This document summarizes a presentation on using hyphenated GPC-IR technology to de-formulate complex polymer mixtures. The presentation discusses the DiscovIR-LC system and its features for GPC-IR and HPLC-IR analysis. It provides several case studies demonstrating how GPC-IR can be used to identify individual polymer components, characterize copolymer compositions, analyze polymer additives and degradation, and more. The speaker concludes that GPC-IR is a powerful tool for de-formulating complex polymer systems and problem solving in various industries.

1. American Coatings Conference
May 7, 2012
De-Formulating Complex Polymer Mixtures
by GPC-IR Hyphenated Technology
Ming Zhou, PhD
Director of Applications Engineering
Spectra Analysis Instruments, Inc.
Marlborough, MA
Contact: ZhouM@Spectra-Analysis.com
1

2. OUTLINE
 Introduction: GPC-IR Technology
 DiscovIR-LC System & Features
 GPC-IR to De-Formulate Complex Polymer Mixtures
 Case #1: To De-Formulate a Hot Melt Adhesive
 Case #2: To De-Formulate Polymeric Additives in Lubricant Oil
 Case #3: To De-Formulate a Conductive Ink
 Summary
2

3. Hyphenated Technologies &
Major Applications
LC-MS LC-IR
Separation
Liquid Chromatography
Detection & Mass Infra Red
Data Analysis Spectroscopy Spectroscopy
Applications Small Molecules Copolymer Compositions
Proteins Polymer Mixtures
Additive Analysis
LC = GPC or HPLC

4. GPC-IR Hyphenated System
GPC

5. LC-IR Hyphenated System
System Control Deposition Hyphen GPC
Data Processing Microscopic FTIR Desolvation or HPLC

6. Schematic View of LC-IR System
GPC
or
HPLC

7. How is the Solvent Removed?
N2 Addition
Cyclone
From LC Cyclone Evaporator
Evaporator
Thermal Nebulization
Air Cooled
Condenser
Patent pending:
PCT/US2007/025207
Chilled
Condenser
Particle Stream to DiscovIR
Waste Solvent

8. ZnSe Sample Disk
 Rotate at tunable speed
15-0.3 mm/min
 Unattended overnight runs/10h
 The yellow ZnSe disk is under
vacuum without moisture or
CO2 interference
 Disk Temp: - 50C ~ 100C
 Transmission IR analysis is
done on the solid deposit.
 Re-usable after solvent
cleaning
 Mid-IR transparent
8

9. What is Direct Deposition FTIR?
Separated Dot Depositing on Disk Separated Dots from HPLC-IR Continuous Polymer Tracks (GPC-IR)

10. Direct Deposition IR in Action
10

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

12. GPC-IR: Direct Deposition &
Data Processing
ZnSe Disk
12

14. OUTLINE
 Introduction: GPC-IR Technology
 DiscovIR-LC System & Features
 GPC-IR to De-Formulate Complex Polymer Mixtures
 Case #1: To De-Formulate a Hot Melt Adhesive
 Case #2: To De-Formulate Polymeric Additives in Lubricant Oil
 Case #3: To De-Formulate a Conductive Ink
 Summary
14

15. Case #1: De-Formulate an Adhesive
GPC (Size) or IR (Composition)
GPC: Chromatographic IR: Fingerprinting
Separation of Components of Chemical Compositions
• Provides size distribution (MWD). • Unambiguous identification only
• No identification of species. practical for single species.
• Additives not identified. • Compounded IR spectra for mixtures
• Composition drift not determined.
Hot-melt adhesive (Mixture) Hot-melt adhesive (Mixture)
GPC only: 2 or 3 peaks ? IR only: Compounded spectra
.04
C .2
.03
B? .15
.02
.1
A .05
.01
0
0
2 4 6 8 10 12 14 4000 3500 3000 2500 2000 1500 1000

16. GPC-IR Data 3D View: De-Formulate
the Adhesive Polymer Mixture
.05
.04
absorbance
.03
.02
14
13
12
.01
11GPC
10 Elution
9
0
Time, min
8
4000 3500 3000 2500 2000 1500 1000
IR Wavenumber, cm-1
1724

17. GPC-IR De-Formulation
of the Adhesive Polymer Mixture
IR Max (Band) Chromatogram at 2929 cm-1 C
B?
A
IR Band Chromatogram at 1724 cm-1

18. GPC-IR Database Search to Identify
Peak A at 10 Min. as EVA Polymer
CH2 A
2929
C=O
1724

19. GPC-IR to Identify Components
C & B by Spectral Subtraction
Component C
Paraffin
Component B

20. GPC Confirmation of the De-Formulated
Components with Known Stds A, B & C
B C
A
A
B
C

21. Case #2: To De-Formulate Lubricant
Additives in Motor Oil: GPC-IR 3D View
SAE 15W-40 Heavy Duty Oil in THF
Low MW Mineral Oil (~85%) Diverted after 12.2 min
Additive Y
12
Additive X 11
10
Elution
9 Time
8 (Min. & MW)
3500 3000 2500 2000 1500 1000
Wavenumber, cm-1

22. De-Formulation of Motor Oil
Additive X @ RT 9.2 Min
Shell Rotella T Heavy Duty 15W-40
9.2 minute eluant
4000 3500 3000 2500 2000 1500 1000
wavenumber, cm-1
IR Database Search: Styrene-Acrylate Copolymer

23. Lubricant De-Formulation of
Motor Oil Additive Y @ RT 12 Min
Shell Rotella T Heavy Duty 15W-40
12 minute eluant
4000 3500 3000 2500 2000 1500 1000
wavenumber, cm-1
IR database Search: Polyisobutenyl Succinimide (PIBS)

24. Summary: Additive De-Formulation in
Motor Oil Lubricant by GPC-IR
 De-formulated Polymeric Additives X & Y in Motor Oil Lubricant
 Additive X @ Retention Time 9.2 Min
• Narrow MW Distribution ~ Average 600K (GPC)
• Styrene-Acrylate Copolymer (IR Database Search)
• Viscosity Index Improver
• No Comonomer Compositional Drift
Stable [700cm-1/1735cm-1] Band Ratio
 Additive Y @ Retention Time 10-12 Min
• Broad MW Range: 8-30K (GPC)
• Polyisobutenyl Succinimide (PIBS) (IR Database Search)
• A Dispersant to Disperse Metal Particles
• Small Comonomer Compositional Drift
[dimethyl (1367 cm-1) / imide (1700 cm-1)] Ratio Change < 10%
 Polymer Degradation Study
• To Detect Oxidized Intermediates
• Oil Change Schedule

25. Case #3: De-Formulate a Flexible
Conductive Ink by GPC-IR
 Silver Ink Paste Filled with Ag Particles (~80% Wt)
• Designed to screen print flexible circuitry / membrane switch
• Extremely flexible after curing at 150oC for 30 min.
• Very conductive even under 20x folding / crease tests (ASTM F1683)
 Sample Preparation
• Ink paste was dissolved in THF and the decant was filtered with 0.45
mm PTFE filter before GPC injection with ~0.5% polymer conc.
 GPC Settings
• LC system: Agilent 1200
• GPC Column: 2 x Jordigel DVB Mixed Bed, 25 cm X 10 mm ID
• Mobile Phase: THF at 1.0 ml/min Flow Rate
• Injection Volume: 60 ml
 IR Detection
• DiscovIR-LC® solvent-removing direct-deposition solid phase FTIR
• Cyclone Temperature: 130oC
• Condenser Temperature: 15oC
• ZnSe Disk Temperature: -10oC

26. De-Formulating the Conductive Ink
GPC-IR Chromatogram Using 2 x GPC Columns
Column: 2 x Jordigel DVB Mixed Bed
Mobile Phase: THF at 1.0 ml/min.
Sample Conc.:~5 mg/ml in THF
Injection Volume: 60 μl
IR Detector Res.: 8 cm-1
ZnSe Disk Temp.: -10oC
Cyclone Temp.: 130oC
Condenser Temp.: 15oC
Disk Speed: 12 mm/min
B
C

27. Stacked IR Spectra of Components A, B, C
at Different GPC Times (~ MWD Centers)

28. Comparison of Max Band Chromatogram
(Black) & Selected Band Chromatograms
Band 1690 cm-1
Max Band
Default Band 1510 cm-1
A
Band 730 cm-1
B
C
Elution Time (Min.)

29. Commercial IR Database Search (FDM)
for Polymer A (Red): Polyester Suppliers
Index %Match Compound Name Library
434 96.63 Amoco Resin PE-350 Coatings Technology
450 95.96 Dynapol LH-812 Coatings Technology
467 95.65 Vitel VPE-222F Coatings Technology
443 95.06 Dynapol L-411 Coatings Technology
466 94.45 Vitel PE-200 Coatings Technology

30. In-House Database Match of Polymer A
(Red Spectrum) with Flex Resin (Blue Std)

31. Commercial IR Database Search (FDM)
for Component B (Blue): PU Supplier
Index %Match Compound Name
503 88.13 Spensol L-53  UROTUF L-53
949 87.51 Polyester Polyol 0305
424 87.33 Polycaprolactone
944 87.29 Polyester Polyol 0200
212 86.86 UCAR Cyracure UVR-6351

32. Commercial IR Database Search (FDM)
for Component C (Red): Cross-linker Supplier
Index %Match Compound Name
834 92.47 Desmodur LS-2800, CAS# 93919-05-2, MW 766
3249 65.30 Caffeine; 1,3,7-Trimethylxanthine
9302 64.76 Monophenylbutazone
615 62.15 Betulinic acid; 3-Hydroxylup-20(29)-en-28-oic acid
860 62.05 Spenlite M-27

33. Summary: De-Formulation of
the Conductive Ink by GPC-IR
 Identified Polymer Components & their Suppliers in the Silver Ink Paste
 Polymer A
• High MW and Broad MW Distribution (GPC)
• Aliphatic Polyester Resin (IR Database Search)
• IR Spectrum Match with a Known Standard Resin (Pure)
• Very Flexible Polymer with Strong Adhesion on Kapton & Mylar
 Polymer B
• Medium MW and Narrow MW Distribution (GPC)
• Aliphatic PUD: Spensol L-53 (IR Database Search)
• Very Elastomeric and Highly Flexible
 Component C
• Low MW Additive (GPC)
• Desmodur LC-2800 (IR Database Search)
• Latent Cross-linking Agent: Ketoxime Blocked HDI Trimer
• De-blocking at 130-150oC  Tri-functional HDI Trimer for Cross-linking
 C+B + A during Curing (150oC / 30 min)
• De-blocked C Cross-linking with Polymer B
• Interpenetrating with Polymer A

34. GPC-IR Applications: Model Cases
 De-Formulate Complex Polymer Mixtures:
PolyX + Poly(A-B) + Additives
PolyX + PolyY + Poly(A-B-C) + Additives
 Characterize Copolymer Compositions across MWD:
Poly(A-B), Poly(A-B-C), Poly(A-B-C-D), …
 Polymer Blend Ratio Analysis across MWD: PolyX + PolyY
 Polymer Additive Analysis by HPLC-IR: Add. (SM or PolyX)
 Analyze Polymer Changes: Degradation or Modification
34

35. Summary: GPC-IR to De-Formulate
Complex Polymer Mixtures
 GPC-IR is Powerful to De-Formulate Complex Polymer Systems
 Identify Polymer Components by IR Database Search
 Find Specific Raw Material Supplier or the 2nd Supplier
 Compatible with Commercial IR Libraries & In-house IR Database
 Applicable to Coatings, Adhesives, Inks, Sealants, Elastomers,
Plastics, Rubbers, Composites, Biopolymers, Drug Formula, …
 Useful for Competitive Analysis / IP Protection
 For Problem Solving / Trouble Shooting / Contamination Analysis
 Get the Powerful Tool before Your COMPETITORS Get it !
35

36. Acknowledgment
William Carson
Tracy Phillpott
Tom Kearney
Frederic Prulliere
George Giansanti
Thank YOU ! 36

37. GPC-IR Application Summary
 Introduction: GPC-IR Technology & DiscovIR-LC System
 GPC-IR Applications: Case Studies
 De-Formulate Complex Polymer Mixtures: Adhesive, Ink,
Lubricant Additives, PP/EP/EB, PVP/HPC/HPMC Excipient
 Characterize Copolymer Composition Variations across MWD:
SBR, SEBS, PVP/VAc, PMMA/BA/MAA/S/DAAM
 Polymer Degradation Analysis: HPMCAS, PEA/MAA, PEG
 Polymer Blend Ratio Analysis across MWD: EVA/PBMA
 Polymer Additive Analysis by HPLC-IR: Antioxidants, PDMS
 HT GPC-IR to Analyze Polyolefin Branching: EP, EB, EH, EO
37
 Copolymerization Process Control: Poly(A-B-C)

38. Polymer Additive Analysis
HPLC (RP)-IR of Polymer Extract
HPLC Conditions:
Columns: guard+ Eclipse C18
50mm x 46mm 5um
Mobile phase: Grad. 75-100% AcN
(5min)-100%AcN(5min) in Water,
1ml/min
DiscovIR Conditions:
Nebulizer 2.2W,
Carrier gas 400cc,
Disk Speed 3mm/min,
Disk Temp. -10ºC,
Pressure Chamber: 6.58 torr
Condenser (single) temp. 10ºC,
Cyclone temperature: 200ºC

39. Additive Identification by HPLC-FTIR
Database Searchable

40. Polymer Additive Analysis
by LC-IR for PDMS in THF
PolyDiMethyl Siloxane is Difficult to be Detected by UV or RI.
IR is an Universal Detector for Organics

41. Additive Analysis
LC-IR Application Scope
• Stabilizers: AO, HALS, UV Stabilizers, Anti-hydrolysis
• Surfactants: Polymeric silicones, Foaming Agents
• Flexibilizer: Toughners
• Thickeners: Dispersants
• Colorants: Polymeric
• Curing Agents: Crosslinkers
• Processing Aids: Mold Release Agents, Lubricants
• Biocides: Anti-foul Agents
• Anti-Static Agents
• Anti-Flammable Agents
• Anti-Caking / Settling Agents
• Corrosion Inhibitors
• Catalysts
• Plasticizers
• Contaminants, Leachables, Impurities, By-Products
41

42. Polymer & Small Molecule Analysis by
GPC-IR for ABS Plastic w/ No Extraction Step
GPC-IR Chromatogram (Blue) for ABS Sample and Ratio Plot of
Nitrile/Styrene (2240 cm-1/1495 cm-1).
Polymers
Identification Small Molecules
Compositional Additives
Variations Impurities
Degradants

43. Polymer Additive Analysis
GPC-IR for ABS Plastic w/ No Extraction Step
IR spectra at different elution times across the low MW peak of the SEC
analysis of ABS. Spectra indicate presence of multiple components.

44. Hyphenated Techniques to Characterize
Copolymers Poly(A-B)
Absorbance GPC/SEC
A/B composition
molar mass
ratio
high MW low MW SEC Time
Composition Hyphenated (Coupling) Techniques
Analysis:
IR
polymer chains
LC—NMR: Fractionation (Batching)
NMR LC-MS: for Low MW Portion
comonomer A
MS 2D LC: HPLC x SEC; IPC x SEC
HPLC GPC-IR comonomer B
44

45. GPC-IR to Characterize Compositional
Variations of Copolymers Poly(A-B)
IR Spectra
A
B
Absorbance
A/B composition
molar mass
ratio
high MW low MW GPC Time
polymer chains
comonomer A
comonomer B
45

46. Summary: GPC-IR Applications
Profile Polymer Compositions = f (Sizes)
Cross Linking Break Down
IR Spectra B A
A/B Ratio
Absorbance
High MW Low MW GPC
Elution
Time
 Map out Copolymer Compositions (A/B Ratio) across MWD (Sizes)
 Study Lot-to-Lot or Supplier-to-Supplier Variations
 Characterize Polymer Degradation from Processing:
 Loss of functional group (Reduced A/B)
46
 Cross-linking ( Higher MW)
 Break down ( Lower MW) & Detect low MW degradant
 De-Formulate Complex Polymer Mixtures

47. GPC-IR to Characterize MMA Copolymers by
IR Peak Ratios of Co-Monomer Contributions
Sample S MAA BA MMA DAAM Ratios
A 5% 12.5% 10% 60% 12.5% A/E, S/E
DAAM / E
B 15% 10% 75% Acid/Ester
C 25% 15% 10% 50% A/E, S/E
D (50:50 Acid/Ester
B/C Mix) 12.5% 15% 10% 62.5% S/Ester
Co-Monomers: S MAA BA MMA DAAM
CH3
C
=O 1734
1700 1536
704 1734
1605
2
1366
right peak
CH3
of doublet
Peak Ratios: 704/1734 1700/1734 Total Ester 1734 Base 1536/1734, 1366/1734
E = Total (MMA+BA) 1536/1366 (Ratio Check)

48. IR Spectrum Comparison (1800-1300cm-1) of
All 4 Samples at 23.2 Min. (~MWD Center)
normalized to carbonyl peak height: Ester (Total MMA + BA)
1734
Sample A: Black
Sample B: Blue
Sample C: Violet
Sample D: Green
COOH
1700
DAAM
Styrene 1366
1605 DAAM
1536

49. Summary: Characterizing MMA
Copolymers by GPC-IR
Sample S MAA BA MMA DAAM RESULTS
(Acid) (Ester) (Ester) Ratios across
MWD
A 5% 12.5% 10% 60% 12.5% Stable S/E Ratio
A/E Small Drift
DAAM/E Small Drift
B 15% 10% 75% S/Ester = 0
Acid/Ester Drifting
DAAM/Ester =0
C 25% 15% 10% 50% Stable S/E Ratio
A/E Small Drift
DAAM/Ester =0
D (50:50 S/Ester Drifting
B/C Mix) 12.5% 15% 10% 62.5% Acid/Ester Drifting
DAAM/Ester =0
49

50. Copovidone PVP/VAc Compositional
Drifts from Different Manf. Processes
.6
Copovidone: sample A
50
sample B
.5
% acetate comonomer
sample C
45
.4
Molecular Weight
max. IR absorbance
Distribution Comonomer Composition
.3
Distribution
40
Bulk 40% VAc
.2
35
.1
0 30
Molecular Weight
106 105 104 103 102
Copovidone A gave clear tablets while Copovidone C led to cloudy ones.