GPC-IR technology to deformulate complex polymer systems and to characterize copolymer compositional variations

1. Advanced Polymer Characterization
Akron Workshop -- 7/17/2012
GPC-IR to Characterize Copolymer
Compositions and
to Deformulate Complex Polymer Mixtures
Ming Zhou, PhD
Director of Applications Engineering
Spectra Analysis Instruments, Inc.
Marlborough, MA
Contact: ZhouM@Spectra-Analysis.com
1
Tel. 508-281-6276

2. OUTLINE
 Introduction: GPC-IR Technology & DiscovIR-LC System
 GPC-IR Applications: Case Studies
 Deformulate Complex Polymer Mixtures:
Adhesive, Lubricant Additives, Conductive Ink
 Characterize Copolymer Composition Variations across MWD:
SBR, PVP/VAc, PMMA/BA/MAA/S/DAAM
 Polymer Degradation Analysis: HPMCAS, PEA/MAA
2

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

4. GPC-IR Hyphenated System:
Principle and Information Output
GPC for the Separation of
the Polymers by MW or Size
Infrared Spectroscopy for
Compositional Information

5. Principle of a GPC-IR Hyphenated
System
GPC
DiscovIR-LC •Chromatography eluant is
nebulized and stripped of
mobile phase in the Hyphen
•Analytes deposited as a track
on a rotating ZeSn disk.
•Track passes through IR
energy beam of built-in
interferometer.
•A time-ordered set of IR
spectra are captured as a data
file set.

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

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

8. Hyphen: A Proprietary Desolvation
Technology
N2 Addition
Cyclone
Thermal
Cyclone Evaporator
From LC
Evaporator
Nebulization
Air Cooled
Condenser
Patent
pending:
Chilled PCT/US2007/
Condenser 025207
Particle Stream to DiscovIR
Waste Solvent

9. Desolvation Stage #1:
The Thermal Nebulization
•The thin-wall stainless steel capillary tube nebulizer is regulated to
evaporate approximately half the solvent (electric heating).
•Solvent expansion upon conversion to vapor increases the nebulizer
back pressure and create a high-speed jet of micrometer-sized liquid
droplets that contain all the solute.
•Gradients are acceptable as it is a self regulating system (gradient
changes monitored by changes in electrical resistance).

10. Desolvation Stage #2:
Inside the Cyclone Evaporator
•Centrifugal force holds the
droplets (solute) near the cyclone
wall. Just before the droplet goes
to dryness, its volume to surface
ratio becomes small enough that
it is dragged out of the cavity by
the exiting solvent vapor.
•Evaporative cooling protects the
solute from both evaporation and
degradation by limiting the
maximum solute temperature to
the solvent boiling point. The
solvent boiling point is reduced
by operating the cyclone in a
vacuum.

11. At the Condensers
Series of
Condensers
• After ejection from the cyclone, solvent vapor is
removed by diffusion to, and condensation on, the
cooled condenser walls.
• Stokes drag from the nitrogen gas maintains the
dried droplets in an aerosol suspension and limits
their loss by diffusion to the condenser walls.
• The condenser consists of an air cooled stage
followed by a Peltier cooled stage.
• The condensed solvent is collected in a waste
bottle.

12. ZnSe Sample Disk
 Rotate at tunable speed
10-0.3 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
12

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

14. Direct Deposition IR in Action
14

15. Features of DiscovIR-LC System
 Real-Time On-line Detection
 Microgram Sensitivity
 All GPC/SEC Solvents: e.g. THF, TCB, HFIP, Chloroform, DMF
 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

16. GPC-IR: Direct Deposition &
Data Processing
ZnSe Disk
16

17. 17

18. OUTLINE
 Introduction: GPC-IR Technology & DiscovIR-LC System
 GPC-IR Applications: Case Studies
 Deformulate Complex Polymer Mixtures:
Adhesive, Lubricant Additives, Conductive Ink
 Characterize Copolymer Composition Variations across MWD:
SBR, PVP/VAc, PMMA/BA/MAA/S/DAAM
 Polymer Degradation Analysis: HPMCAS, PEA/MAA
18

19. Characterizing Polymer Mixtures by
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 practical for single species.
 polymers • Compounded IR spectra for mixtures.
 additives
GPC only: 2 or 3 peaks ? IR only: Compounded spectra
.04
C .2
.03
B? .15
.02
.1
.01 A .05
0
0
2 4 6 8 10 12 14 4000 3500 3000 2500 2000 1500 1000

20. Case #1: Deformulate an Adhesive
Polymer Mixture: GPC-IR 3D View
Competitive study of an adhesive:
.05

for cost & margin comparison

for technical evaluation
.04
.03
ec na b os ba
.02
r
14
13
12
.01
11
10 GPC
Elution
9
0
Time, min
8
4000 3500 3000 2500 2000 1500 1000
2929
IR Wavenumber, cm-1 1724
C=O

21. GPC-IR Deformulation
of the Adhesive Polymer Mixture
B? C
A
Max (Band) Chromatogram at 2929 cm-1
B
A
Selected Band Chromatogram at 1724 cm-1

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

23. GPC-IR to Identify Components
C & B by Spectral Subtraction
Component C
Paraffin
Component B
Glycerol Rosin Ester

24. GPC Confirmation of the Identified
Components with Known Stds A, B & C
B C
A
A
B
C

25. Case #2: Deformulate Lubricant Additives
in SAE 15W-40 Motor Oil

Identification of additives like
stabilizers, viscosity modifiers, etc.

Stability: ageing & failure analysis
Additive Y
12
11
Additive
X
10 GPC
Elution
9
Time
8 (Min. & MW)
3500 3000 2500 2000 1500 1000
Wavenumber, cm-1
Low MW mineral oil (~85%) diverted after 12.2 min

26. Deformulation of Motor Oil
Additive X at RT 9.2 Minutes
IR database search: Styrene-Acrylate Copolymer

27. Deformulation of Motor Oil
Additive Y at RT 12 Minutes
IR database search: Polyisobutenyl Succinimide (PIBS)

28. Additive Deformulation in
Motor Oil Lubricant by GPC-IR
• De-formulated polymeric additives X & Y in motor oil lubricant
• Additive X at retention time 9.2 minutes
 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 at retention time 10-12 minutes
 Broad MW range: 8-30K (GPC)
 Polyisobutenyl Succinimide (PIBS) (IR database search)
 Dispersant for metal particles
 Small Comonomer Compositional Drift
[dimethyl (1367 cm-1) / imide (1700 cm-1)] Ratio Change < 10%
• Polymer degradation study
 Analyze polymer breakdown or cross-linking by GPC
 Detect oxidized intermediates by IR
 Oil change schedule

29. Case #3: Deformulate a Flexible
Conductive Ink by GPC-IR
Silver ink paste filled with Ag particles (~80% Wt)
• Designed to screen print flexible circuitry
such as membrane switches
• Extremely flexible after curing at 150°C for 30 minutes
• Very conductive even under 20x folding / crease stress tests
(ASTM F1683). 5 times better than the next competitor
• Understand the unique formulation technology
• Deformulate the complex polymer system

30. Deformulating the Conductive Ink
GPC-IR Chromatogram
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.: -10°C
Cyclone Temp.: 130°C
Condenser Temp.: 15°C
Disk Speed: 12 mm/min

31. Stacked IR Spectra of Components
A, B, C at their MWD Apexes
NH

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

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

34. Commercial IR Database Search
for Component C (Red): Cross-linker
Index % Match Compound Name
834 92.47 Desmodur LS-2800, CAS# 93919-05-2, MW 766, Cross-linking Agent
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

35. Reverse-Engineering the Conductive
Ink by GPC-IR Deformulation
• C: Desmodur LS-2800
C • Ketoxime blocked HDI trimer
• Latent cross-linking agent
Curing (150oC / 30 min)
B
• De-blocked C cross-linking
with Polymer B Chains
• Interpenetrating with Polymer A
A • Lock Ag fillers in place to form
conductive circuitry
• Super flexibility & elasticity
• Superior end-use properties

36. Summary: GPC-IR to Deformulate
Complex Polymer Mixtures
• GPC-IR is well adapted for the de-formulation of complex polymer systems
Separation of all the components of a mixture (polymer and small molecules)
Detection of each component by IR (solid phase transmission)
Identification by IR database search (commercial & proprietary databases)
• Useful:
 For competitive analysis / IP protection
 To find specific raw material supplier
 For problem solving / trouble shooting / contamination analysis
• Applicable to coatings, adhesives, inks, sealants, elastomers,
plastics, rubbers, composites, biopolymers …

37. OUTLINE
 Introduction: GPC-IR Technology & DiscovIR-LC System
 GPC-IR Applications: Case Studies
 Deformulate Complex Polymer Mixtures:
Adhesive, Lubricant Additives, Conductive Ink
 Characterize Copolymer Composition Variations across MWD:
SBR, PVP/VAc, PMMA/BA/MAA/S/DAAM
 Polymer Degradation Analysis: HPMCAS, PEA/MAA
37

38. Copolymers: Poly(A-B), Poly(A-B-C),…
 Copolymers provide enhanced characteristics of individual
comonomer constituents.
 In copolymers, important properties depend not only on MWD,
but also on the chemical composition distribution.
 Compositional drift refers to small variations of the
concentration of the comonomers across MWD.
 Copolymer product properties can be controlled/optimized by
controlling composition drift characteristics.

39. GPC-IR to Characterize Compositional
Variations of Copolymers Poly(A-B)
IR Spectra
A
molar mass
B
Absorbance
A/B composition
ratio
high MW low MW GPC Time
polymer chains
comonomer A
comonomer B
39

40. Case #4: GPC-IR to Characterize
Composition Drifts of SBR Copolymers
Monomers: S & B
Random
SBS Block

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

42. GPC-IR Analysis of SBR
IR Spectra at Different Elution Times
Compositional analysis of SBR based on characteristic IR absorbance
bands for styrene (1495 cm-1) and butadiene (968 cm-1).
B
968
S
1495

43. Compositional Drifts across MWD
for Styrene/Butadiene Copolymer
B
Bulk Average – 10% Styrene
S/B Ratio
S
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)

44. Compositional Drifts across MWD
for Styrene/Butadiene Copolymer
B Bulk Average – 44% Styrene
S/B Ratio
S
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)

45. Compositional Variations for
Various SBS Copolymers (Bimodal)
Dotted Curves:
MWD
Solid Curves:
S/B Ratios

46. GPC-IR Spectrum of Copovidone
Excipient - PVP/VAc Copolymer
Peak 1680 cm-1 from VP comonomer
Peak 1740 cm-1 from VAc comonomer

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

48. Case #5: GPC-IR to Characterize
Compositions of MMA Copolymers
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
1366
2
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

49. 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

50. Styrene/Ester Ratios across MWD by IR
Peak Ratios for MMA/BA/MAA Copolymer
704/1734 Peak Height Ratio, No Styrene Sample B
IR Spectrum at Red Marker
IR Spectrum at Blue Marker

51. Styrene/Ester Ratios across MWD by IR
Peak Ratios for MMA/BA/MAA/S Copolymer
704/1734 Peak Height Ratio Sample C
IR Spectrum at Red Marker
IR Spectrum at Blue Marker

52. Styrene/Ester Ratios across MWD by IR
Peak Ratios for Sample D = 50%B+50%C
704/1734 Peak Height Ratio Sample D
IR Spectrum at Red Marker
IR Spectrum at Blue Marker

53. GPC-IR Chromatogram Comparison (B & C
MWD Mismatch) of Samples B, C & D
Sample B
MMA/BA/MAA
No Styrene Terpolymer
Sample C
MMA/BA/MAA/S
Stable Styrene Level Tetrapolymer
Sample D
50%B + 50%C
Styrene Level Variation across MWD

54. 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
54

55. OUTLINE
 Introduction: GPC-IR Technology & DiscovIR-LC System
 GPC-IR Applications: Case Studies
 Deformulate Complex Polymer Mixtures:
Adhesive, Lubricant Additives, Conductive Ink
 Characterize Copolymer Composition Variations across MWD:
SBR, PVP/VAc, PMMA/BA/MAA/S/DAAM
 Polymer Degradation Analysis: HPMCAS, PEA/MAA
55

56. Excipient Degradation from
Hot Melt Extrusion (HME) Process
 Hot Melt Extrusion Process: To Make Solid Dispersions
for Low Solubility Drugs to Improve Bioavailability
 Degradation Issues
• Excipient & API Degradation at High Temp. (100-200C)
• Discoloration / Residues
• Degradant / API Interactions
 Process Variables
• Temperature
• Time (Screw Speed)
• Torque
• Screw / Die Designs
56

57. Case #6: GPC-IR to Analyze HPMCAS
Degradation from HME Processing
Polymer Change ?
Unprocessed
Processed at 160C
Degradant ?
Processed at 220C

58. Degradant ID from HPMCAS (220C)
in Hot Melt Extrusion Process
IR Database Search Result: Succinic Acid

59. HPMCAS Polymer Degradation
in Hot Melt Extrusion Process
-C=O
OH
Functional Group Ratio Changes from High Temp Process (Sample
C)

60. Matrix Study: HPMCAS Excipient
Stability & Degradation from HME
Sample # Extrusion Sample Sample Degradant Polymer
Temp. Color in THF Formed ? Change?
(~0.5%)
Ref. Not White Clear None None
Processed Powder Solution
A 180 C Yellowish Clear
Powder Solution
B 200 C Yellowish Some ? ?
Powder Residue
C 220 C Brownish Some ? ?
Powder Residue
60

61. Degradant Level Comparison of
HPMCAS Samples after HME
Band Chromatograms at 1670 cm-1
Sample C: Violet (220C)
Sample B: Brown (200C)
Sample A: Aqua (180C)
Sample R: Blue (Ref.)
Degradant
at 14.6 Min.
Normalized to Additive Level
Additive
at 14.1 Min.

62. Degradant Level Increases with
Higher HME Processing Temp.
~190oC
Samples: Ref. A B C

63. HPMCAS Matrix Study Summary:
Degradation & Stability from HME
Sample # Extrusion Sample Sample Degradant Polymer
Temp. Color in THF Formed Change
(~0.5%)
Ref. Not White Clear None None
Processed Powder Solution
A 180 C Yellowish Clear Little None
Powder Solution Succinic
Acid
B 200 C Yellowish Some Succinic
Powder Residue Acid
C 220 C Brownish Some Succinic Higher
Powder Residue Accid OH/C=O
Ratio
63

64. GPC-IR Analysis of HPMCAS
Degradation in HME Process
 Detected Degradants: Succinic Acid & Derivatives
 Detected Functionality Change: Ratio Hydroxyl Vs. Carbonyl
 Help Understand Polymer Degradation Mechanism
 Study Excipient / Drug API Interactions
 Define Safe Process Window: Quality by Design (QbD)
 Polymer Blends with Plasticizers and Additives
HOOC-CH2-CH2-C=O
CH3-C=O
Figures: Schematic Structures of HPMC-AS Polymeric Excipient

65. Case #7: GPC-IR to Analyze PEA/MAA
Degradation from HME Process
Sample # Extrusion Screw Sample Sample Degradant Polymer
Temp. Speed Color in THF Formed Changed
(~0.5%) ? ?
S0 Not White Clear
Processed Solution
S1 130 C 250 rpm Off Clear
White Solution
S2 160 C 250 rpm Off Clear
White Solution
S3 190 C 250 rpm Brownish Some ? ?
Residue
Note: Samples S1-S3 contain 20% plasticizer TEC to assist extrusion process. 65

66. IR Spectra of PEA/MAA Samples at
Polymer MWD Apex (ET ~9.4 Min.)
S0 – Green Ref COOEt
S1 – Violet 130C 1735
S2 – Blue 160C
S3 – Black 190C
COOH
1705
NCE?
1805 cm-1
CO-OH
66

67. PEA/MAA Crosslinked to Anhydride
from COOH at Higher HME Temp
COOEt
1735 S0 – Green Ref
S1 – Violet 130C
S2 – Blue 160C
COOH S3 – Black 190C
1705
NCE?
1805 cm-1
67

68. PEA/MAA Matrix Study Summary:
Degradation & Stability from HME
Sample # Extrusion Screw Sample Sample Degradant Polymer
Temp. Speed Color in THF Formed Change
(~0.5%)
S0 Not White Clear None None
Processed Solution
S1 130 C 250 rpm Off Clear Trace
White Solution Anhydrides
S2 160 C 250 rpm Off Clear Anhydrides Acid/Ester
White Solution Ratio
Decreased
S3 190 C 250 rpm Brownish Some Anhydrides Acid/Ester
Residue Ratio
Decreased
68

69. Common Polymeric Excipients for Hot
Melt Extrusion Studied by GPC-IR
?
HOOC-CH2-CH2-C=O
HPMCAS ~ 190C COCH3
PEA/MAA ~ 160C
HO
O
O
N
l
O m
n
Copovidone > 200C O
O
O
H - (OCH2CH2 )n - OH SoluPlus > 200C
PEG HO
 Excipient Combinations with Plasticizers and Additives
69

70. IR Band Identifications
of SoluPlus Copolymer
HO
Group VAc VCap Note
PEG VCap
O
O C=O 1738 cm-1 1642 cm-1 Peak Ratios for
N
Compositional
l
O
Drifts w/ MWD
m
n
O Acetyl 1244 cm-1 Internal Ratio
O Check vs.
O Peak 1738
VAc
CH3 1374 cm-1
HO
Peak 1642 cm-1 from VCap comonomer Methyl Acetyl
1374 1244
Peak 1738 cm-1 from VAc comonomer

71. SoluPlus Stability: VAc/VCap Ratios
Drift Similarly across MWD after HME
All VAc/VCap Ratios
Within Lot-to-Lot
Variations
R – Green Unprocessed Reference
A – Black Processed at 120C @ 125rpm
B – Blue Processed at 120C @ 250rpm
C – Brown Processed at 180C @ 125rpm
D – Violet Processed at 180C @ 250rpm
71

72. GPC-IR Matrix Study Summary:
SoluPlus Stability in HME Processing
Sample # Temp. Screw Sample Solution Degradant Polymer
(C) Speed Color in DMF Formed Changed ?
(rpm) (~2%) ?
R Not White Clear Not VAc/VCap
(Ref.) Processed Powder Solution Detected Ratio Drift
w/ MWD
A 120 125 Off Clear Not Same
White Solution Detected VAc/VCap
Ratio Drift
B 120 250 Off Clear Not Same
White Solution Detected VAc/VCap
Ratio Drift
C 180 125 Yellowish Clear Not Same
White Solution Detected VAc/VCap
Ratio Drift
D 180 250 Yellowish Clear Not Same
White Solution Detected VAc/VCap
72
Ratio Drift

73. Summary: GPC-IR Applications in
Polymer-Related Industries
 DiscovIR-LC is a Powerful Tool for Polymers, Additives & Materials Analysis
 Deformulate complex polymer mixtures: identify polymer components
 Characterize copolymer composition variations across MWD
 Characterize polymer changes: degradation or modification
 Useful:
 For competitive analysis / IP protection
 To find specific raw material supplier or qualify a second supplier
 For new copolymer R&D and process scale-up
 To characterize polymer degradation: ageing study, failure analysis
 For problem solving / trouble shooting as general analytical capability
 Applicable to Coatings, Adhesives, Inks, Sealants, Elastomers,
Plastics, Rubbers, Composites, Biopolymers ……

74. Summary: GPC-IR to Deformulate
Complex Polymer Systems
IR Spectra
X? Y? Z?
IR ID A-B Copolymer C Polymer Additive
IR Database Product Name Product # Brand Name
Search & Supplier & Supplier & Supplier

75. Summary: GPC-IR to Characterize
Copolymer Compositions across MWD
IR Spectra B
A/B
Ratios A
A-B C
Composition Supplier-to-Supplier Built-in Feature/Difference for ID
Drifts & Lot-to-Lot Variations Copolymer R&D / Process Control
Variations & Incoming QC for Users

76. Summary: GPC-IR to Characterize Copolymer
Degradation from Ageing / Processing
A/B
Ratios Degradation
A-B C Degradants
Degradation Loss of Functional Group A (Reduced A/B Ratios)
Polymer Breakdown ( Lower MW Degradants)
Cross-linking ( Higher MW with New Functional Groups)
Confirm No Degradation / Stability

77. DiscovIR-GPC to Characterize
Polymer Stability in Lubricant Oils
X0  ID: SEBS
Ageing @ 170C
G0: 0 hr
G12: 12 hr
G24: 24 hr
G36: 36 hr
G48: 48 hr
X1
X3
Y0
X2
X4
Note: Base oil was diverted at 25 min.

78. DiscovIR-GPC to Characterize
Polymer Degradation in Oils
X0  ID: SEBS
Ageing @ 170C
G0: 0 hr Oxidizing
G12: 12 hr Ethers (1000-1200 cm-1)
G24: 24 hr Oxiranes (806 cm-1)
G36: 36 hr
G48: 48 hr
X1
X3
Y0
X2
X4

79. DiscovIR-GPC to Characterize
Polymer Degradation in Oils
X0  ID: SEBS Oxidative
Breakdown
Ageing @ 170C
Carbonyls
G0: 0 hr Oxidizing Oxiranes
G12: 12 hr Ethers Ethers
G24: 24 hr Oxiranes
G36: 36 hr
G48: 48 hr
X1
X3
Y0
X2
X4

80. Summary: GPC-IR Applications
Profile Polymer Compositions = f (Sizes)
Cross Linking Break Down
IR Spectra B A
A/B Ratio
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)
80
 Cross-linking ( Higher MW)
 Break down ( Lower MW) & Detect low MW degradant
 De-Formulate Complex Polymer Mixtures

81. 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
81

82. Comparison of Max Band (Black)
& Selected Band Chromatograms
Band 1690 cm-1
Max Band
Band 1510 cm-1
Default
At 1730 cm-1 A
Band 730 cm-1 B
C
Elution Time (Min.)

83. 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 in Green).
Polymers Small Molecules
Additives
Impurities
Degradants

84. 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.

85. SEC-IR to Characterize Compositional
Heterogeneity of Acrylate Copolymers
Ref.: Mark Rickard et al, FACSS2011, Dow Chemical Midland
Corporate R&D Analytical Sciences

86. GPC-IR to Characterize Compositional
Heterogeneity of Acrylate Copolymers
Monomer Monomer Normalization
Homopolymer FT-IR spectra Frequency Frequency
0.80 PBMA_reference1
0.75
PBMA
PEA_reference 1168
1149
EA 1026 (cm-1) 1731 (cm-1)
PMMA_reference
0.70 PBA_reference
0.65
PEA
BMA 1072 (cm-1) 1731 (cm-1)
0.60
0.55
PMMA
0.50
PBA MMA 1149 (cm-1) 1731 (cm-1)
Absorbance
0.45 1072
0.40 1026
0.35
BA 1168 (cm-1) 1731 (cm-1)
0.30
0.25
0.20
0.15
0.10
0.05
1350 1300 1250 1200 1150 1100 1050 1000 950 900
Wavenumbers (cm-1)
Compositional profiles for each monomer were constructed via
intensity ratios at selected IR bands normalized to the ester carbonyl intensity.