HPLC2010 Boston Presentation

1. HPLC2010 Boston: P2422M
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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2. GPC-IR Hyphenated System
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3. How Does It Work?

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

5. What is Direct Deposition FTIR?

6. Direct Deposition FTIR and Data Processing

7. LC-IR Hyphenated Technology for Polymer Analysis
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8. 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

9. HT GPC-IR Test Conditions
 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
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10. High Temp GPC-IR Spectra for
Polyolefin Branching Analysis
Ethylene-Propylene Copolymer (40% PP), Solvent TCB @ 150C

11. 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).

12. GPC-IR Branching Analysis of Ethylene-Propylene Copolymers
GPC-IR Chromatogram of EP Copolymer Overlaid with Peak Ratio Abs1378/Abs1468
(Molecular Weight Distribution)
Copolymer Compositional Drift ~ CH3 Branching ~ Peak Ratio A1378/A1468

13. GPC-IR Spectra of Ethylene-Hexene Copolymers
Butyl Branching ~ Peak Ratio A1378/A1368

14. Butyl Branching Analysis of Ethylene-Hexene
Copolymers by GPC-IR
N butyls/1000 c
26
24
22
20
N butyls/1000 c
18
16
14
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)

15. GPC-IR Branching Analysis of
Ethylene-Propylene Copolymers
GPC-IR Chromatograms Overlaid with Area Ratios
(Molecular Weight Distribution)
Area Ratio = Area (2940-3100cm-1) / Area (2940-2800cm-1)
Higher Sensitivity than Peak Ratio Method at Low Branching Levels

16. GPC-IR Branching Analysis of Ethylene-Octene
Copolymers by Chemometrics
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

17. GPC-IR Branching Analysis of Dow ENGAGE® Polyolefins
Branching Levels (Area Ratios) with a GPC-IR Chromatogram
Ethylene-Octene: 8100, 8200
8401, 8540
Ethylene Propylene: ENR 6386
(Molecular Weight Distribution)
Area Ratio = Area (Peak 1375 cm-1) / Area (Peak 1465 cm-1)

18. 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

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

20. 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.

21. 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