2011 Int’l Polyolefin ConferenceFull Scan GPC-IR Characterization of Polyolefin Copolymers and Blends           Ming Zhou,...
OUTLINE GPC-IR Hyphenated Technology: Instrumentation GPC-IR Applications: Case Studies• Copolymer Compositional Analysi...
Hyphenated Technologies &                              Major Applications                    LC-MS                        ...
GPC-IR Hyphenated System                      GPC–Desolvation–IR AnalyzerDell Desktop ComputerThermo-GRAMS /32 Software ...
LC-IR Hyphenated SystemGPC orHPLC
How is the Solvent Removed?                         Nitrogen Addition                                             CycloneF...
Direct Deposition FTIR &Data Processing (GPC-IR)  ZnSe Disk                           7
ZnSe Sample Disk   Rotate at std speed    3mm/min or slow speed    0.3mm/min   Auto sampler compatible   Unattended ove...
What is Direct Deposition FTIR?Separated Dot Depositing on Disk   Separated Dots from HPLC-IR   Continuous Polymer Tracks ...
Features of DiscovIR-LC System Real-Time On-line Detection Microgram Sensitivity Compatible with all HPLC Solvents and ...
11
Compositional Drift Analysis of                                 Copolymer Poly(A-B) by GPC-IR                             ...
Compositional Drift Analysis of                                    Poly(A-B) by Various Techniques                     GPC...
GPC-IR Spectrum Snapshot of                          Styrene/Butadiene Copolymer                                          ...
Compositional Drifts across MWD                              for Styrene/Butadiene Copolymer                              ...
GPC-IR Spectrum Snapshot & Band                         ID for SEBS Block Copolymers                BB2                   ...
SEBS Ratio Overlay w/ MWDBB1/BB2 (Flat), B/BB1, S1/BB1, S2/BB1
High Temperature GPC-IR Test                        Conditions for SCB Analysis GPC: Waters 150C Solvent : TCB Temperat...
High Temp GPC-IR Spectra for                    Polyolefin Branching AnalysisEthylene-Propylene Copolymer (40% PP), Solven...
High Temp GPC-IR Removes                            TCB Solvent for SCB Analysis            Polyethylene Sample with & wit...
Polyolefin Branching Analysis by                              GPC-IR for EP Copolymer GPC-IR Chromatogram of EP Copolymer ...
HT GPC-IR Spectra of                       Ethylene-Hexene Copolymers                                            CH2CH2CH2...
Butyl Branching Analysis of                                          Ethylene-Hexene Copolymers                           ...
Polyolefin Short Chain Branching                         Analysis by ChemometricsGPC-IR Chromatograms Overlaid with Area R...
GPC-IR Branching Analysis of                           Dow ENGAGE® PolyolefinsBranching Levels (Area Ratios) with a GPC-IR...
GPC-IR Branching Analysis of                         Ethylene-Octene Copolymers       GPC-IR Chromatograms Overlaid with A...
HT GPC-IR to Identify Branch                               Types in IR Fingerprint RegionAt slower disk speed (0.3mm/min),...
Polyolefin Mixture Analysis                     (De-Formulation) by GPC-IR                              ethylene/propylene...
Polyolefin Mixture Analysis                   (De-Formulation) by GPC-IR   GPC-IR Chromatogram with Specific Wavenumbers  ...
Summary High Temp GPC-IR Takes Snapshot IR Pictures of Polyolefin Copolymers forCompositional Drifts and Short Chain Bran...
LC-IR Applications   GPC-IR is a Powerful Tool to Characterize Copolymers & Polymer Mixtures   Polyolefin Branching Anal...
Polymer Blend Ratio Analysis by                     GPC-IR for EVA/PBMA Mixture   IR spectral bands of EVA & PBMA are clos...
Polymer Blend EVA/PBMA Ratios with                                                     MWD from Spectral Peak Ratios      ...
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SPE2011 Full Scan GPC-IR Characterization Of Polyolefin Copolymers And Blends-2-22-2011

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SPE2011 Full Scan GPC-IR Characterization Of Polyolefin Copolymers And Blends-2-22-2011

  1. 1. 2011 Int’l Polyolefin ConferenceFull 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 1
  2. 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 2
  3. 3. Hyphenated Technologies & Major Applications LC-MS LC-IRSeparation Liquid ChromatographyDetection & Mass Infra RedData Analysis Spectroscopy SpectroscopyApplications Small Molecules, Proteins Copolymers & MixturesPharma API’s Polymeric Excipients
  4. 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. 5. LC-IR Hyphenated SystemGPC orHPLC
  6. 6. How is the Solvent Removed? Nitrogen Addition CycloneFrom LC Cyclone Evaporator Thermal Evaporator Nebulization Air Cooled Condenser Patent pending: PCT/US2007/025207 Chilled Condenser Particle Stream to Deposition Disk Waste Solvent
  7. 7. Direct Deposition FTIR &Data Processing (GPC-IR) ZnSe Disk 7
  8. 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. 8
  9. 9. What is Direct Deposition FTIR?Separated Dot Depositing on Disk Separated Dots from HPLC-IR Continuous Polymer Tracks (GPC-IR)
  10. 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. 11
  12. 12. Compositional Drift Analysis of Copolymer Poly(A-B) by GPC-IR A A/B Ratio BAbsorption High MW Low MW Molar Mass Ratio 10/8 12/12 2/4 Total 24/24 A% 56% 50% 33% 50%
  13. 13. Compositional Drift Analysis of Poly(A-B) by Various Techniques GPC-IR A/B RatioAbsorption 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. 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. 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. 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. 17. SEBS Ratio Overlay w/ MWDBB1/BB2 (Flat), B/BB1, S1/BB1, S2/BB1
  18. 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) 18
  19. 19. High Temp GPC-IR Spectra for Polyolefin Branching AnalysisEthylene-Propylene Copolymer (40% PP), Solvent TCB @ 150C
  20. 20. High Temp GPC-IR Removes TCB Solvent for SCB Analysis Polyethylene Sample with & without TCB SolventDiscovIR-LC Removes TCB Completely and Gives Clean IR Spectrum (Blue).
  21. 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. 22. HT GPC-IR Spectra of Ethylene-Hexene Copolymers CH2CH2CH2-CH3Butyl Branching ~ Peak Ratio A1378/A1368 -(CH-CH2)m-(CH2-CH2)n-
  23. 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. 24. Polyolefin Short Chain Branching Analysis by ChemometricsGPC-IR Chromatograms Overlaid with Area Ratios of EP Copolymer (Molecular Weight Distribution) Area Ratio = Area (2940-3100cm-1) / Area (2940-2800cm-1)
  25. 25. GPC-IR Branching Analysis of Dow ENGAGE® PolyolefinsBranching 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. 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. 27. HT GPC-IR to Identify Branch Types in IR Fingerprint RegionAt slower disk speed (0.3mm/min), GPC-IR deposits much thicker polymer films togive much higher sensitivity in IR Fingerprint Region with unique bands for branchtype 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. 28. Polyolefin Mixture Analysis (De-Formulation) by GPC-IR ethylene/propylene copolymer polypropyleneSample 3 (Blue) is a mixture of polypropylene homopoylmer,ethylene/propylene copolymer & ethylene/butene copolymer
  29. 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. 30. Summary High Temp GPC-IR Takes Snapshot IR Pictures of Polyolefin Copolymers forCompositional Drifts and Short Chain Branching Analysis with MWD Short Chain Branching Levels can be Analyzed either by Peak Height Ratiosor Peak Area Ratios for Ethylene Copolymers with Propylene, Butene, Hexeneand Octene. GPC-IR can Analyze Short Chain Branching Levels of Ethylene Copolymersfrom 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 inFingerprint Region (1500-700 cm-1), Capable to De-Formulate ComplexPolyolefin Mixtures such as PP, EP & EB Blend. Full Scan GPC-IR is a Powerful Tool to Characterize Polyolefin Copolymersand Mixtures. 30
  31. 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 31
  32. 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. 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)

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