G. Yuan, C. Zhao, C. C. Han, J. Chen and Y. Liu, Soft Matter. 11, 2494 (2015).



ISPAC 2018 - Session: Macromolecular Architectures

46

T.15 - Synthesis and Characterization of Polyolefins with Precise Control

of Branch Frequency and Branch Length

S. V. Orski1, L. A. Kassekert2, W. S. Farrell1, M. A. Hillmyer2, and K. L. Beers1

1 Materials Science & Engineering Division, National Institute of Standards & Technology (NIST),

Gaithersburg, Maryland 20899, United States 2 Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455-0431, United States

Separations of commercial polyolefins, which often involve mixtures and

copolymers of linear, short-chain branched, and long-chain branched polyethylenes, can be

very challenging to optimize as species with similar hydrodynamic sizes or solubility often

co-elute using various chromatographic methods. To better understand the effects of

polyolefin structure on the dilute solution properties of polyolefins, a family of highly

controlled short-chain branched polyolefins with control of alkyl branch frequency and

branch length were synthesized by ring-opening metathesis polymerization (ROMP) of alkyl

substituted cyclooctene monomers. This synthetic approach utilizes strained cyclic alkenes

to generate controlled, regioregular polyalkenamers. Quantitative post-polymerization

hydrogenation generates the final branched polyolefins with ideal head-to-tail addition of

monomer, resulting in a fixed branch frequency and branch length across the molar mass

distribution.

A series of linear polyolefins with comparable molar masses, but varied short-chain

branch length, were analysed by ambient and high temperature size exclusion

chromatography (SEC) with differential refractive index, viscometric, and multi-angle light

scattering detectors to quantify molar mass, molar mass distribution, intrinsic viscosity ([η]),

and radius of gyration (Rg) of each polymer. An additional flow-through infrared detector

also measured the degree of short-chain branching across the elution curve. A systematic

decrease of intrinsic viscosity is observed with increasing branch length across the entire

molar mass distribution. These regularly branched polyolefins can potentially serve as useful

standards to calibrate the short-chain branching distribution of polyolefins with higher

branching content as well as the branching index correction factor as a function of molar

mass. Such calibrations will help improve accuracy in measurements of long-chain and

short-chain branching distributions in polyolefins, especially in samples that contain both

types of branching.

Figure 1: Intrinsic viscosity of the model branched polyolefins as a function of molar mass.


47

T.16 - Functional electrospun membranes featuring grafted polymer

brushes: The characterization challenge

Yan Liu1,2, Jinghong Ma2, G. Julius Vancso1,2

(1) University of Twente, Materials Science and Technology of Polymers, MESA+ Institute for

Nanotechnology, Enschede, the Netherlands; [email protected]; (2) Donghua University, Shanghai, PRC

We report on the preparation, characterization, and catalytic activity of microporous

membranes consisting of of polycaprolactone (PCL) microfibers featuring gel-brush layers

of poly(hydroxyethyl methacrylate) (PHEMA). The brush coating on the fibers of these

membranes was loaded by Pd nanoparticles (NP) by in-situ reduction of Pd2+, coordinated

to carboxylate groups in the brush [1]. Reaction was performed in aqueous Pd(NO3)2

electrolytes by using NaBH4. Gel-brushes were obtained via surface-initiated ATRP

polymerization. The membrane mats prior to functionalization were fabricated by

electrospinning of PCL solutions. The PCL included mixtures of Br terminated PCL chains

with non-functional polymer. Electrospun fibers thus featured Br at their surface, which

functioned as initiators, and allowed us to polymerize polymer gel-brushes on the fibers. (A

scheme is appended showing the steps of the preparation.) We used FTIR, wettability

measurements, surface morphology imaging by TEM and SEM and thermal analysis to

characterize the membranes.

The membranes obtained had a large specific surface area and high porosity, which enabled

high concentrations of metal nanoparticle loadings. The membranes obtained showed

pronounced catalytic activity due to the presence of Pd NPs, which were stabilized by the

brush. As a proof-of-principle experiment we performed catalytic reduction of 4-nitrophenol

to 4-aminophenol in continuous flow-through catalysis.

References

[1] Benetti, E.M., Sui, X., Zapotoczny, S., Julius Vancso, G. Surface-grafted gel-brush/metal nanoparticle

hybrids (2010) Advanced Functional Materials, 20 (6), pp. 939-944.



48

T.17 - Characterization of the chemical composition distribution of 1-

octene based POP/POE by HPLC

J.H. Arndt1, R. Brüll1, T.Macko1, P. Garg2, J. Tacx2

1 Fraunhofer Institute for Structural Durability and System Reliability, Plastics Division, Schlossgartenstrasse

6, 64289 Darmstadt, Germany, 2 SABIC Technology & Innovation, STC Geleen, P.O. Box 319, 6160 AH

Geleen, The Netherlands

Ethylene/1-octene (EO) copolymers with high 1-octene content, marketed as polyolefin

plastomers (POP) and elastomers (POE), are materials of ever rising popularity and

commercial importance. Their chemical composition distribution (CCD) i.e., the distribution

of 1-octene units among individual macromolecules, has never been systematically studied.

An important reason is the low crystallinity of many of these materials, oftentimes

precluding the use of crystallization-based separation techniques such as analytical

temperature rising elution fractionation (a-TREF) [1] or crystallization analysis fractionation

(CRYSTAF) [2].

The more recently established high temperature high performance liquid chromatography

(HT-HPLC) [3,4] has no such limitations and thus holds potential to study the CCD. For this

study nine POP/POE samples covering a wide compositional range were selected. Different

solvent combinations were tested in order to identify the one giving the highest resolution

i.e., the biggest separation of molecules of different 1-octene content. The study shows a

good agreement between the CCD of the samples calculated theoretically based on

Stockmayer distributions and the CCD obtained experimentally.

Acknowledgments: The authors would like to thank C. Melian and R. Chitta for NMR and

aTREF measurements contributing to this work.

References

[1] M. Zhang, D.T. Lynch, and S.E. Wanke, J. Appl. Polym. Sci. 75, 960 (2000).

[2] B. Monrabal, N. Mayo and R. Cong, Macromol. Symp. 312, 115 (2012).

[3] T. Macko and H. Pasch, Macromolecules 42, 6063 (2009).

[4] T. Macko, R. Brüll, R.G. Alamo, Y. Thomann, V. Grumel, Polymer 50, 5443 (2009).


49

T.18 - Striving for Perfection: “Defect”-Free Polymer Networks for

Improved Metrology

J.M. Sarapas, E.P. Chan, D.N. Vaccarello, E.M. Rettner, K.L. Beers

National Institute of Standards and Technology; [email protected]

Polymer networks are ubiquitous across academia and industry, providing solutions and

platforms to address problems ranging from biotherapeutics to commodity rubbers. Despite

their broad application, networks are often engineered in such a way that promotes local

heterogeneities, which can complicate or even drive the resulting properties. Here, we target

the synthesis of extremely soft entanglement-free materials by employing a bottlebrush

polymer architecture between crosslinks.[1] This was achieved through ring-opening

metathesis polymerization (ROMP) of mono- and di-norbornene functionalized poly(n butyl

acrylate) (PnBA). By varying the ratio of mono-norbornene macromonomer to di-

norbornene crosslinker, networks with dramatically different properties were generated.

Network moduli were determined in the dry state, with values ranging from 1 to 10 kPa,

approaching the softest known bulk networks. Importantly, network modulus scaled with

estimated crosslinking density through an exponent of -0.81, in good agreement with rubber

elasticity. Swelling ratios were also correlated to dry state modulus, revealing an exponential

relationship again in good agreement for general polymer networks. These results indicate

that bottlebrush polymer networks follow the same fundamental physics as non-brush

networks while mitigating entanglements, highlighting their potential as model materials to

better inform industrial and academic materials.

Figure 1: Depiction of bottlebrush polymer network formation.

References

[1] - J.M. Sarapas, E.P. Chan, E.M. Rettner, K.L. Beers, Macromolecules 51, 2359-2366 (2018).

ISPAC 2018 - Plenary: Molecular Architectures

50

T.04 - Molecular Engineering with Anionic Polymerization

Professor Lian R Hutchings

Durham Centre for Soft Matter, Department of Chemistry, Durham University, Durham, DH1 3LE. United

Kingdom.

[email protected]

Anionic polymerization is well-known for its fine control of molecular structure and has

been widely adopted for the synthesis of a variety of molecular architectures. Anionic

polymerization also lends itself well to the synthesis of copolymers with precise sequence

distributions. We present recent highlights of research at Durham University in two broad

areas – i) the synthesis of long-chain branched (co)polymers and ii) the synthesis of

sequence-controlled copolymers.

In the first case we will review the synthesis of complex branched (co)polymers by the

“macromonomer” approach1 and highlight the use of temperature gradient interaction

chromatography (TGIC) as useful characterization tool2,3. We will also describe the

synthesis of randomly branched polymers by anionic chain transfer polymerization.

In the second case we will describe the synthesis of a series of copolymers including perfect

alternating copolymers, sequence-controlled terpolymers and telechelic polymers4.

Moreover, in each case, the resulting sequence is entirely controlled by copolymerization

kinetics with all monomers present from the start on the reaction. As such these

copolymerization reactions are effectively a contrived statistical copolymerization whereby

all monomers undergo polymerisation simultaneously in what we (and others) have

described as a “fire and forget” approach. Sequence analysis in many cases relies on careful

MALDI-ToF MS characterization.

References

1. Hutchings, L. R.; Agostini, S.; Hamley, I. W.; Hermida-Merino, D. Macromolecules 2015, 48, 8806.

2. Hutchings, L. R.; Kimani, S. M.; Hoyle, D. M.; Read, D. J.; Das, C.; McLeish, T. C. B.; Chang, T.; Lee, H.;

Auhl, D. In Silico Molecular Design, Synthesis, Characterization, and Rheology of Dendritically Branched

Polymers: Closing the Design Loop. ACS Macro Letters 2012, 1, 404.

3. Hutchings, L. R. Complex Branched Polymers for Structure-Property Correlation Studies: The Case for

Temperature Gradient Interaction Chromatography Analysis. Macromolecules 2012, 45, 5621.

4. Hutchings, L. R.; Brooks, P. P.; Parker, D.; Mosely, J. A.; Sevinc, S. Monomer Sequence Control via Living

Anionic Copolymerization: Synthesis of Alternating, Statistical, and Telechelic Copolymers and Sequence

Analysis by MALDI ToF Mass Spectrometry Macromolecules 2015, 48, 610.


51

T.05 - New Opportunities for Precision Polyolefins: Design,

Characterization and Dynamic Behavior of Nanostructured Polyolefin

Block Copolymers

Lawrence R. Sita

Department of Chemistry and Biochemistry, University of Maryland, College Park, MD USA.

[email protected]

Abstract: Living coordinative chain transfer polymerization (LCCTP) is a new

polymerization process that can provide access to a large variety of ‘precision polyolefins’

of tunable molecular weight, very narrow polydispersity, and quantitative end-group

functionalization from readily available and inexpensive α-olefin monomers. This talk will

provide an overview of recent studies by our group that have served to expand the structural

range and bulk properties of: 1) microphase-separated polyolefin-polyolefin block

copolymers, 2) atactic-isotactic stereoblock, sterogradient and stereoirregular polyolefin

block copolymers, and 3) microphase-separated (sub-10 nm) sugar-polyolefin conjugates.

An arsenal of spectroscopic and analytical methods have been employed to establish the

nanostructured morphologies and the dynamic behavior of these materials, including

reversible order-to-order and disorder-to-order phase transitions within the bulk solid state

and ultrathin films.


52

T.06 - Polyhomologation: A Powerful Tool Towards Well-

Defined Polyethylene-Based Polymeric Materials

Nikos Hadjichristidis

King Abdullah University of Science and Technology (KAUST), Physical Sciences and Engineering Division, Catalysis Center, Polymer Synthesis Laboratory, Thuwal, Saudi Arabia

Polyethylene (PE) is and will continue to be the most widely used industrial polymer in

the world, benefiting from its product versatility, hydrophobicity, mechanical strength,

flexibility, resistance to the harsh environment, easy processability, recyclability, along with

low cost. Covalently linked to PE (block copolymers) polar blocks, such as polystyrene,

poly(methyl methacrylate), polycaprolactone, polyethyleneoxide and polypeptides offers

significant improvements in adhesion and compatibility of PE with other polar polymers and

thus broadens its applications. Consequently, the design/synthesis of block copolymers of

PE with polar chains is important to both academia and industry.

In 1997, Shea and co-workers1, inspired from the well-known in organic chemistry

homologation reaction, discovered a borane initiated/mediated C1 living polymerization of

dimethylsulfoxonium. This C1 polymerization, coined by Shea polyhomologation, has been

proven as an efficient tool to synthesize well-defined and perfectly linear hydroxyl-

terminated polyethylene. The OH-terminated PE can be used either as macroinitiator for ROP

of cyclic ethers/esters or for living/radical after transformation, to afford well defined

PE/polar block copolymers with perfectly linear PE and high molecular weight homogeneity.

Along these lines the synthesis of PE-based materials (homo/block copolymers,

hybrids with silica) will be discussed, as well as their potential applications (e. g. PE

reinforcing agents and Aggregation Induced Emission).2-14 Novel powerful procedures are

needed for the analysis/characterization of these complex PE-based macromolecular

architectures.

[1] Luo, J., Shea, K. J. Acc. Chem. Res. 2010, 43, 1420-1433.

[2] Zhang, H., Alkayal, N., Gnanou, Y., Hadjichristidis, N. Chem. Commun. 2013, 49, 8952-8954.

[3] Zhang, H., Gnanou, Y., Hadjichristidis, N. Polym. Chem. 2014, 5, 6431-6434.

[4] Zhang, H., Alkayal, N., Gnanou, Y., Hadjichristidis, N. Macrom. Rapid Commun. 2014, 35, 378-390.

[5] Alkayal, N., Hadjichristidis, N. Polym. Chem. 2015, 6, 4921-4926.

[6] Zhang, Z., Zhang, H., Gnanou, Y., Hadjichristidis, N. Chem. Commun. 2015, 51, 9936-9938.

[7] Zhang, H., Gnanou, Y., Hadjichristidis, N. Macromolecules 2015, 48, 3556-3562.

[8] Wang, D., Zhang, Z., Hadjichristidis, N. ACS Macro Letters 2016, 5, 387-390.

[9] Zhang, H., Hadjichristidis, N. Macromolecules 2016, 49, 1590-1596.

[10] Zheng, Z., Altaher, M., Zhang, H., Wang, D., Hadjichristidis, N. Macromolecules 2016, 49, 2630-

2638.

[11] Wang, D., Hadjichristidis, N. Chem. Comm. 2017, 53, 1196-1199

[12] Wang, D., Zhang, Z., Hadjichristidis, N. Polym. Chem., 2017, 8, 4062-4073.

[13] Jiang, Y., Zhang, Z., Wang, D., Hadjichristidis, N. Macromolecules 2018, 51, 3193-3202.

[14] Zapsas, G., Ntetsikas, K., Kim, J., Bilalis, P., Gnanou, Y., Hadjichristidis, N., Polym. Chem. 2018,

9, 1061-1065.

ISPAC 2018 - Session: Condensed Phase Spectroscopy

53

T.21 – Bulk heterojunction interfacial structure from REDOR NMR

R. C. Nieuwendaal1, D. M. DeLongchamp1, L. J. Richter1, C. R. Snyder1, R. L. Jones1, S.

Engmann1, A. Herzing1, M. Heeney2, Z. Fei2, A. B. Sieval3, J. C. Hummelen3, D. Reid4, J.

J. dePablo4,

1Materials Measurement Laboratory, National Institute of Standards and Technology, 100 Bureau Drive,

Gaithersburg, MD, 2Department of Chemistry, Imperial College, London SW7 2AZ, England, 3Stratingh

Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands, 4Institute for Molecular Engineering, University of Chicago, Chicago IL, 60637. [email protected]

Robust relationships between structure and function are generally lacking in organic

photovoltaic (OPV) thin film active layers. To predict performance there exists a need for

tools that can measure structure on length scales fine enough to be relatable to inter-

molecular energy transfer. Electron microscopy lacks sufficient spatial resolution due to a

lack of electron density contrast, and scattering curves can be ambiguous because there

typically is not a unique fitting model.

In this talk, I will give highlights of recent 13C {2H} rotational echo double resonance

(REDOR) measurements to characterize the donor/acceptor interfaces in bulk heterojunction

thin films. Heteronuclear couplings are measured between 13C nuclei on the acceptor C60

cage and thiophene hydrogens on the donor main chain, which has been isotopically enriched

with 2H. I will discuss models of the interface that are used to fit the REDOR dephasing

curve, and the constraints that these models have on local composition and packing. We will

also show that the REDOR measurements can help solve the mystery of which model to use

in fitting small angle neutron scattering curves.

Figure 1: Heteronuclear dipolar couplings measured at the donor/acceptor interface with REDOR NMR.


54

T.22 - Characterization of modified silicas with industrial interest

A. A. Bernardes, A. Marchi Netto, M. S. L. Miranda and R. Brambilla

I&T, Braskem S.A., Via Oeste, lote 5, Triunfo-RS, 95853-001,Brazil

[email protected]

Hybrid silicas prepared by sol-gel process have found several applications, for

example, as support in metallocene catalysis for olefin polymerization. Silica support allows

better distribution of catalytic sites, leading to polymers with well-controlled molar mass and

polydispersity. Therefore, a non-hydrolytic silica sol-gel route was developed encompassing

catalyzed polymerization of tetraethoxysilane (TEOS), silicon tetrachloride (SiCl4) and

different contents of octadecyltrimethoxysilane (ODS) [1].

The produced silicas were characterized by a set of key analytical technics. ATR-

FTIR and DRIFTS evidenced the formation of new siloxane groups (Si-O-Si) and the

presence of isolated, vicinal and germinal silanol groups on the silica surface; a solution 29Si-

NMR experiment detailed different 29Si species in the hybrid material. The silanol groups

could be elucidated through a 1H-MAS-NMR experiment, with bands attributed to H-

bounded hydroxyls, aliphatics and isolated silanol protons [2].

Predominance of gauche defects over trans conformation of the alkyl chain were

investigated by 13C-CP/MAS-NMR, although increasing the order as increasing the

octadecylsilane. Complementarily, 29Si-CP/MAS-NMR experiments revealed the nature of

the functional species on the modified silicas surface and hydroxyl groups neighborhood [2].

Finally, SEM images revealed no changes on morphology after the silica modification.

10 8 6 4 2 0 -2 -4

(b)

Chemical shift [ppm]

H-bonded

hydroxyls Isolated silanols

Methyl and methylene groups

(a)

50 40 30 20 10 0 -10

1, 18


3 - 16

Trans

Gauche

2, 17

O

SiO

O

CH2 CH2 (CH2) CH214

CH3

1 2 3-16 17 18

(b)

(a)

(d)

(c)

(e)

(f)

50 0 -50 -100 -150 -200

Q4

Q3

-15 -30 -45 -60 -75

T3

T2

(b)


(a)

(d)

(c)

(g)

(e)

(f)

Q2

Figure 1: Solid-state NMR spectra of the modified silicas (all of them with the

organic content increasing from down to up): a) 1H-MAS-NMR b) 13C-

CP/MAS-NMR c) 29Si-CP/MAS-NMR

Any of these individual techniques proved to be invaluable for the complete

characterization of the hybrid material [3]. Ongoing, metallocene catalyst is being

immobilized at these supports for olefin copolymerization trials.

A. A. Bernardes thanks CNPq-RHAE (472571/2014) for financial support.

References

[1] - K. Albert and E. Bayer, Journal of Chromatography 544, 345-370 (1991)

[2] - L. Bourget et al, Journal of Non-Crystalline Solids 242, 81-91 (1998)

[3] - A. A. Bernardes et al, Journal of Non-Crystalline Solids 466, 8-14 (2017)

a) b) c)


55

T.23 - Relating Post Yield Mechanical Behavior in Polyethylenes to

Spatially-varying Molecular Deformation Using Infrared Spectroscopic

Imaging: Homopolymers

Prabuddha Mukherjeea, Ayanjeet Ghosh a, Nicolas Spegazzinia, Mark J Lambornb, Masud

M Monwarb, Paul J DesLauriersb* and Rohit Bhargava*ac

aBeckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign,

Urbana, IL 61801, USA bChevron Phillips Chemical Company LP, Bartlesville, OK 74004, USA

cDepartments of Bioengineering, Chemical and Biomolecular Engineering, Electrical and Computer

Engineering, Mechanical Science and Engineering and Chemistry, University of Illinois at Urbana-

Champaign, Urbana, IL 61801, USA

email: [email protected]

Stress-strain curves derived from tensile specimens are the primary characteristic of bulk

polymers’ mechanical properties. Current tools, however, cannot provide molecular insights

from this single bulk measurement. Hence, we use Fourier transform infrared (FT-IR)

spectroscopic imaging to optically and non-destructively measure molecular structure and

its spatial dependence in tensile specimens in high density polyethylene homopolymers. To

overcome the limitations of FT-IR imaging, we use an emerging approach involving the use

of tunable quantum cascade lasers that allows imaging through thick samples and facile

polarized light imaging. Crystal structure and orientation are obtained from spatially varying

measurements of molecular properties in the necking region. Local molecular

(re)arrangements to characterize mechanical properties of drawn samples are deduced from

spectral data. A modified Eyring model was developed to quantitatively understand spatial

dependence in terms of a conformational volume. We report the strain rise in high density

polyethylene homopolymers is governed by the degree of association between the crystalline

domains. Together, the new measurement technology and analysis reported here can relate

molecular composition, microscopic gradients and orientation to bulk mechanical properties

of semi-crystalline polymers.

Schematic illustration of how the spatial variation of molecular response in a polymer can be used to evaluate

mechanical properties spectroscopy and imaging. (Left) The physical process of necking, demonstrating the

focus of the study on the necking region. (Middle) A representative stress-strain curve for HDPE overlaid on

the cartoon of a necked polymer. (Right) Drawn tensile samples exhibit optical anisotropy beyond the yield

point that arises from molecular reorganization and are seen in polarized infrared spectra. Anisotropy

measurements by imaging allows visualization of the spatial distribution of molecular orientation in the entire

sample, with localized sensitivity.


56

T.24 - Influencing liquid crystalline gel formation in cellulose ionic liquid

solutions by adding water and nanoparticles

Ashna Rajeev, Abhijt P Deshpande, Basavaraja M. Gurappa

Polymer Engineering and Colloidal Science Lab, Dept of Chemical Engineering,

Indian Institute of Technology Madras, India. 600036

[email protected]

Liquid crystalline gels find application in different fields such as, display and storage

devises, sensors etc. Recently, it was reported that cellulose dissolved in 1-ethyl-3-

methylimidazolium acetate (EmimAc) shows sol-gel transition accompanied by a liquid

crystalline phase transition at high cellulose concentrations [1].

In this work we report the preparation of liquid crystalline gel phase from cellulose/ionic

liquid solutions by altering the solvent environment due to the addition of water which is an

anti-solvent for cellulose. We studied the characteristics of cellulose/ionic liquid/ water

mixtures at 5-15 wt% of cellulose concentrations by combining rheological and polarisation

optical microscopy observations. We observed the formation of non-aligned Cholesteric

liquid crystalline phase at low cellulose concentration and spherulite-like assemblies at high

cellulose concentration. Further we investigated the enhancement of gel properties by

incorporating spherical as well as shape anisotropic nanoparticles at different nanoparticle:

cellulose weight ratios, into the cellulose/ionic liquid/water gel matrix.

Figure 1: Polarization optical microscopy image showing non-aligned holesteric liquid crystalline phase in

10 wt% cellulose/BmimCl solution.

References

[1] – H. Song et al., Biomacromolecules, 12, 1087 (2011).

ISPAC 2018 - Session: Advances in Chromatography

57

T.25 - Characterization of branched polycarbonate by comprehensive

two-dimensional liquid chromatography with multi-detector setup and

correlation with Monte-Carlo simulations

Nico Apel1, Elena Uliyanchenko2, Vaidyanath Ramakrishnan2, Tibor Macko1, Robert

Brüll1

1Fraunhofer Institute for Structural Durability and System Reliability (LBF), Division Plastics, Group

Material Analytics, Schlossgartenstr. 6, 64289 Darmstadt, Germany, [email protected] 2SABIC, Plasticslaan 1, 4612 PX Bergen op Zoom, the Netherlands

Branching is often applied to influence rheological properties of plastics. Exemplarily,

branching increases polymer melt elasticity at low shear rates and reduces viscosity at high

shear rates (shear thinning) and as a result the processing of plastics as well as its final

properties are influenced by branching. In this sense branching is an important driver of

material innovation, and appropriate analytical protocols are required to determine these

parameters.

Because branching distribution coexists with other molecular distributions (e.g. with regard

to molecular weight and functionality-type) such materials are very complex in their

composition. Thus, an in-depth characterization of branched polymers requires an adequate

combination of multiple analytical techniques. While separations based on molecular size

and end-group type are relatively straightforward, by size-exclusion chromatography (SEC)

and liquid chromatography at critical conditions (LCCC), respectively, to date no specific

technique for a separation based on branching level available.

In this work, we describe two-dimensional liquid chromatography analysis of branched

polycarbonate. Utilizing differences in end-group composition and in the hydrodynamic

volume between branched and linear chains, we were able to achieve a separation of

structures with different branching levels [1]. In the first dimension, a shallow solvent

gradient was applied with a mobile phase composition in proximity to the critical point of

adsorption allowing for a separation according to end-groups [1]. This separation was then

hyphenated to SEC as a second dimension and complimented with a multi-detector setup

(UV, refractive index, light scattering detectors and a viscometer) [2]. This allowed access

to (semi)quantitative information on the end-group, molecular weight and branching

distributions in the sample. The resulting experimental data were then correlated with

Monte-Carlo simulations of the polymerisation of branched sample validating the underlying

simulation model [2].

References

[1] Apel, N.; Uliyanchenko, E.; Moyses, S.; Rommens, S.; Wold, C.; Macko, T.; Brüll, R. Separation of

Branched Poly(bisphenol A)carbonate Structures by Solvent Gradient at Near-Critical Conditions and

Two-Dimensional Liquid Chromatography. Anal. Chem. 2018, accepted, DOI:

10.1021/acs.analchem.8b00618

[2] Apel, N.; Ramakrishnan, V.; Uliyanchenko, E.; Moyses, S.; Rommens, S.; Wold, C.; Macko, T.; Brüll,

R., Correlation between Comprehensive 2D Liquid Chromatography and Monte- Carlo Simulations for

Branched Polymers. 2018, Submitted to Macromolecules.


58

T.26 - Valorisation of multi-dimensional analytical approaches to unlock

complex products characterization. The particular case of apolar

commercial synthetic polymers.

Jessica S. Desport1, Gilles Frache1, Marcel Wirtz2

1Materials Research and Technology Department, Luxembourg Institute of Science and Technology,

Belvaux, Luxembourg 2Goodyear Innovation Center Luxembourg, Colmar‐Berg, Luxembourg

At first sight, liquid adsorption chromatography and polymers look rather mismatched since

polymers are a mixture of congeners having different length and thus retention time is

strongly affected by the number of repeated units of a given chain. Despite this apparent

incompatibility, efforts have been made to develop methods addressing a separation

exclusively based on chemical nature or architecture. However, analysis consistency is often

being significantly affected by samples complexity. Indeed, modern advances in

macromolecular synthesis have delivered a path toward more complex structures and

architectures. As a result, conventional analytical techniques, like chromatography or mass

spectrometry, taken individually, may only provide with a partial picture of the sample. This

is all the more important when considering commercial products. Indeed, commercial

polymeric materials are typically heterogeneous both in terms of mass and chemical

distributions. Besides, they often consist of a mixture, including additives such as anti-

oxydants, or modifiers. In this work, characterization of industrial polymer products was

addressed. Implementing a suitable coupling of analytical tools appeared to provide the most

powerful and comprehensive strategy to achieving product breakdown and in-depth

molecular elucidation (Figure 1). Two-dimensional chromatography (LCCxGPC,

GPECxGPC, LCCxLCC) was used as core technique to achieve molecules separation based

on size and chemical nature while mass spectrometry permitted the identification of the

different molecular populations. The particular apolar nature of the samples required a

screening of ionization techniques (MALDI, ESI), analyzers (Orbitrap, TOF), as well as

sample preparation to optimize intact ions detection. All data generated were processed as

material “fingerprints”, either via contour plot images or Kendrick plots, allowing for a fast

and valuable comparison of commercial batches.

Figure 1: Multi-dimensional analytical toolbox for advanced polymer characterization.


59

T. 27 - Size Exclusion Chromatography Characterization of Poly(Ester

Urethane) Degradation Products

Dali Yang

MST-7: Engineered Materials, MST Division, Los Alamos National laboratory

Los Alamos, NM 87545, USA, [email protected]

Poly(ester urethane) (PEU) is a multiblock copolymer obtained by the polymerization of

4,4’-diphenylmethane diisocyanate (MDI) chain-extended with 1,4-butanediol (BDO) as

the rigid hard segment and polybutylene adipate (PBA) as the flexible soft segment. With

these two segments, the polymer exhibits good abrasion resistance, high elongation, low

temperature flexibility. It can be processed by means of solution coating, extrusion, and

melt coating. Therefore, these polymers are widely used as adhesive for inks and lacquers,

fabric coating, binder for magnetic media[1], and composite material formation[2]. Recent

years, poly(ester urethane) gains more and more interests in biomedical applications and

biomaterial fields because of its elasticity, sufficient mechanical strength and

biodegradability[3]. It is essential to understand these properties change as the material

ages and to identify the chemical degradation mechanisms. Over the years, numerous

studies have been conducted and have determined several mechanisms of degrading the

poly(ester urethanes) depending on exposure environments, such as hydrolysis and non-

hydrolysis reactions caused by the presence of moisture or/and oxidant.[4] To accelerate

the aging processes in experiments, the polymers are often aged under elevated

temperatures resulting in chain scissions and branched structures, which make the

identification of the chemical structures of the degraded products challenging.

Figure 1: Chemical structure of Estane – a type of poly(ester urethane) polymers.

In this contribution, we systematically characterized a set of naturally aged Estanes with the

molecular weight ranging from 135 – 20 kDa. The combination of size exclusion

chromatography with UV/Vis, viscometer, MALS detectors allows us to fully analyze the

degraded polymers, leading to new information about (i) chemical structures of oligomer

and polymer fractions, (ii) Mark-Houwink correlations, and (iii) their dn/dc values. This

work was supported by the US Department of Energy through the Los Alamos National

Laboratory Enhanced Surveillance Program.

1. References

2. [1] https://plastics.ulprospector.com/datasheet/e122063/estane-5703-tpu.

3. [2] Salazar MR, Pack RT. J of Polymer Science: Part B: Polymer Physics. 2002;40:8; and Salazar M, R.,

Kress JD, Lightfoot JM, Russell BG, Rodin WA, Woods L. Polymer Degrdation and Stability. 2009;94:9.

4. [3] Pierce B. F., Brown A. H., Sheares V. V. Macromolecules, 2008;14:8; Mou Z., Y.-X Chen E., ACS

Sustainable Chem. Eng., 2016;4:12; Fang J., Ye S.H., Huang Y.X., Mo X.M., Wagner W. R. Acta

Biomater. 2014;10:11; Gugerell A., Kober J., Laube T., Walter T. et al. POLS ONE, 2014;9(3):14.

5. [4] Brown D. W., Lowry R. E., Smith L. E. Macromolecules, 1980;13:8 and Jellinek, H. H. G.,

Wang, T. J. Y. Journal of Polymer Science 1973;11:16.

NH

C

O

O

H2C

NH

C

O

OC

COO

O

O

O

m = 1-3n = 4-6

PolyesterSo SegmentPolyurethane(MDI)HardSegment


60

T.28 - Polymer separation beyond SEC – expanding the range

from molecules to particles

Robert Reed1, Bassem Sabagh2, Paul Clarke2, Gerhard Heinzmann3

1) Postnova Analytics Inc, Salt Lake City, UT, USA,

2) Postnova Analytics UK Ltd, Malvern, UK,

3) Postnova Analytics GmbH, Landsberg, Germany

Size exclusion chromatography (SEC or GPC) is an immensely useful and valuable tool for

polymer solution characterization. However, despite its universality, the characterization of

polymers in solution for molecular weight and size/structural information by SEC is highly

restricted by the requirement that the polymer is fully dissolved in the mobile phase and has

no interaction with the column packing material. Furthermore, any formation of polymer

particles or other supramolecular structures such as vesicles (polymersomes) results in

erroneous or incomplete size or molecular weight distributions.

As SEC cannot be used after the formation of polymer latex or other supramolecular

structures means we must resort to batch techniques such as static light scattering (MALS)

or dynamic light scattering (DLS). These batch techniques yield very limited information

about the distribution of molecular weight or size and furthermore may give misleading

information due to the weighting of the data by larger species.

This paper describes and presents a flow technique to complement SEC that can separate

polymers and polymer structures in solution or suspension and can be coupled on-line to

DLS and MALS to get accurate distribution information. We will show several examples of

how highly valuable analytical data can be obtained from polymers, polymer latex, polymer

particles and polymer vesicles that is not obtainable in any other way.


61

Wyatt Technologies Lecture

W.01 - Structure and Dynamics in Polymer-Grafted Nanoparticle

Systems

Michael J. A. Hore, Yuan Wei, and Yifan Xu

Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, OH

USA. [email protected]

When grafted to spherical nanoparticles, polymers can adopt a variety of conformations

depending on the nanoparticle size and polymer grafting density.[1] At moderate grafting

densities, a high concentration of polymer near the nanoparticle (“concentrated polymer

brush”, CPB region) core creates confinement effects that cause the polymer chain to be

stretched, with a thickness that scales with the degree of polymerization (N) as h ~ N0.8. Past

a cutoff distance rc, that can be calculated by scaling theories, the concentration decreases

with increasing distance from the core (“semi-dilute polymer brush”, SDPB region) and the

polymer chain adopts a more random conformation. In this talk, we discuss recent progress

in characterizing the structure and dynamics of polymers that are grafted to spherical

nanoparticles by small-angle neutron scattering (SANS) and neutron spin echo spectroscopy

(NSE), respectively. New core-shell-chain (CSC) and core-chain-chain (CCC) form factors,

which account for excluded volume in the polymer chains, are able to capture the predictions

from scaling theories, and are in good agreement with scaling relationships observed from

dynamic light scattering (DLS) and electron micrograph analysis.[2] NSE measurements

show that the confinement experienced in the CPB region can have a significant impact on

the relaxation dynamics of the polymers, which may in turn have implications for the

processing and mechanical properties of nanocomposites containing such particles.

Figure 1: Selective deuteration scheme utilized to measure structure and dynamics in the concentrated

polymer brush (CPB) and semi-dilute polymer brush (SDPB) regions of polymer-grafted silica nanoparticles.

References [1] W. R. Lenart and M. J. A. Hore, Nano-Structures & Nano-Objects 2017 (in press).

[2] M. J. A. Hore, J. Ford. K. Ohno, R. J. Composto, and B. Hammouda, Macromolecules 2013, 46, 9341-

9348.


62

W.02 - Recent Advances in X-ray Scattering Methods for Soft Materials

Kevin G. Yager

Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY USA. [email protected]

X-ray scattering methods have been used to great effect in the study of polymer materials,

from resolving the nanoscale morphology of self-assembling materials to quantifying the

molecular packing of semiconducting polymers. This talk will discuss recent efforts to

further expand the utility of x-ray scattering in the study of soft materials. While traditional

scattering focuses on the ensemble average, emerging techniques that emphasize variability

can undercover additional information. Variance along scattering rings can be analyzed to

extract hidden information about grain structure. Angular correlation methods can be

combined with coherent scattering to amplify the signal from the sample above background.

New methods for improving data quality will also be discussed. X-ray detector images can

be ‘healed’ in a physically meaningful-way, and grazing-incidence scattering (GISAXS)

images can be ‘unwarped’ by either altering measurement geometry or through data analysis.

Finally, recent work in the use of deep learning to analyze scattering images will be

presented.


63

Pfizer Consumer Healthcare Lecture

W.03 - Soft matter structure measurement by Polarized Resonant

Soft X-ray Scattering

Dean M. DeLongchamp

National Institute of Standards and Technology, Gaithersburg, MD

In many applications of soft matter, the connection between structure and performance is

complex, and conventional structure measurements are not sufficient to provide a

predictive structural model. Nanoscale variations in molecular orientation and composition,

particularly in amorphous regions, are thought to be critical, but few techniques can probe

them. I will describe our approach to polarized resonant soft X-ray scattering (P-RSoXS),

which combines principles of spectroscopy, small-angle scattering, real-space imaging, and

molecular simulation to produce a molecular scale structure measurement for soft materials

and complex fluids. Progress and designs for a new P-RSoXS beamline will be shown.

Results from model systems including commodity plastics, block copolymers, and organic

photovoltaics blends will be discussed. An emphasis will be placed on connections

between P-RSoXS and small angle neutron scattering (SANS), including different contrast

approaches, different experimental considerations, and unique measurement capabilities of

each technique.

ISPAC 2018 – Poster Session

64

P.01 - (LF)TD-NMR FOR THE STUDY OF POLYMERIC NETWORKS

Denise Besghini, Michele Mauri, Roberto Simonutti,

Department of Materials Science, University of Milano-Bicocca, via R. Cozzi 55, 20125

Milan

Polymer networks, including rubbers and hydrogels, are ubiquitous materials. The

determination of their structure-property relationship is fundamental for their rational

improvement. Low Field (LF) Time Domain (TD) Nuclear Magnetic Resonance (NMR) is

a powerful technique to probe molecular-level dynamics, through 1H relaxation times T1 e

T2. Important variations in chain dynamics, such as phase transitions, can be easily monitored

with the study of T2 at varying temperatures. In Figure 1, a methylated cellulose

thermogelating material1 shows increased T2 upon temperature increase, followed by a

sudden drop at the gelation point. The reversibility of the process, the formation of a

metastable phase and the associated hysteresis phenomena can be monitored, obtaining

results in line with rheological testing.

Left: T2 relaxation time of methylcellulose gels during a temperature cycle (from 10 to 75 °C). Right,

distribution of dipolar coupling in an heterogeneous reversibly crosslinked rubber, compared to a more

homogeneous sample.

TD-NMR can also measure dipolar couplings (Dres), which are linearly proportional to

crosslinks density (CLD), according to the equation 𝐶𝐿𝐷 =𝐷𝑟𝑒𝑠

4𝜋𝐴. This has been exploited to

measure the evolution of crosslinking in conventional rubbers and their blends,2.and to prove

the formation of polar crosslinks clusters in more innovative modified EPDM rubbers

crosslinked via reversible Diels-Alder chemistry3. Figure 1 (right) highlights the bimodal

distribution of Dres in an heterogeneous system as compared to a more homogeneous one.

Access to CLD distribution is the most outstanding advantage of TD-NMR compared to

traditional method for the determination of CLD, such as equilibrium swelling

measurements. These examples highlight that TD-NMR is a comprehensive tool to

characterize in details polymeric networks, making it suitable for both academic and

industrial applications.

1. P. Nasatto, F. Pignon, J. Silveira, M. Duarte, M. Noseda and M. Rinaudo, Polymers, 2015, 7, 777.

2. M. K. Dibbanti, M. Mauri, L. Mauri, G. Medaglia and R. Simonutti, Journal of Applied Polymer

Science, 2015, 132, n/a-n/a.

3. L. M. Polgar, E. Hagting, P. Raffa, M. Mauri, R. Simonutti, F. Picchioni and M. van Duin,

Macromolecules, 2017, 50, 8955-8964.


65

P.02 - Crystallization and Alkaline Hydrolysis Studies of Poly(3-

hydroxybutyrate)

N. Vasanthan , A. Tappadiya

Department of Chemistry and Biochemistry, Long Island University, One University Plaza, Brooklyn, NY

11201, [email protected]

Poly(3-hydroxybutyrate) (PHB) is a microbially synthesized polymer, which is often

purified by alkaline treatment. The effect of microstructure on alkaline hydrolysis has been

studied by varying concentration of base and the temperature. The morphologies of PHB

films before and after degradation were evaluated using DSC and FTIR spectroscopy. The

hydrolytic degradation study by weight loss measurement revealed that the crystallinity of

PHB greatly decreased the hydrolytic ability of PHB. The crystallization of PHB and the

effect of base on hydrolysis was investigated by time dependent FTIR spectroscopy. The

normalized absorbance of 3010 cm-1 and 1183 cm-1 were used to characterize the crystalline

and the amorphous phases of PHB, shown in Figure 1. FTIR spectroscopy reveal that the

extent of hydrolysis decreased with increasing crystallinity. The crotonic acid was detected

as a major product after hydrolysis, confirmed by UV/Visible and proton NMR

spectroscopy. The normalized absorbance of the crystalline band at 3010 cm-1 band remained

constant, suggesting that there is no significant change in crystallinity with degradation. The

normalized amorphous band at 1183 cm-1 showed a decrease in absorbance ratio, suggesting

degradation of the amorphous phase.

.

Figure 1: FTIR spectra of PHB films cold crystallized at different temperatures in the region (a)1500-900 cm-

1 and (b) 3050-2850 cm-1.

References

1. Doi Y, Steinbuchel A, Eds. Biopolymer, Polyesters I-Biological Systems and Biotechnological Production;

John Wiley and Sons: Weinheim, Germany, 2001;3

2. Gross RA, Kalra B. Biodegradable polymers for the Environment Science 2002;297:803-7.

3. Matsusaki H, Abe H, Doi Y. Biomacromolecules 2000;1:17.

4. Steinbuchel A, Valentine H E. FEMS Microbiol Lett 1995;128:219.

5. Tapadiya, A, Vasanthan, N. International Journal of Biological Macromolecules, 2017, 102, 1130


66

P.03 - Use of Cottonseed Protein in Wood Adhesives

H. N. Cheng, Zhongqi He, and Michael K. Dowd

Southern Regional Research Center, USDA Agricultural Research Service,

1100 Robert E. Lee Blvd., New Orleans, LA 70124, USA


Wood adhesives are industrially important materials used to bond wood products together.

Currently most wood adhesives are based on formaldehyde resins and polyurethanes. In

the past 20 years, there has been increasing attention paid to green technologies, which is

reinforced by the environmental concern regarding formaldehyde and the desire to move

away from petroleum derived raw materials. As a result, there is growing interest in using

agro-based materials as wood adhesives, particularly soy proteins [1,2].

Another material studied as a bio-based wood adhesive is cottonseed protein, which has

been found to have good dry adhesive strength and hot water resistance [3]. In this

presentation, a selected review will be made of the recent developments relating to

cottonseed protein and its applications in wood adhesives. In particular, the addition of

denaturants to cottonseed protein isolate (CPI, >85% protein), such as sodium dodecyl

sulfate, guanidine hydrochloride, and urea, has been found to improve dry adhesive

strength but not hot water resistance [4]. The addition of selected amino acids [5], low-

molecular-weight carboxylic acids [5], or phosphorus-containing compounds [6] to CPI

have been shown to enhance dry adhesive strength, and the addition of phosphorus

compounds has been found to improve hot water resistance [6]. Blends of cottonseed

protein and soy protein with xylan, starch, and cellulose have been studied; in several

cases, adhesive performance was retained even when the cottonseed or soy protein was

mixed with up to 50-75% polysaccharide [7]. A lot of work has also been done on water-

or buffer-washed cottonseed meals; their adhesive performance was found to be

comparable to that of CPI [8-11], which would reduce the cost of manufacturing the

adhesive. Since one factor in new product development is performance/cost ratio, an

increase in adhesive performance or a decrease in cost would likely improve the chances of

a product reaching the marketplace.

References: [1] A. Pizzi and K.L. Mittal (eds.). Wood adhesives. CRC Press, Boca Raton, FL, 2011.

[2] Z. He (ed.). Bio-based wood adhesives: preparation, characterization, and testing. CRC Press, Boca

Raton, FL, 2017.

[3] H.N. Cheng, M.K. Dowd and Z He. Ind. Crop Prod. 46, 399 (2013).

[4] H.N. Cheng, C. Ford, M.K. Dowd and Z. He. J. Adhes. Sci. Technol. 31, 2657 (2017).

[5] H.N. Cheng, C. Ford, M.K. Dowd and Z. He. Int. J. Adhes. Adhes. 68, 156–160 (2016).

[6] H.N. Cheng, C. Ford, M.K. Dowd and Z. He. Int. J. Adhes. Adhes. 77, 51 (2017).

[7] H.N. Cheng, C. Ford, M.K. Dowd and Z. He. Ind. Crop Prod. 85, 324 (2016).

[8] Z. He, D.C. Chapital, H.N. Cheng and M.K. Dowd. Int. J. Adhes. Adhes. 50, 102 (2014).

[9] Z. He, H.N. Cheng, D.C. Chapital and M.K. Dowd. J. Am. Oil Chem. Soc. 91, 151 (2014).

[10] Z. He, D.C. Chapital, H.N. Cheng and O.M. Modesto. J. Adhes. Sci. Technol. 30, 2109 (2016).

[11] Z. He, H.N. Cheng, K.T. Klasson, O.M. Olanya and J. Uknalis. Polymers 9, 675 (2017).


67

P.04 - Interface evolution during reaction between incompatible polymer

layers

G. Yuan1,2, M. Wang3, C. C. Han4

1Georgetown university, 2NIST center for neutron research, [email protected]; 3Institute of

Chemistry, Chinese Academy of Sciences, [email protected]; 4Shenzhen university,

[email protected]

Bisphenol-A polycarbonate (PC) and amorphous polyamide (aPA) were used as reactive

system to study the interfacial interchange reaction between condensation polymers [1, 2].

Aminolysis is the main process during thermal annealing at 160 – 180 oC. The

simultaneously scission of PC chains and formation of PC-aPA copolymer chains during the

reaction process, act as interfacial compatibilization agents between incompatible

homopolymers. The reaction kinetics was probed by Fourier transform infrared and the

interfacial morphology development was analyzed by neutron reflectometry and atomic

force microscopy. The influence of a reactive compatibilizer, hyperbranched

polyethylenimine, on the interfacial fracture toughness was also demonstrated by augmented

double cantilever beam method (Figure 1). With the well-controlled miscibility between PC

and aPA, an excellent multi-layered composite material can be formed, in which PC

decreases water take-up of aPA, whereas aPA enhances the solvent resistance of PC.

Figure 1: Fracture energy, Gc , as a function annealing time in planar layer samples with and without hPEI at

the interface.

[1] M.Wang, G. Yuan and C.C. Han, Polymer. 54, 3612 (2013).

[2] M.Wang, G. Yuan and C.C. Han, Chinese Journal of Polymer Science, 33, 652 (2015).




68

P.05 - Application of gel time measurement and high-performance liquid

chromatography to describe the storage stability of resole resin solutions

S. Blaschke1, C. Schwarzinger1, A. Heidegger2, V. Föge2, F. Nickel2

1Institute for Chemical Technology of Organic Materials, Johannes Kepler University Linz,

Altenbergerstrasse 69, 4040 Linz, Austria, 2Miba Frictec GmbH, Peter Mitterbauer Strasse, 4661 Roitham,

Austria

[email protected]

The polycondensation of thermosetting phenolic resin solutions is a highly temperature

dependent reaction. Therefore, the temperature of storage has a strong influence on the shelf

life. While other stability studies based their investigations on the study of the change in

viscosity and molecular weight distribution [1] or infrared spectroscopy (FT-IR) and

dynamic scanning calorimetry (DSC) [2], simple gel time measurements proved to be

sufficient. It could be shown that commercial resole resin solutions can be fitted into

Arrhenius like models to extrapolate the temperature dependent changes of the liquid

material over arbitrary temperature range.

Figure 1: Arrhenius plot (I) based on the decrease in gel time during storage for three different commercial

resole resins and corresponding plot (II) illustrating a comparison of storage stability of those three resins.

Additional high-performance liquid chromatography (HPLC) studies of the content of free

monomers revealed that the change in the content of free phenol seems to correlate with the

change in gel time during storage, while the content of free formaldehyde decreases in

another pattern.

References

[1] M. K. Gupta and R. R. Hindersinn, Polym. Eng. Sci. 27, 976 (1987).

[2] H. L. Wu, D. Z. Zhang, X. Wang and S. P. Lu, J. East China Univ. Sci. Technol. 43, 335 (2017).


69

P.06 - pyPRISM: A Computational Tool for

Liquid-State Theory Calculations of Macromolecular Materials

Tyler B. Martin,1 Thomas E. Gartner III,2 Ronald L. Jones,1 Chad R. Snyder,1 Arthi

Jayaraman2,3

[email protected], 1National Institute of Standards and Technology, 2Chemical and Biomolecular

Engineering, University of Delaware, 3Materials Science and Engineering, University of Delaware

Polymer Reference Interaction Site Model (PRISM) theory describes the equilibrium spatial-

correlations of liquid-like polymer systems including melts, blends, solutions, block

copolymers, ionomers, polyelectrolytes, liquid crystal forming polymers and

nanocomposites. Using PRISM theory, one can calculate thermodynamic (second virial

coefficient, χ interaction parameters, potential of mean force) and structural (pair correlation

functions, structure factor) information for these macromolecular materials. Here, we

present a Python-based, open-source framework, pyPRISM, for conducting PRISM

theory calculations.[1,2] This framework aims to simplify PRISM-based studies by

providing a user-friendly scripting interface for setting up and numerically solving the

PRISM equations. pyPRISM also provides data structures, functions, and classes that

streamline PRISM calculations, allowing pyPRISM to be extended for use in other tasks

such as the coarse-graining of atomistic simulation force-fields or the modeling of

experimental scattering data. The goal of providing this framework is to reduce the barrier

to correctly and appropriately using PRISM theory and to provide a platform for rapid

calculations of the structure and thermodynamics of polymeric fluids and nanocomposites.

Figure 1: pyPRISM graphic (top) and example results for a polymer nanocomposite.

[1] – Martin, T.B.; Gartner, T.E III; Jones, R.L.; Snyder, C.R.; Jayaraman, A.; pyPRISM: A Computational

Tool for Liquid State Theory Calculations of Macromolecular Materials, Macromolecules,

10.1021/acs.macromol.8b00011

[2] – https://github.com/usnistgov/pyprism, http://pyprism.readthedocs.io


https://github.com/usnistgov/pyprism

http://pyprism.readthedocs.io/


70

P.07 - Thermal-Gradient NMR of EPDM: A way to learn about the

mechanism of separation of Hypercarb columns?!

F. Malz1, R. Brüll1, Z. Zhou2, R. Cong3, D. Mekap3, W. deGroot3

1Fraunhofer Institute for Structural Durability and System Reliability, Division Plastics, Germany, 2Core

R&D Analytical Sciences, The Dow Chemical Company, US, 3Performance Plastics Characterization and

Testing Group, The Dow Chemical Company, US

High temperature liquid chromatography (HT-LC) has emerged as an important analytical

tool to analyze polyolefins in terms of their chemical composition distributions [1,2,3]. The

method separates the macromolecules according to the differences in their interactions, in

solution, with a graphite stationary phase. It is vital to gain insight into the nature of these

interactions. To achieve this goal high-temperature nuclear magnetic resonance spectroscopy

(HT-NMR) can be applied in a unique manner in the form of thermal-gradient NMR (TG-

NMR) [4]. The result of a TG-NMR experiment is a course of signal intensity as a function

of the temperature. Recently, the interaction of ethylene homopolymer with graphite was

monitored by TG-NMR for the first time [5].

Figure 1: Results from TG-NMR of PE in ODCB-d4, blue: without graphite, red: with graphite.

The investigation was extended to EPDM terpolymers. The EPDM separation depends on

the content of E and ENB. Therefore, EPDM samples with different ENB contents were

analyzed by TG-NMR. The objective of this research work was to analyze differences in the

TG-NMR traces of the different EPDM samples.

References

[1] – D. Mekap, T. Macko, R. Brüll., R. Cong, A.W. deGroot and A.R. Parrott, Ind. Eng. Chem. Res. 53,

15183 (2014).

[2] – A.W. deGroot, D. Gillespie, R. Cong, Z. Zhou and R. Paradkar, chapter 5 “Molecular Structural

Characterization of Polyethylene” in Handbook of Industrial Polyethylene and Technology: Definitive Guide

to Manufacturing, Properties, Processing, Applications and Markets, Wiley, 2017.

[3] – R. Cong, A.W. deGroot, A.R Parrott, W. Yau, L. Hazlitt, R. Brown, M. Miller and Z. Zhou,

Macromolecules 44, 3062 (2011)

[4] – Z. Zhou, R. Cong, Y. He, M. Paradkar, M. Demirors, M. Cheatham and A.W. deGroot, Macromol.

Symp. 312, 88 (2012)

[5] – D. Mekap, F. Malz, R. Brull, Z. Zhou, R. Cong, A.W. deGroot and A.R. Parrott, Macromolecules 47,

7939 (2014)


71

P.08 - Analysis and quantification of polycarbonate end-groups by liquid

chromatography at critical conditions

Elena Uliyanchenko1, Stijn Rommens1, Nico Apel2, Robert Brüll2

1SABIC, Plasticslaan 1, 4612 PX Bergen op Zoom, the Netherlands, [email protected]

2Fraunhofer Institute for Structural Durability and System Reliability (LBF), Division Plastics, Group Material

Analytics, Schlossgartenstr. 6, 64289 Darmstadt, Germany

Knowledge on end-group functionality and their distribution in polymers is very important in

industrial material development: specific functional groups may serve as compatibilizers for

otherwise immiscible polymer blends, they may be used to modify material properties or to

facilitate further reactions e.g., to produce block copolymers. Furthermore, end-cappping may be

introduced during the polymerization to control molecular weight and to minimize the presence of

reactive groups, which prevents degradation and, thus, extends durability of the final materials. In

all these cases, monitoring the content and type of end-group functionalities is important, as this

information directly relates to the properties of the materials (structure-property relationship).

In addition to end-group distribution, almost all polymers exhibit a distribution with regard to

molecular weight, which complicates their characterization. Liquid chromatography at critical

conditions (LCCC) is a unique technique that allows separating polymers based on end-groups

excluding the influences of molecular weight on the elution time. The separation occurs at the

thermodynamic equilibrium conditions where enthalpic and entropic contributions compensate

each other. For each type of polymer, this happens at a specific combination of stationary phase,

mobile phase and temperature. Thus, determination of the critical conditions is usually challenging

and time-consuming.

In this study we discuss LCCC separation of poly (bisphenol A carbonate) (PC) and its applications

in industry. Although LCCC for PC was described earlier [1], this separation had limited practical

use, as it was not able to measure all end-group combinations present in a common PC sample. In

this work we further explore and optimize LCCC separation of PC and demonstrate the possibility

to detect additional end-groups and structures. Moreover, we apply this method to quantify

different functionality types and compare the results with those from other analytical techniques.

In a next step, this LCCC separation is coupled to size-exclusion chromatography in a two-

dimensional setup to additionally obtain molecular weight data for each type of polymer chains.

The extracted information provides valuable insights into material properties (e.g. aging) as well

as the underlying production processes (e.g. end-capping efficiency) and, thus, facilitates a

material optimization based on the molecular structure of the PC.

1. References

[1] L. Coulier, E.R. Kaal, Th. Hankemeier, J. Chromatogr. A, 1130 (2006) 34-42



72

P.09 - Analysis of charge states of water soluble polymers by

Capillary electrophoresis

Mitsuyoshi Kawashima1), Yoshiomi Hiroi1)

Koutatsu Matsubara1), Katsumi Chikama1)

1)Nissan Chemical Industries, LTD [email protected]

Introduction In recent years, water soluble polymers are used in various material fields.

Their polymer structures are analyzed by NMR, FT-IR, and size exclusion chromatography

(SEC), but it is difficult to analyze their charge states that seems to strongly influence of

material properties. Capillary electrophoresis (CE) is an analytical technique that separates

ions by their electrophoretic mobilities and often used for separation of biopolymers[1].

Therefore, we have applied CE to the charged synthetic polymers, and discussed the

relationship between charge state and mobility.

Experiment Amphoteric polymers comprising a cationic and an anionic monomer were

synthesized (Figure1). The different charge polymers were obtained by changing the charging

ratio of monomers. They were analyzed by capillary zone electrophoresis (CZE) and the

mobilities were calculated. The electrophoresis solution was 20 mM sodium tetraborate

decahydrate (pH 9.3). The capillary temperature was 25 ° C, the voltage was applied at 30

kV.

Results and Discussion It was revealed that as the proportion of anionic monomer increased,

the mobility(absolute value) of the polymer increased. It shows that the mobility depends on

the charge state of the polymer. Furthermore, plotting charging ratio of the monomer and the

mobility of the polymer revealed that they were correlated (Figure2). This indicates that the

separation of CZE is dominated by the charge state of the polymer.

Figure 1: (Left) Amphoteric polymer. (R1=Anion unit, R2=Cation unit and (Right) Charging ratio and mobility

[1] - Vladislav Dolník, Electrophoresis, 20, 3106~3115 (1999)


73

P.10 - Liquid Chromatography with porous graphitic carbon as stationary

phase for the characterization of stabilizers David Kot, Nico Apel, Tibor Macko, Robert Brüll

Fraunhofer Institute for Structural Durability and System Reliability LBF, Schlossgartenstraße 6, 64289

Darmstadt; [email protected]

Stabilizers play a very important role throughout the entire life cycle of synthetic polymers.

They are introduced to prevent oxidation occurring in processing such as extrusion or injection

molding due to aging caused by shear and extensional flow and resulting in relaxation processes

which may lead to shrinkage or warpage of the polymer material. Other stabilizers also inhibit

photooxidation triggered by light or prevent chemical aging like hydrolysis, post-condensation

or post-polymerization. These stabilizers interrupt the circle of degradation, either by absorbing

UV light or reacting with initially formed degradation products and, thus, preventing their

propagation. Some stabilizers combine even more than one desired effect, inhibiting both the

thermal and the oxidative degradation. That has led to a variety of different stabilizers ranging

from processing stabilizers, phenolic antioxidants and hindered amine (light) stabilizers. In

order to further extend the lifetime of the polymers, the synthesis and the modification of

existing stabilizers has been pushed forward in the last years. Exemplarily, stabilizers have been

developed with increased molecular weights (oligomers) reducing the tendency to migrate in a

synthetic material, or stabilizers which are functionalized several times and in this way stronger

inhibit degradation.

This constant change in the portfolio of stabilizers requires the continuous development of

appropriate analytical methods for their characterization. The growing need for quantitative

characterization as well as the possibility to separate a variety of stabilizers in a one-shot

approach have made liquid chromatography (LC) the method of choice. Till now reversed

phases and normal phases have routinely been used as stationary phase for the separation and

identification of stabilizers in LC measurements [1]. For some stabilizers, and especially the

ones exhibiting higher molecular weights, no chromatographic methods exist, which allow a

satisfying separation and quantitative determination applying these stationary phases.

Therefore, another stationary phase was tested and can serve as an appropriate material, namely

porous graphitic carbon allows the application of elevated temperatures because of the robust

carbon material which is even stable at temperature as high as 160 °C [2]. The specific

interaction between porous graphitic carbon and stabilizers is a key for their separation and

identification.

We will show the separation of a number of selected stabilizers with LC using the porous

graphitic carbon as stationary phase for the first time. Separation of different phenolic

antioxidants, UV stabilizers as well as process stabilizers from each other will be presented.

Moreover, separation of high molecular weight hindered amine stabilizers at elevated

temperatures, which could not be achieved before using others stationary phases, will be

described.

References

[1] M. S. Dopico-García, R. Noguerol-Cal, M. M. Castro-López, M. C. Cela-Pérez, E. Piñón-Giz, J. M. López-

Vilariño, M. V. González-Rodríguez, Cent. Eur. J. Chem. 10, 3 (2012)

[2] Thermo Scientific, Hypercarb Columns, Applications Notebook, Issue 1, June 2009


74

P.11 - Tackling Industrial Needs Using Multi-Detector Size Exclusion and

Hydrodynamic Chromatography

A. K. Brewer1

Arkema Inc, King of Prussia, PA, [email protected]

Since their inception the principle uses of size-exclusion chromatography (SEC) and

hydrodynamic chromatography (HDC) have been to determine the molar mass averages and

distributions of natural and synthetic polymers and the characterization of mono- and

polydisperse particles, respectively. In general these properties have been characterized

through the application of calibration curves via a single-detector instrumental set-up e.g. SEC-

refractive index (RI) or HDC/SEC-UV. Over the years, as the complexity of polymers and

particles has increased, the ability to obtain accurate and precise distributions of both their

physical and chemical properties has led to the implementation of multi-detector size-based

separation techniques.

Here, we will discuss two different size-based separation techniques (SEC and HDC) coupled

to a multi-detector system consisting of, multi-angle light scattering (MALS), quasi-elastic

light scattering (QELS), differential viscometry (VISC) and differential refractory (RI). The

multi-detector SEC set-up will be used to determine the solution based macromolecular

properties such as; absolute molar mass, polymeric size (radius of gyration, hydrodynamic

radius, and viscometeric radius), polymer branching and their distributions of high molar mass

polymers. The characteristics obtained from these experiments as well as supporting

experiments, e.g. batch mode MALS and rheology, allow for the study of the effects of changes

in molar mass, chemical composition, and polymer branching on end-use properties and

polymer performance.

The multi-detector HDC set-up will be applied to the characterization of latex particles, as

several factors influence their end-use applications, including the size and shape of the latex

particles and their aggregates. Characterizing the size and shape of these particles by methods

such as SEC, microscopy or other particle size methodologies is challenging. Issues with SEC

analyses occur due to the large size of the particles as well as their sometimes fragile

morphology, while microscopy issues are chiefly due to the inability to analyze the particles in

their natural aqueous state. Multi-Detector HDC will be used for the determination of size,

shape and morphology across the elution profile of latex particles. This approach will also be

used to characterize flocculated latex particles arising from samples varying in pH and age.

The multi-detector HDC approach results are comparable to those obtained by atomic force

microscopy and rheology.



75

P.12 - Asymmetric flow field flow fractionation – gaining insight into long

chain branching of PP

J.H. Arndt1, R. Brüll1, G.P. Horchler1, T. Macko1, A. de Azeredo2, M.E. Cangussu2, A.

Lobo2, A. Simanke2

1Fraunhofer Institute for Structural Durability and System Reliability, Plastics Division, Schlossgartenstrasse

6, 64289 Darmstadt, Germany, 2Braskem SA, Via Oeste, Lote 5, Passo Raso, Triunfo, 95853, RS, Brasil

Long chain branching (LCB) is an important molecular metric which determines the

viscoelastic properties of the polymer melt [1]. In the case of polypropylene LCB is

introduced to improve the limitations of the material resulting from the molecular weight

distribution. The incorporation can be achieved by using suitable catalysts during

polymerization or by post reactor modification via physical or chemical processes [1, 2].

With the aim to understand and optimize the introduction of LCB a detailed knowledge about

its distribution along the molar mass axis is mandatory. Asymmetric flow field flow analysis,

AF4, is a fractionation approach which overcomes the shortcomings of size exclusion

chromatography with regard to peculiar co-elution of branched and low molecular weight

fractions [3-6].

Figure 1: (Left) Elution profile and molar masses as a function of elution time for a PP sample containing

LCB and (right) radius of gyration as a function of molar mass obtained from AF4.

References

[1] J. Tian, W. Yu, C. Zhou, Polymer 47, 7962 (2006).

[2] E. Borsig, M. van Duin, A.D. Gotsis, F. Picchioni, Eur. Polym. J. 44, 200 (2008).

[3] S. Podzimek, T. Vlcek, C. Johann, J. Appl. Polym. Sci. 81, 1588 (2001).

[4] T. Otte, H. Pasch, R. Brüll, T. Macko, Macromol. Chem. Phys. 212, 401 (2011).

[5] H. Pasch, A.C. Makan, H. Chirowodza, N. Ngaza, W. Hiller, Anal. Bioanal. Chem. 406, 1585 (2014).

[6] H. Pasch, M. I. Malik, Advanced Separation Techniques for Polyolefins, Springer International Publishing,

Cham, 2009.


76

P.13 - Asymmetric flow field flow fractionation – a novel approach for

routine analysis of polyolefins

J.H. Arndt1, R. Brüll1, G.P. Horchler1, T. Macko1, D. Mekap2, E.P.C. Mes2, D.T. Gillespie3,

D. Meunier3, W. de Groot3

1Fraunhofer Institute for Structural Durability and System Reliability, Plastics Division, 2The Dow Chemical

Company, Herbert H. Dowweg 5, 4542 NM Hoek, Netherlands, 3Performance Plastics Characterization and

Testing Group, The Dow Chemical Company, 2301 Brazosport Blvd., Freeport, TX 77541, US

The distributions with regard to molar mass (MMD) and long chain branching (LCBD) are

important molecular metrics of polyolefins. Size exclusion chromatography is currently well

established in routine analysis for their determination. Yet, the separation principle based on

diffusion in a porous stationary phase entails limitations, such as peculiar co-elution, shear

degradation and the exclusion limit [1,2]. Asymmetric flow field flow fractionation (AF4) poses

an attractive alternative technique, overcoming these deficits [3]. Yet, operating AF4 at

temperatures as high as 160 °C [4,5] has long been a challenge due to the limited durability of

the membrane.

Efforts in this regard have led to significant progress, thus for the first time enabling to probe

the effects of various flow profiles on the separation efficiency.

Fig. 1 Results of AF4 analyses of a narrowly distributed polyethylene sample, using a two-step linear cross flow

gradient (a) or a one step exponential gradient (b) respectively.

References

[1] A.W. deGroot, W.J. Hamre, J. Chromatogr. 1993, 648, 33.

[2] S. Podzimek, Macromol. Symp. 2013, 330, 81.

[3] J.C. Giddings, Science 1993, 260, 1456.

[4] E.P.C. Mes, H. de Jonge, T. Klein, RR. Welz, D.T. Gillespie, J. Chromatogr. A 2007, 1154, 319.

[5] T. Otte, H. Pasch, T. Macko, R. Brüll, F..J. Stadler, J. Kaschta, F. Becker, M. Buback, J. Chromatogr. A

2011, 1218, 4257.

a) b)


77

P.14 - The Characterization of Polyamide Aging by Means of Pyrolysis-

GC-MS

A. Ibrahimi Berisha, C. Schwarzinger Institute for Chemical Technology of Organic Materials, Johannes Kepler University, Austria;

[email protected]

Polyamides play an important role in our daily lives and are used in a very versatile way,

especially when tough, highly stable materials are desired.

The aim of this work is to artificially age polyamides under different conditions such as high

oxygen pressure, increased temperature and various liquids for 1 to 10 days [1]. The

polymers were hereafter analyzed with Pyrolysis GC-MS. It could be shown that aging in

general leads to the formation of new pyrolysis products compared to virgin material and

that depending on the liquids used other breakdown products can be identified suggesting

different aging mechanisms.

Figure 1 shows the aging of polyamide 6.6 as seen by pyrolysis-GC-MS when the sample is

aged in water. Main pyrolysis product in all cases is cyclopentanone (4) and after aging 2-

pyrrolidinone (7), 2-piperidone (9) can be found. The amount of caprolactame (11), the

monomer for polyamide 6, is also increased. The results in salt water are very similar,

whereas the use of sodium hypochlorite solution seems to favor a different degradation

mechanism.

Figure 1: Py-GC-MS analysis of PA-6.6 before and after aging for 1,3, and 10 days.

References

[1] - C. Schwarzinger, I. Hintersteiner, B. Schwarzinger, W. Buchberger, B. Moser: “Analytical pyrolysis in

the determination of the aging of polyethylene”; J. Anal. Appl. Pyrol. 113 (2015) 315-322.


78

P.15 - Asymmetric flow field flow fractionation – new perspectives for

routine analysis of polyolefins

J.H. Arndt1, R. Brüll1, G.P. Horchler1, T. Macko1, Y. Yu2

1Fraunhofer Institute for Structural Durability and System Reliability, Plastics Division, Schlossgartenstrasse 6,

64289 Darmstadt, Germany, 2Chevron Phillips Chemical Company LP, Bartlesville Research & Technology

Center Bartlesville, OK 74003, USA

Size exclusion chromatography coupled with multi-angle light scattering (SEC-MALS) is

widely used to analyze the molar mass distribution and long-chain branching (LCB) of

polyolefins. [1,2] The fractionation is based on the exclusion of macromolecules from a porous

stationary phase according to their hydrodynamic volume. Due to the separation principle,

fundamental limitations are inherent to SEC and cannot be overcome. These include peculiar

co-elution, shear degradation and the size exclusion limit [3,4]. On the other side, asymmetric

flow field flow fractionation (AF4) enables to overcome these drawbacks due to the absence of

any stationary phase [5-7]. Thus, ultra-high molar mass fractions can be studied as well as the

content of long-chain branching along the molar mass distribution.

a

)

b

)

Fig. 1 Elution profile and molar masses as a function of elution time (a) as well as radius of gyration as a

function of molar mass (b, indicative of LCB) obtained from AF4 analysis of a long-chain branched

polyethylene sample containing ultrahigh molar mass material.

References

[1] P.J. Wyatt, Anal. Chim Acta, 1993, 1, 272.

[2] Y. Yu, P.J. DesLauriers, D.C. Rehlfing, Polymer, 2005, 46, 5165.

[3] A.W. deGroot, WJ. Hamre, J. Chromatogr. 1993, 648, 33.

[4] S. Podzimek, Macromol. Symp. 2013, 330, 81.

[5] J.C. Giddings, Science 1993, 260, 1456.

[6] E.P.C. Mes, H. de Jonge, T. Klein, R.R. Welz, D.T. Gillespie, J. Chromatogr. A 2007, 1154, 319.

[7] T. Otte, H. Pasch, T. Macko, R. Brüll, F..J. Stadler, J. Kaschta, F. Becker, M. Buback, J. Chromatogr. A

2011, 1218, 4257.


79

P.16 - Stepwise Elution of Methylcellulose Esters with increasing DSMe by

NP-HPLC

Patrick Sudwischer, Anika Wubben, Inga Unterieser, Julia Cuers, Petra Mischnick

Technische Universität Braunschweig, Institute of Food Chemistry, Germany

[email protected]

The physicochemical properties of cellulose ethers depend on the molecular weight

distribution, the degree of substitution (DS), and also on the distribution of the substituents

in the glucosyl unit and over the polymer chains. The chemical modification of cellulose

does not necessarily proceed uniformly over the entire material. This results in

heterogeneities with respect to the distribution of substituents. For a detailed analysis of the

1st order heterogeneity, the material must be fractionated according to DS. Preparative

chromatography of cellulose ethers, for instance methyl cellulose (MC), is hampered by the

viscosity of the solutions [1]. Furthermore, MC can be regarded as a very complex

copolymer which has a continuum of critical eluent compositions in the chromatographic

fractionation [2].

MCs of various DSMe were separated on a normal phase (silica gel) HPLC with a

gradient of 2-propanol (2-PrOH) in dichloromethane (DCM). Prior to chromatography, all

free OH were converted to 4-methoxybenzoates. This transformation results in a reduction

of viscosity and increase in the chemical difference of the polymer chains. Furthermore, a

chromophore is introduced in the polymer which enables detection by UV light of the

4-methoxybenzoate derivatives.

Figure 2: left : Correlation of the DSMe and % 2-PrOH in DCM, required to elute MeOBzMC from

silica gel, right : Exponential approximation of the 2-PrOH steps in DCM in the HPLC gradient

system with determination of the DSMe of the peaks from the CPA curve.

A set of nine cellulose derivatives in the range of DS(Me/MeOBz) = 0/3.0 to 3.0/0 showed

increasing retention with an increasing DSMe in NP-chromatography. Elution required an

increasing amount of 2-PrOH in DCM to elute it from silica gel (Fig. 1 left). The Separation

with gradient chromatography depends on an absorption/desorption mechanism (Fig. 1

right).

References

[1] R. Adden et al., Macromol. Chem. Phys. 207 (2006) 954 – 965

[2] P. Kilz et al., Anal. Bioanal. Chem. 407 (2015) 193 – 215


80

P.17 - Expediting 2D-LC Separations of Synthetic Polymers Using

Advanced Polymer Chromatography (APC) M. Jančo1, L. Bai2

1 Analytical Sciences, Core R&D, the Dow Chemical Company, Collegeville, PA, USA,

[email protected] 2 Home and Personal Care R&D, Collegeville, PA, USA

Analysis of synthetic polymers often utilizes size exclusion chromatography

(SEC) and interactive high performance liquid chromatography (HPLC) to reveal

molecular weight and chemical compositional distributions, respectively. The traditional

SEC and HPLC methods are time-consuming, resulting in long separations when

coupled in 2D-LC mode. In spite of the improved resolution of 2D-LC separations, the

longer analysis time has hindered wide-spread adoption of 2D technique in fast-pace

industry settings.

In this work, sub-3 micron particle column technology for polymer SEC (Waters

ACQUITYTM Advanced Polymer Chromatography, APC) and sub-2 micron particle

column for UHPLC are used for 2D-LC separations in the LC X SEC format. The

improved efficiency provided by the APC columns allows for significant reduction of

the overall analysis time. Several examples are given to illustrate the application in the

analysis of synthetic polymers.

On the other hand, aiming to improve the efficiency and increase throughput in

the first dimension (the interactive HPLC dimension), this work also evaluates the use

of sub-2 micron particle columns using ultrahigh-pressure liquid chromatography

(UHPLC). Using narrow polystyrene standards with molecular weights ranging from 5k-

1M, we compared the peak widths generated from the use of columns packed with 10

µm, 5 µm, 3.5 µm, and 1.7 µm particles. The peak widths are shown to get narrower as

particle sizes become smaller when other parameters remain constant. The increased

peak capacity helps to gain resolution in the LC dimension. However, there are also

potential issues in using sub-2 micron particle columns in comprehensive 2D-LC

separations: when the 1st dimension peaks are so narrow that they do not allow sufficient

number of slices (more than 3 slices) to be sampled across each peak. Therefore the

shape/width of the peak reconstructed by 2D-LC software using a limited number of

slices remains questionable.

In conclusion, ultra-high pressure 2D-LC (UHPLCxAPC) utilizing small particle

size columns has shown the potential to significantly shorten the runtime of 2D-LC,

making this technique a practical tool for industrial use. The increased peak capacity can

provide better resolution for such separations. However, cautions need to be taken in

situations when the number of slices across the eluting peaks are limited.


81

P.18 - Crystallization and Alkaline Hydrolysis Studies of Poly(3-

hydroxybutyrate)

N. Vasanthan , A. Tappadiya

Department of Chemistry and Biochemistry, Long Island University, One University Plaza, Brooklyn, NY

11201, [email protected]

Poly(3-hydroxybutyrate) (PHB) is a microbially synthesized polymer, which is often

purified by alkaline treatment. The effect of microstructure on alkaline hydrolysis has been

studied by varying concentration of base and the temperature. The morphologies of PHB

films before and after degradation were evaluated using DSC and FTIR spectroscopy. The

hydrolytic degradation study by weight loss measurement revealed that the crystallinity of

PHB greatly decreased the hydrolytic ability of PHB. The crystallization of PHB and the

effect of base on hydrolysis was investigated by time dependent FTIR spectroscopy. The

normalized absorbance of 3010 cm-1 and 1183 cm-1 were used to characterize the crystalline

and the amorphous phases of PHB, shown in Figure 1. FTIR spectroscopy reveal that the

extent of hydrolysis decreased with increasing crystallinity. The crotonic acid was detected

as a major product after hydrolysis, confirmed by UV/Visible and proton NMR

spectroscopy. The normalized absorbance of the crystalline band at 3010 cm-1 band remained

constant, suggesting that there is no significant change in crystallinity with degradation. The

normalized amorphous band at 1183 cm-1 showed a decrease in absorbance ratio, suggesting

degradation of the amorphous phase.

.

Figure 1: FTIR spectra of PHB films cold crystallized at different temperatures in the region (a)1500-900 cm-

1 and (b) 3050-2850 cm-1.

References

6. Doi Y, Steinbuchel A, Eds. Biopolymer, Polyesters I-Biological Systems and Biotechnological Production;

John Wiley and Sons: Weinheim, Germany, 2001;3

7. Gross RA, Kalra B. Biodegradable polymers for the Environment Science 2002;297:803-7.

8. Matsusaki H, Abe H, Doi Y. Biomacromolecules 2000;1:17.

9. Steinbuchel A, Valentine H E. FEMS Microbiol Lett 1995;128:219.

10. Tapadiya, A, Vasanthan, N. International Journal of Biological Macromolecules, 2017, 102, 1130


82

P.19 - Thermo-Responsive Monosaccharide-Polyolefin Amphiphilic

Conjugates Displaying Order-Order Transitions

K. K. Lachmayr1, T. S. Thomas1, K. Yager2, L. R. Sita1*



States

[email protected]

The self-assembly of amphiphiles gives rise to important scientific and industrial

materials. Thus, the ability to design new classes of molecular and macromolecular

amphiphilic building blocks tunable, well-defined nanostructures is highly desirable. We

have previously reported the use of end-group functionalized poly(α-olefinates) (xPAOs)

as a highly versatile class of non-polar building blocks for amphiphilic materials made

through living coordinate chain-transfer polymerization (LCCTP) Herein, we report the

use of xPAOs in sugar-polyolefin conjugates, specifically consisting of β-D-Galactose as

the sugar “head” group chemically linked to an atactic polypropylene “tail” (Gal-aPP).

This system displays rich phase behavior within ultrathin films with multiple order-to-

order transitions upon heating. Additionally, upon cooling from above the order-disorder

transition temperature, a novel body centered cubic phase can be accessed. These results

demonstrate the ability of sugar-polyolefin conjugates to be used as a thermo-responsive

‘smart’ materials.

References

[1] –T. S. Thomas, W. Hwang, and L. R. Sita, Angew. Chem. Int. Ed. 55, 4683 (2016).



83

P.20 - The Use of 2-D Chromatographic Techniques to Interpret

Macromolecular Structures

J. McConville1, D. Lohmann1, W. Radke2, P. Kilz2

1 PSS USA Inc, Amherst, MA, USA, 2 PSS GmbH, Mainz, Germany

[email protected]

The task of characterizing polymeric materials has become more challenging as advances in

polymer synthesis gave rise to a variety of novel complex materials with predetermined

chemical composition, functionality and architecture. The molar mass, the chemical

composition, the architecture and other parameters are fine-tuned for optimal structure-

property function relationships. No single analytical technique alone provides adequate

information regarding these different distributions.

The coexistence of these property distributions require multidimensional (combined)

chromatographic methods. 2-D Chromatography combines the separation power of two

different chromatographic techniques, e.g. HPLC and GPC/SEC.

Accurate and precise results can be directly derived for each sample component in a single

2-D run, e.g. molar mass, chemical composition, end group, functionality, degree of

branching, architecture, aggregation, etc., depending on the specificity of the selected

separation techniques.

Different application examples obtained with various hyphenations will be presented.

Optimization of the on-line setup with respect to ease-of-use and fully automated transfer

from the first to the second dimension will be discussed. Options for data presentation using

different plot and evaluation types and access to the final results will also be shown.


84

P.21 - Synthesis, Characterization and Application of reversible Ultra-

hydrophobic Polymer Surfaces

D. Lohmann3, T. Hofe2, K. Oleschko2, M. Stamm1, P. Uhlmann1,

1 Leibniz Institute of Polymer Research Dresden, Department Nanostructured Materials, Dresden, Germany,

2 PSS GmbH, Mainz, Germany, 3 PSS USA Inc, Amherst, MA, USA

[email protected]

The ultra-hydrophobic properties of a lotus leaf are based on a hierarchal surface structure.

This structure can be perfectly modelled by the use of a polymer particle in the µm range and a tri-

block polymer coating in the nm range. Multifunctional polymer surfaces based on this structure

exhibit ultra-hydrophobic and super-hydrophilic behaviour. To realize multi-functionality it is

necessary to combine the different functionalities in one polymer molecule. This is achieved by the

production of core-shell-nanoparticle layers on a variety of surfaces which lead to easy-to-clean or

self-cleaning properties.

The synthesis of the tri-block copolymers using controlled living polymerization techniques

and the preparation of the core-shell-nanoparticles will be presented.

In addition, modern LC techniques to determine the molar mass and the composition of the polymers

will be introduced, including the advantages and possibilities of 2-dimensional separation techniques

including FT-IR identification.

The synthesized tri-block polymers consist of a block responsible for the anchoring to the

substrate, a “hydrophilic” block and a “hydrophobic” block. This offers the possibility to combine

the anchoring to a substrate with reversible switching of the wetting behavior in one molecule. The

wetting behavior of the prepared tri-block polymer brushes can be switched by external stimuli.

Super-hydrophilic and ultra-hydrophobic surface behavior was achieved and will be discussed as a

function of grafting density, molar mass and composition. .

Applications for the possible industrial use of these new surface properties will be shown.


85

P.22 - Thermo-Responsive Monosaccharide-Polyolefin Amphiphilic

Conjugates Displaying Order-Order Transitions

K. K. Lachmayr1, T. S. Thomas1, K. Yager2, L. R. Sita1*



States

[email protected]

The self-assembly of amphiphiles gives rise to important scientific and industrial materials.

Thus, the ability to design new classes of molecular and macromolecular amphiphilic

building blocks tunable, well-defined nanostructures is highly desirable. We have

previously reported the use of end-group functionalized poly(α-olefinates) (xPAOs) as a

highly versatile class of non-polar building blocks for amphiphilic materials made through

living coordinate chain-transfer polymerization (LCCTP) Herein, we report the use of

xPAOs in sugar-polyolefin conjugates, specifically consisting of β-D-Galactose as the

sugar “head” group chemically linked to an atactic polypropylene “tail” (Gal-aPP). This

system displays rich phase behavior within ultrathin films with multiple order-to-order

transitions upon heating. Additionally, upon cooling from above the order-disorder

transition temperature, a novel body centered cubic phase can be accessed. These results

demonstrate the ability of sugar-polyolefin conjugates to be used as a thermo-responsive

‘smart’ materials.

References

[1] –T. S. Thomas, W. Hwang, and L. R. Sita, Angew. Chem. Int. Ed. 55, 4683 (2016).



86

P.23 - Controlled Deuteration in Polyethylene via Polyhomologation

W. S. Farrell, K. L. Beers

National Institute of Standards and Technology, [email protected]

The use of deuterium labelling in conjunction with small angle neutron scattering (SANS)

provides a powerful method to probe the confirmation of semicrystalline polymers,

especially in regard to tie-chain estimation. Although polyethylene is the most widely

consumed polyolefin, and such investigations are of great industrial interest, preparation of

polyethylene with deuterium labeling has been challenging historically, either not allowing

for high degrees of deuteration, or not permitting labeling of selective portions of the

polymer chain, such as chain-ends. In this work, we demonstrate a new route to deuterated

polyethylene using polyhomologation to prepare well-defined polyethylene with

controllable amount of deuteration which is uniform across the molar mass distribution.

This initial investigation has been extended to include selective deuterium labeling of

chain-ends as well, which should enable identification of chain-end location in

semicrystalline polyethylene by SANS. Furthermore, the deuterated polyethylene

produced is hydroxy-terminated, making these functional polymers candidates for the

preparation of more complex architectures, such as deuterated polyethylene bottlebrush

polymers.



87

P.24 - The best of both worlds: combining multi-detector GPC

and UPLC to achieve complex polymer characterization

at ULPLC speeds and resolutions

V. Shahi1, M.R. Pothecary1, C. Schindler1, J.D. Stenson2, L. Meeker2, B. MacCreath2

1Malvern Panalytical, Houston, Tx, USA, 2Waters Corporation, Milford, MA, USA

[email protected]

Gel-permeation chromatography (GPC) is the most widely used tool for the measurement of

molecular weight and molecular weight distribution of natural and synthetic polymers.

Advanced detectors such as light scattering are increasingly used to overcome the limitations

of conventional GPC measurements and offer absolute molecular weight. A viscometer

measures intrinsic viscosity, a key structure factor that can be used to calculate branching

levels and can be combined with molecular weight data to calculate hydrodynamic radius.

In combination these data allow detailed structural information of a polymer to be generated

in a single GPC measurement which can be compared with other samples in Mark-Houwink

plots. This can be used to study substitution or branching levels.

Typical analytical SEC measurements can take approximately 25 to 45 minutes and consume

25 to 45 ml of solvent. This is time-consuming and can be expensive in terms of solvent.

Ultra-high pressure liquid chromatography (UPLC) systems use novel SEC column gel

technologies with robust, small particles (<3 µm) to achieve similar or better sample

resolution using smaller columns. This increases productivity, while significantly reducing

run-time and cost. An additional benefit of the reduced solvent use is to effectively make

UPLC a ‘greener’ technology than traditional analytical SEC.

Until recently issues with band-broadening, or dispersion, limited the ability to connect

multi-detector and UPLC system as the loss in resolution and data quality was too great. In

this presentation, we will show how Malvern’s OMNISEC REVEAL and the Waters

Acquity APC systems can now be combined to bring complete multi-detector measurements

at UPLC resolutions and efficiencies. This talk will include a discussion of the pitfalls of

combining these two techniques and a range of measurements to show how a large number

of applications can now be addressed in this manner.


88

P.26 - One-pot synthesis and characterization of “designer” delivery

systems for controlled release of therapeutic agents.

Vidya Chamundeswari Narasimhan1, Joachim Say Chye Loo1, 2.

1 School of Materials Science and Engineering, Nanyang Technological University, Singapore.

2 Singapore Centre for Environmental Life Sciences Engineering, Nanyang Technological University,

Singapore.


Micro particles and nanofibers are attractive candidates for drug delivery applications owing

to their tunability for targeted and sustained drug release. Our research focuses on

encapsulation techniques to enable for controlled and sustained release of therapeutic agents,

and materials characterization. These carriers are fabricated using a combination of natural,

synthetic and food grade polymers. During the development of our technologies, the long-

term economic viability, employing green manufacturing and scalable techniques, were

taken into consideration while minimizing negative effects to both human health and the

environment. We have developed multi-layered particles, floatable microcapsules, and

hydrophilic-hydrophobic (core-shell) particles and electrospun 3-dimensional and bi-layered

scaffolds for drug delivery applications. All the carrier systems were subjected to

morphological, rheological and chemical characterizations to ensure the successful

encapsulation of bioactive agents. With these inventions, we demonstrated how these

distinctive “designer” systems can modulate the release profiles of anticancer drugs, and

how co-delivery can potentially provide better antitumor response and enhance rate of repair

of damaged tissues. Currently these systems can facilitate sustained release of biomolecules

for applications in bone infections; gastrointestinal release, magnetic diagnostics,

musculoskeletal regeneration and cancer therapy. These technologies hold an immense

potential in the field of regenerative medicine and biomaterials.

References:

1. V Narasimhan, YS Lui, YJ Chuah, JS Tan, D Wang, SCJ Loo. Sustained Releasing Sponge-like 3D

Scaffolds for Bone Tissue Engineering Applications. 2017. Accepted Biomedical Materials

2. JS Baek, CC Choo, NS Tan, SCJ Loo. Sustained-releasing Hollow Microparticles with Dual-

anticancer Drugs Elicit Greater Shrinkage of Tumor Spheroids. 2017. 8: 80841-80852. Oncotarget

3. HM Tay, S Kharel, R Dalan, ZJ Chen, KK Tan, B Boehm, SCJ Loo, HW Hou. Rapid purification

of sub-micron particles for enhanced drug release and microvesicles isolation. 2017. 9, e434 NPG

Asia Material 4. JS Baek, EW Yeo, YH Lee, NS Tan, SCJ Loo. Controlled Releasing Nano-encapsulating

Microcapsules to Combat Inflammatory Diseases. 2017. 11:1707-1717 Drug Design, Development

and Therapy 5. S Kharel, WL Lee, XY Lee, SCJ Loo. Osmogen-Mediated One-Step Technique of Fabricating

Hollow Microparticles for Encapsulation and Delivery of Bioactive Molecules. 2017. 17, 1600328

Macromolecular Bioscience 6. N Yang, K Sampathkumar, SCJ Loo. Recent Advances in Complementary and Replacement

Therapy with Nutraceuticals in Combating Gastrointestinal Illnesses. 2017. 36: 968-979. Clinical

Nutrition


Author Index

89

A Ali, S. .................................................... 24

Apel, N...................................... 57, 71, 73

Arndt, J.H. .......................... 48, 75, 76, 78

Audus, D. .............................................. 31

Azeredo, A. de ...................................... 75

B Bai, L. ................................................... 80

Beers, K. L. ..................................... 46, 86

Beers, K.L. ............................................ 49

Berisha, A. I. ......................................... 77

Bernardes, A. A. ................................... 54

Besghini, D. .......................................... 64

Bhargava, R. ......................................... 55

Birdsall, R. ............................................ 29

Biswas, Atanu ....................................... 38

Blaschke, S. .......................................... 68

Botha, C. ............................................... 39

Boudara, V. A. H. ................................. 19

Brambilla, R.......................................... 54

Brewer, A. K. ........................................ 74

Brüll, R. ...... 48, 57, 70, 71, 73, 75, 76, 78

Brun, Y. ................................................ 26

C Cangussu, M.E. ..................................... 75

Carriere, J. T. A. ................................... 42

Chan, E.P. ............................................. 49

Chang, T. .............................................. 41

Chard, K................................................ 31

Cheng, H. N. ................................... 38, 66

Chikama, K. .......................................... 72

Clarke, P. .............................................. 60

Cong, R. ................................................ 70

Cotts, S.................................................. 22

Cuers, J. ................................................ 79

D Das, C. .................................................. 19

de Groot, W. ......................................... 76

de Pablo, J. ............................................ 31

deGroot, W. .......................................... 70

DeLongchamp, D. M. ........................... 63

den Doelder, J. ...................................... 18

Deshpande, A. P. .................................. 56

DesLauriers, P. J. .................................. 55

Desport, J. S. ......................................... 58

Dowd, M. K. ......................................... 66

F Farrell, W. S.................................... 46, 86

Föge, V. ................................................ 68

Foster, I. ................................................ 31

Frache, G. ............................................. 58

François, I. ............................................ 29

G Ganesh, S. ............................................. 23

Garg, P. ................................................. 48

Gartner III, T. E. ............................. 34, 69

Ghosh, A. .............................................. 55

Gillespie, D.T. ...................................... 76

Gough, J. .............................................. 29

Gurappa, B. M. ..................................... 56

H Hadjichristidis, N. ................................ 52

Han, C. C. ............................................. 67

Han, C.C. .............................................. 45

He, Z. .................................................... 66

Heidegger, A. ....................................... 68

Heinzmann, G. ...................................... 60

Helgeson, M. E. .................................... 20

Hillmyer, M. A. .................................... 46

Hiroi, Y. ................................................ 72

Hofe, T. ................................................ 84

Höpfner, J. ............................................ 39

Horchler, G.P. ........................... 75, 76, 78

Hore, M. J. A. ....................................... 61

Hutchings, L. R. ................................... 50

J Jančo, M. ........................................ 28, 80

Jayaraman, A. ................................. 34, 69

Jones, M. .............................................. 29

Jones, R. L. ..................................... 34, 69

K Kassekert, L. A. .................................... 46

Kaur, G. ................................................ 23

Kawashima, M. .................................... 72

Kilz, P. .................................................. 83

Kot, D. .................................................. 73

Kotula, A. P. ......................................... 21

Kübel, J. ................................................ 39

Kumari, S. ............................................ 23

L Lachmayr, K. K. ............................. 82, 85

Lamborn, M. J. ..................................... 55

Lavric, S. .............................................. 27

Lee, Y. J. .............................................. 43

Lequieu, J. ............................................ 31

Liu, Y. .................................................. 47

Author Index

90

Lobo, A. ................................................ 75

Lohmann, D. ............................. 27, 83, 84

Loo, J. S. C. .......................................... 88

Luo, J. ................................................... 45

M Ma, J. .................................................... 47

MacCreath, B. ................................. 29, 87

Macko, T. ............... 48, 57, 73, 75, 76, 78

Malz, F. ................................................. 70

Martin, T. B. ................................... 34, 69

Matsubara, K. ....................................... 72

Mauri, M. ........................................ 37, 64

McConville, J. ...................................... 83

Meeker, L. ............................................ 87

Mekap, D. ....................................... 70, 76

Meredig, B. ........................................... 32

Mes, E.P.C. ........................................... 76

Meunier, D. ........................................... 76

Meunier, D. M. ..................................... 40

Miranda, S. L. ....................................... 54

Mischnick, P. ........................................ 79

Monwar, M. M. .................................... 55

Morlock, S. ........................................... 39

Morrison, D. ......................................... 29

Mukherjee, P. ....................................... 55

N Narasimhan, V. C. ................................ 88

Netto, A. M. .......................................... 54

Nickel, F. .............................................. 68

Noda, I. ................................................. 42

Nowak, S. R. ......................................... 44

O O’Leary, M. .......................................... 29

Oleschko, K. ......................................... 84

Orski, S. V. ........................................... 46

P Patil, S. ................................................. 23

Plankeele, J.-M. .................................... 29

Pothecary, M. R. ................................... 87

Prabhu, V.M ......................................... 24

Preis, J. ................................................. 27

Q Qin, J. ................................................... 31

R Rabolt, J. F. ........................................... 42

Radke, W. ....................................... 27, 83

Rajeev, A. ............................................. 56

Ramakrishnan, V. ................................. 57

Ramprasad, R. ...................................... 30

Rasmussen, C. J. .................................. 26

Read, D. J. ............................................ 19

Reed, R. ................................................ 60

Rettner, E.M. ........................................ 49

Rommens, S. .................................. 25, 71

Rowlette, J. ........................................... 43

Roy, A. ................................................. 42

S Sabagh, B. ............................................ 60

Saha, P. ................................................. 23

Sarapas, J.M. ........................................ 49

Schindler, C. ......................................... 87

Schwarzinger, C. ............................ 68, 77

Shahi, V. ............................................... 87

Simanke, A. .......................................... 75

Simonutti, R. .................................. 37, 64

Sita, L. R. ........................... 44, 51, 82, 85

Smits, G. F. .......................................... 33

Snyder, C. R. .................................. 34, 69

Spegazzini, N. ...................................... 55

Stamm, M. ............................................ 84

Stenson, J. D. ........................................ 87

Sudwischer, P. ...................................... 79

T Tacx, J. ................................................. 48

Tappadiya, A. ................................. 65, 81

Tawfilas, M. ......................................... 37

Tchoua, R. ............................................ 31

Thomas, T. S. ................................. 82, 85

U Uhlmann, P. .......................................... 84

Uliyanchenko, E. ...................... 25, 57, 71

Unterieser, I. ......................................... 79

V Vaccarello, D.N. ................................... 49

Vancso, G. J. ........................................ 47

Vargas Lara, L. F. ................................ 35

Vasanthan, N. ................................. 65, 81

Verma, S. .............................................. 23

W W. Radke .............................................. 83

Wang, M. .............................................. 67

Ward, L. ............................................... 31

Wei, Y. ................................................. 61

Wilhelm, M. ......................................... 39

Wirtz, M. .............................................. 58

Wubben, A. .......................................... 79

X Xu, Y. ................................................... 61

Author Index

91

Y Yager, K.................................... 44, 82, 85

Yager, K. G. .......................................... 62

Yang, D. ................................................ 59

Yu, Y. ................................................... 78

Yuan, G. ......................................... 45, 67

Z Zhao, C. ................................................ 45

Zhou, Z. ................................................ 70

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