Presentation slides at 2011 Int\'l Polyolefin Conference: Full Scan GPC-IR Characterization Of Polyolefin Copolymers And Blends

1. 2011 Int’l Polyolefin Conference
Full Scan GPC-IR Characterization of
Polyolefin Copolymers and Blends
Ming Zhou, William Carson,
Sidney Bourne & Tom Kearney
Spectra Analysis Instruments, Inc.
March 1, 2011
Contact: ZhouM@Spectra-Analysis.com
Tel. 508-281-6276
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2. OUTLINE
 GPC-IR Hyphenated Technology: Instrumentation
 GPC-IR Applications: Case Studies
• Copolymer Compositional Analysis: SBR, SEBS
• Polyolefin SCB Analysis by High Temp GPC-IR: EP, EB, EH & EO
• Polyolefin Blend De-Formulation: PP+EP+EB
 Summary
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3. Hyphenated Technologies &
Major Applications
LC-MS LC-IR
Separation Liquid Chromatography
Detection & Mass Infra Red
Data Analysis Spectroscopy Spectroscopy
Applications Small Molecules, Proteins Copolymers & Mixtures
Pharma API’s Polymeric Excipients

4. GPC-IR Hyphenated System
GPC–Desolvation–IR Analyzer
Dell Desktop Computer
Thermo-GRAMS /32 Software Package
•Library Search & Creation
•Ratio Chromatograms 4
•CFR 21-Part 11 Compliant

5. LC-IR Hyphenated System
GPC or
HPLC

6. How is the Solvent Removed?
Nitrogen Addition
Cyclone
From LC
Cyclone Evaporator
Thermal Evaporator
Nebulization
Air Cooled
Condenser
Patent pending:
PCT/US2007/025207
Chilled
Condenser
Particle Stream to Deposition Disk
Waste Solvent

7. Direct Deposition FTIR &
Data Processing (GPC-IR)
ZnSe Disk
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8. ZnSe Sample Disk
 Rotate at std speed
3mm/min or slow speed
0.3mm/min
 Auto sampler compatible
 Unattended overnight runs
 The yellow ZnSe disk is
under vacuum without
moisture or CO2 interference
 Re-usable after solvent
cleaning
 Transmission IR analysis is
done on the solid deposit.
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9. What is Direct Deposition FTIR?
Separated Dot Depositing on Disk Separated Dots from HPLC-IR Continuous Polymer Tracks (GPC-IR)

10. Features of DiscovIR-LC System
 Real-Time On-line Detection
 Microgram Sensitivity
 Compatible with all HPLC Solvents and Gradients
• e.g. Water, ACN, Methanol, THF, Chloroform
 Compatible with all GPC/SEC Solvents: e.g. TCB, DMF, HFIP
 High Quality Solid Phase Transmission IR Spectra
 Fully Automated Operation: No More Manual Fractionation
 Multi-Sample Processing: 10 Hr ZnSe Disk Time

11. 11

12. Compositional Drift Analysis of
Copolymer Poly(A-B) by GPC-IR
A
A/B Ratio B
Absorption
High MW Low MW Molar Mass
Ratio 10/8 12/12 2/4 Total 24/24
A% 56% 50% 33% 50%

13. Compositional Drift Analysis of
Poly(A-B) by Various Techniques
GPC-IR
A/B Ratio
Absorption
Regular IR Bulk 50% (NMR)
(MS)
High MW Low MW Molar Mass
Ratio 10/8 12/12 2/4 Total 24/24
A% 56% 50% 33% 50%

14. GPC-IR Spectrum Snapshot of
Styrene/Butadiene Copolymer
Cove this
The three bands filled in red arise from the styrene
comonomer (1605, 1495, and 698 cm-1)
The green filled band (968 cm-1) is
generated by the butadiene
comonomer.
There is no significant overlap of any of these bands by the other
comonomer species.

15. Compositional Drifts across MWD
for Styrene/Butadiene Copolymer
Bulk Average – 10% Styrene
Compositional Changes with GPC Elution Time (MWD) for Comonomers Styrene
(1495cm-1), Butadiene (968 cm-1) and their Ratios Styrene/Butadiene (1495cm-1 /968 cm-1)

16. GPC-IR Spectrum Snapshot & Band
ID for SEBS Block Copolymers
BB2
CH2-CH3
2924
-(CH2-CH)k-(CH2-CH2)m-(CH2-CH)n-(CH2-CH)l –
BB = Backbone S E B S
BB1
1465 S2
B 700
S1 1379
1493

17. SEBS Ratio Overlay w/ MWD
BB1/BB2 (Flat), B/BB1, S1/BB1, S2/BB1

18. High Temperature GPC-IR Test
Conditions for SCB Analysis
 GPC: Waters 150C
 Solvent : TCB
 Temperature: 145C
 Column: J ordi 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 (Standard)
0.3 mm/min (Slower for thicker deposition)
(Better Sensitivity in IR Fingerprint Region)
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19. High Temp GPC-IR Spectra for
Polyolefin Branching Analysis
Ethylene-Propylene Copolymer (40% PP), Solvent TCB @ 150C

20. High Temp GPC-IR Removes
TCB Solvent for SCB Analysis
Polyethylene Sample with & without TCB Solvent
DiscovIR-LC Removes TCB Completely and Gives Clean IR Spectrum (Blue).

21. Polyolefin Branching Analysis by
GPC-IR for EP Copolymer
GPC-IR Chromatogram of EP Copolymer Overlaid with Peak Ratio Abs1378/Abs1468
CH3
-(CH2-CH2)m-(CH2-CH)n-
(Molecular Weight Distribution)
Copolymer Compositional Drift ~ CH3 Branching ~ Peak Ratio A1378/A1468

22. HT GPC-IR Spectra of
Ethylene-Hexene Copolymers
CH2CH2CH2-CH3
Butyl Branching ~ Peak Ratio A1378/A1368
-(CH-CH2)m-(CH2-CH2)n-

23. Butyl Branching Analysis of
Ethylene-Hexene Copolymers
N butyls/1000 c
26
24
22
20
N butyls/1000 c
18
16
CH2CH2CH2-CH3
14
-(CH-CH2)m-(CH2-CH2)n-
12
10
8 9 10 11 12 13 14 15
elution time, min
(Molecular Weight Distribution)
Butyl Branching Numbers per 1000 Backbone Carbons with Elution Time (MWD)

24. Polyolefin Short Chain Branching
Analysis by Chemometrics
GPC-IR Chromatograms Overlaid with Area Ratios of EP Copolymer
(Molecular Weight Distribution)
Area Ratio = Area (2940-3100cm-1) / Area (2940-2800cm-1)

25. GPC-IR Branching Analysis of
Dow ENGAGE® Polyolefins
Branching Levels (Area Ratios) with a GPC-IR Chromatogram
Ethylene-Octene: 8100, 8200 CH2CH2CH2CH2CH2-CH3
8401, 8540
-(CH-CH2)m-(CH2-CH2)n-
(Molecular Weight Distribution)
Area Ratio = Area (Peak 1375 cm-1) / Area (Peak 1465 cm-1)

26. GPC-IR Branching Analysis of
Ethylene-Octene Copolymers
GPC-IR Chromatograms Overlaid with Area Ratios
EP(~40%)
EO (~3%)
EO(~2%)
EO(~1%)
HDPE
(Molecular Weight Distribution)
Area Ratio = Area (2940-3100cm-1) / Area (2940-2800cm-1)
Higher Sensitivity than Peak Ratio Method at Low Branching Levels

27. HT GPC-IR to Identify Branch
Types in IR Fingerprint Region
At slower disk speed (0.3mm/min), GPC-IR deposits much thicker polymer films to
give much higher sensitivity in IR Fingerprint Region with unique bands for branch
type identification.
Branch Type Comonomer IR Bending Branch Identifier
Type Frequency (cm-1)
Methyl Propylene 1377 cm-1 1151
Ethyl Butene 1379 cm-1 772
n-Butyl Hexene 1378 cm-1 894
iso-Butyl 1383, 1385 cm-1 1169
n-Hexyl Octene 1380 cm-1 890

28. Polyolefin Mixture Analysis
(De-Formulation) by GPC-IR
ethylene/propylene copolymer
polypropylene
Sample 3 (Blue) is a mixture of polypropylene homopoylmer,
ethylene/propylene copolymer & ethylene/butene copolymer

29. Polyolefin Mixture Analysis
(De-Formulation) by GPC-IR
GPC-IR Chromatogram with Specific Wavenumbers
EP & EB (720)
Isotactic PP (974)
PP & EP (1155)
EB (772)
Sample 3 is a mixture of polypropylene homopoylmer,
ethylene/propylene copolymer & ethylene/butene copolymer

30. Summary
 High Temp GPC-IR Takes Snapshot IR Pictures of Polyolefin Copolymers for
Compositional Drifts and Short Chain Branching Analysis with MWD
 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.
 At Slow Deposition Speed (0.3mm/min), GPC-IR Provides Rich IR Data in
Fingerprint Region (1500-700 cm-1), Capable to De-Formulate Complex
Polyolefin Mixtures such as PP, EP & EB Blend.
 Full Scan GPC-IR is a Powerful Tool to Characterize Polyolefin Copolymers
and Mixtures.
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31. LC-IR Applications
 GPC-IR is a Powerful Tool to Characterize Copolymers & Polymer Mixtures
 Polyolefin Branching Analysis by High Temp GPC-IR
 Analyze Copolymer Compositional/Structural Variations across MWD
 Characterize Copolymer Modification and Degradation (Failure Analysis)
 De-Formulate Polymer Mixtures and Additives
 Analyze Polymer Blend Ratio across MWD
 Process Control & Optimization
 Plastics, Rubbers, Films, Fibers, Foams, Composites & Biopolymers
 Reactive Polymer Analysis for Coating, Adhesive, Sealant & Elastomer
 Isomer Analysis for Chemicals, Forensics & Pharmaceuticals
 General Analytical Capability: Trouble Shooting
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32. Polymer Blend Ratio Analysis by
GPC-IR for EVA/PBMA Mixture
IR spectral bands of EVA & PBMA are closely overlapped.
The 1152 and 2852 cm-1 bands selected for minimal convolution.

33. Polymer Blend EVA/PBMA Ratios with
MWD from Spectral Peak Ratios
4
3.5
mEVA/mPBMA
y = 1.6162x - 0.2149
3
2.5
2
1.5
1
0.5
0
0 0.5 1 1.5 2 2.5
absEVA(2852)/absPBMA(1152)
(Molecular Weight Distribution)
Calibration Curve: Y = 1.6162 X-0.2149 by Flow Injection Method w/o LC Separation
Y is Mass Ratio, X is Peak Ratio Abs(2852)/Abs(1152)