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Advanced GPC Technology as a Part of Solving Complex Polymer Problems Scott D. Hanton, Chanell Brown, and Dale Willcox

Intertek Allentown

September 2014

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Acknowledgments

• Intertek

• Sherri Bassner

• Todd McEvoy

• Devon Shankweiler

• Air Products

• Dennis Nagy

• Waters

• Damian Morrison

• Michael O’Leary

• Betsy Baer

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Outline

• Intertek introduction

• Polymer analysis

• Traditional GPC

• High performance SEC

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Extensive Global NetworkE

More than

1,000 laboratories and offices

•FTSE 100 company in the Support Services sector

•Revenues of $3.5 billion in 2013.

More than

120 countries

Approximately

36,000 people

Introduction to Intertek

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Intertek Allentown – Yesterday and Today

• Formerly the corporate analytical group for Air Products and Chemicals • Joined Intertek network in July 2010

• Supported R&D, technical service, process scale-up, and manufacturing troubleshooting globally

• Today • ISO 17025 lab located in Allentown, Pennsylvania USA. Forty-six

technical and administrative staff members.

• Problem-solving and non-standardized testing for multiple industries including Materials (ceramics, polymers, composites), Medical Devices, Pharmaceuticals, Chemicals, Construction Materials and more

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Intertek Allentown Your Problem-Solving Partner

Problem-Solving Teams

Inorganic Analysis

Microscopy, metallurgy, surface science, diffraction,

failure analysis, , particle size

Residue ID, ceramics, polymer

structure, electronic and nano-materials

Titrations, trace metals

System stability, impurity analysis, gases/chemicals

Material Properties

Rheology, thermal analysis/hazards,

sorption

Polymer systems, catalysis, reaction

studies, gas separation

Organic Analysis

Chromatography, MS, NMR,

spectroscopy

Chemical structure identification, degradation

analysis, impurity analysis

Mechanical/ environ. Testing

(Pittsfield)

Extractables and

Leachables (Whitehouse)

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Introduction

• Polymer chemistry continues to be vital

• New products

• New uses

• New research

• Significant challenges presented in polymer analysis

• Multiple monomers

• Solubility

• Complex structures

• Complex formulations

• Require multiple and powerful tools to analyze polymers

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Polymeric Materials

Applications

Physical Properties

Molecular Structure Molecular Weight Distribution

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Polymer structures

• Many different polymer structures have been developed

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Polymer Detective

• What is it?

• What are its properties?

• How does it behave?

• What else is in it?

• Where is it?

• How big is it?

• How much of it is there?

• What is its chemical structure?

• How is it connected?

• What’s on the end?

What? Where? How? Who?

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Polymer Analysis Decision Tree

Identity

FTIR

Raman

CHNOS

SEC

Material Properties

Density

Rheology

DSC

TMA

Sorption

Morphology

SEM

AFM

Components

TGA

XRF

GC

LC

Chemical Structure

NMR

MS

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Traditional GPC

Problem-solving through molecular size measurements

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GPC: Characterize MWD of Acrylates

R&D Acrylate Polymers

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GPC: “Good” Sample vs. “Bad” Sample

Acrylonitrile Butadiene Styrene (ABS) tubs

Damaged Tub Undamaged Tub

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1 2

GPC: “Good” Sample vs. “Bad” Sample

Damaged Tub Undamaged Tub

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High Temperature – GPC: “Good” and “Bad” Strap

Sample ID Mn (Daltons) Mw (Daltons) Mp (Daltons) Mz (Daltons) PDI (Mw/Mn)

Bad 6,570 27,100 27,100 54,700 4.1

Good 49,600 172,000 140,000 354,000 3.5

Polypropylene straps

2 3 4 5 6 7 Log MW

Bad Strap

Good Strap

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HT-GPC: “Good” and “Cracked” Lip Balm Squeeze Tubes

Cracked tube

Recent tube Original tube

2 3 5 6 7 4 Log MW

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Amine GPC: Amine and Quaternary Amine Polymers

Obtain useful chromatograms from materials with high amine functionality

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Amine GPC: Polymerization Process Epoxy-Amines

2 3 2.5 Log MW

End

Beginning

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GPC: Monitor Polymer Formation

High Molecular Weight Species

Compare against competitors Polymer formation results in poor performance

Polyamines

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GPC: Monitor Polymer Formation

Polymer Formation

Sample Aged

Sample Air Exposed

Competitor 2

Competitor 1 Sample

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GPC: Trace Determination of Polymer Content

y = 3002.8x - 53039R² = 0.9987

0

500000

1000000

1500000

2000000

2500000

0 100 200 300 400 500 600 700 800

Pe

ak R

esp

on

se (

Are

a C

ou

nt)

Concentration (ppm)

HA Calibration Curve

Series1

Linear (Series1)

Hyaluronic Acid Standard Calibrated from 100 – 800 ppm

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High Performance SEC

Waters’ Advanced Polymer Chromatography (APC)

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Traditional GPC vs APC

• Conventional GPC

− New Solvent equilibration takes 9 – 48 hours

− Operate columns under low backpressure

− Large system volume lead to loss of resolution

− Typical analysis time 30 – 45 minutes

• Advanced Polymer Chromatography (APC)

+ New solvent equilibration time takes 2 – 4 hours

+ Operate columns under high backpressure

+ Sub 3µm hybrid particle column technology combined with low dispersion result in improvements in resolution

+ Typical analysis time 10 – 15 minutes

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APC: Rapid Analysis of Polycarbonate Urethane

Urgent analyses completed in 22 hours, GPC would have taken 3 days

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APC vs GPC: Polyalkyleneglycol (PAG)

APC GPC

R&D analysis – Improved resolution and speed (15 min vs 35 min)

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APC: Low Mass Surfactants

Improved resolution shows starting alcohol in lowest mass products

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APC: Low Mass Surfactants

Compare ethoxylated surfactants with different end groups and number of EO’s

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APC: Oligomer Content in Polysulfones

Competitive analysis – debunk claim of lower oligomer content

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APC: Compare Silicone Putty Samples

Competitive analysis – compare MWD from different vendors

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APC: EO/PO Degree of Polymerization

R&D synthesis analysis – intended PO10/EO20 and PO55/EO40

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APC: Epoxy Resin Comparison

Regulatory analysis – compare MWD of different epoxy resins

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APC: Verify MWD of PC/ABS Polymer

R&D analysis – measure MWD of polycarbonate/acrylonitrile-butadiene-styrene material

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APC: Oil Additives

R&D analysis – measure MWD of additives directly from oil

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APC: Reactive Polymer Analysis

R&D analysis – measure MWD of Polymethylhydrogen Siloxanes

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Amine APC: Modified Amine Capped Surfactants

R&D analysis – measure MWD of Reactants and Products

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APC vs GPC: Chromatogram of Hydrocarbon Resin

APC

GPC

APC Mn (Daltons)

Mw (Daltons)

Mz (Daltons)

PDI (Mw/Mn)

APC 2,410 4,920 8,290 2.0 GPC 1,740 3,530 5,740 2.0

4.0

16.0

APC higher due to lower dispersion

Improved resolution

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APC vs GPC: Silicone Surfactant

APC

GPC

Mn (Daltons)

Mw (Daltons)

Mz (Daltons)

PDI (Mw/Mn)

APC 6,610 38,300 92,600 5.8

GPC 5,930 36,600 94,500 6.2

6.0

15.0

Improved resolution

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APC vs GPC: Poloxamer (EO:PO:EO)

APC Mw = 7,500 D

Traditional SEC Mw = 12,000 D

R&D analysis – MWD difference due to resolution or column interaction?

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Future Work on APC

• SEC of materials with more amine functionality

• Understand differences between mixed bed GPC and narrow pore size APC results

• Different mobile phases

• Aqueous

• HFIP

• Interested in modified column sets for more polar samples

• Explore column interactions

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Summary

• SEC

• Solving polymer science problems related to

• Wide range of polymer chemistry

• Wide range of problems

• APC

• Obtain much faster chromatography

• Observe improved resolution

• Useful for a wide range of polymer chemistry

• Interesting research opportunities to expand methods

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Valued Quality. Delivered.

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Back Up

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Molecular Weight Distribution

• Correlate to the end-use properties of the polymer

• Some properties are listed in table below

Tensile Strength Adhesive Strength Elastomer Relaxation Time

Cure Time Brittleness Elastic Modules

Flex Life Met Viscosity Impact Strength

Hardness Toughness Softening Temperature

Drawability Tear Strength Adhesive Tack

Stress-crack Resistance Coefficient of Friction

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Chromatogram of Glycol Sample APC vs. GPC

APC

GPC

Mn (Daltons)

Mw (Daltons)

Mz (Daltons)

PDI (Mw/Mn)

APC 24,600 37,400 44,800 1.5

GPC 24,000 35,500 42,500 1.5