Characterization of Short Chain Branched

Polyolefins by SEC/GPC-FTIR

William W. Carson; David Dunn; Jim Dwyer;

Ming Zhou; Tom Kearney

Spectra Analysis Instruments, Inc.

June 20, 2010

Contact: CarsonW@Spectra-Analysis.com

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HPLC2010 Boston: P2422M

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GPC-IR Hyphenated System

How Does It Work?

How is the Solvent Removed?

Cyclone

Evaporator

Thermal NebulizationFrom LC

Nitrogen Addition

Chilled

Condenser

Waste Solvent

Particle Stream to DiscovIR

Air Cooled

Condenser

Cyclone

Evaporator

Patent pending:

PCT/US2007/025207

What is Direct Deposition FTIR?

Direct Deposition FTIR and Data Processing

LC-IR Hyphenated Technology for Polymer Analysis

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Features of DiscovIR-LC

Online Fully Integrated System

Fully Automated Operation: No Fractionation

Multi-Sample Processing: 8-40 Hr ZnSe Disk Time

Microgram Sensitivity at Sample Injection Point

Real-Time Chromatography & Spectral Data

Solid Phase Transmission IR Spectra: High Quality w/ Purified Analytes

Database Search Capability & In-House Library Creation

Data Analysis: GRAMS for Chemometrics, 3D LC-IR, Functional Group

Chromatograms & Comparisons at any Wavenumbers or across Peaks

All LC Solvents: Water, ACN, Methanol, THF, Chloroform, HFIP

GPC/SEC: TCB @ High Temperature (150C)

HPLC: Isocratic or Gradient; Normal & Reverse- Phase

Compatible with LC-MS Set-Up in Parallel

HT GPC-IR Test Conditions

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GPC: Waters 150C

Solvent : TCB

Temperature: 145C

Column: Jordi DVB Mix Bed 25cm x 1cm Size 5 mm

Flow Rate: 1 ml/min

Sample: 2.5 mg / ml with 200ppm Irganox 1010

Injection Volume: 100 ml

Transfer Line Temperature: 150C

DiscovIR-LC Conditions:

• Cyclone Temperature: 375C

• Chamber Vacuum: 2 Torr

• Disk Speed: 3 mm/min

High Temp GPC-IR Spectra for

Polyolefin Branching Analysis

Ethylene-Propylene Copolymer (40% PP), Solvent TCB @ 150C

High Temp GPC-IR for Polyolefin Branching Analysis

Polyethylene Sample with & without TCB Solvent

DiscovIR-LC Removes TCB Completely and Gives Clean IR Spectrum (Blue).

GPC-IR Branching Analysis of Ethylene-Propylene Copolymers

Copolymer Compositional Drift ~ CH3 Branching ~ Peak Ratio A1378/A1468

GPC-IR Chromatogram of EP Copolymer Overlaid with Peak Ratio Abs1378/Abs1468

(Molecular Weight Distribution)

GPC-IR Spectra of Ethylene-Hexene Copolymers

Butyl Branching ~ Peak Ratio A1378/A1368

Butyl Branching Analysis of Ethylene-Hexene

Copolymers by GPC-IR

Butyl Branching Numbers per 1000 Backbone Carbons with Elution Time (MWD)

(Molecular Weight Distribution)

N butyls/1000 c

10

12

14

16

18

20

22

24

26

8 9 10 11 12 13 14 15

elution time, min

N b

uty

ls/1

000 c

Area Ratio = Area (2940-3100cm-1) / Area (2940-2800cm-1)

GPC-IR Branching Analysis of

Ethylene-Propylene Copolymers GPC-IR Chromatograms Overlaid with Area Ratios

(Molecular Weight Distribution)

Higher Sensitivity than Peak Ratio Method at Low Branching Levels

Area Ratio = Area (2940-3100cm-1) / Area (2940-2800cm-1)

GPC-IR Branching Analysis of Ethylene-Octene

Copolymers by Chemometrics

GPC-IR Chromatograms Overlaid with Area Ratios

(Molecular Weight Distribution)

Higher Sensitivity than Peak Ratio Method at Low Branching Levels

EP(~40%)

HDPE

EO (~3%)

EO(~2%)

EO(~1%)

Area Ratio = Area (Peak 1375 cm-1) / Area (Peak 1465 cm-1)

Branching Levels (Area Ratios) with a GPC-IR Chromatogram

(Molecular Weight Distribution)

GPC-IR Branching Analysis of Dow ENGAGE® Polyolefins

Ethylene-Octene: 8100, 8200

8401, 8540

Ethylene Propylene: ENR 6386

Sample 3 is a mixture of polypropylene homopoylmer,

ethylene/propylene copolymer & ethylene/butene copolymer

Polyolefin Mixture Analysis (De-Formulation) by GPC-IR

ethylene/propylene copolymer

Sample 3 is a mixture of polypropylene homopoylmer,

ethylene/propylene copolymer & ethylene/butene copolymer

Polyolefin Mixture Analysis (De-Formulation) by GPC-IR

GPC-IR Chromatogram with Specific Wavenumbers

PP & EP

EP & EB

Isotactic PP

EB

Conclusions

High Temp GPC-IR Takes Snapshot IR Pictures of Polyolefin

Copolymers for Compositional Drifts and Short Chain Branching

Analysis with MW Distributions

Short Chain Branching Levels can be Analyzed either by Peak Height

Ratios or Peak Area Ratios for Ethylene Copolymers with Propylene,

Butene, Hexene and Octene.

GPC-IR can Analyze Short Chain Branching Levels of Ethylene

Copolymers from Multiple IR Ranges: 2800-3000, 1500-1300 and

1300-700 cm-1.

GPC-IR is a Powerful Tool to De-Formulate Polyolefin Mixtures.

LC-IR Applications

DiscovIR-LC is a Powerful Tool for Polymer, Excipient & Materials Analysis

Polyolefin Copolymer Branching Analysis by High Temp GPC-IR

Excipient Characterization, Functionality & Degradation Analysis

Copolymer Compositional Drift Analysis across MW Distributions

Polymer Blend Ratio Analysis across MWD

Polymer Additive & Impurity Analysis

De-Formulation for Polymers, Excipients and Additives

Process Control & Optimization

Reactive Polymer Analysis for Coating, Adhesive, Sealant & Elastomer

Plastics, Rubbers, Films, Fibers, Foams, Composites & Biopolymers

Isomer Analysis for Chemicals, Forensics & Pharmaceuticals

General Analytical Capability: Trouble Shooting 21