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: [email protected]
Tel. 508-281-6276 1
Advanced Polymer Characterization Akron Workshop -- 7/17/2012
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
Hyphenated Technologies & Major Applications
Liquid ChromatographyLiquid Chromatography
MassSpectroscopy
Infra RedSpectroscopy
Infra RedSpectroscopy
Separation
Applications Small Molecules Copolymer Compositions
Proteins Polymer Mixtures
Additive Analysis
LC = GPC / SEC or HPLC
Detection &
Data Analysis
LC-MS LC-IR
GPC-IR Hyphenated System: Principle and Information Output
Infrared Spectroscopy for Compositional Information
GPC for the Separation of the Polymers by MW or Size
Principle of a GPC-IR Hyphenated System
•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.
GPC
DiscovIR-LC
LC-IR Hyphenated System
HPLCor GPC
HyphenDesolvation
DepositionMicroscopic FTIR
System ControlData Processing
Hyphen: A Proprietary Desolvation Technology
CycloneEvaporator
Thermal
NebulizationFrom LC
N2 Addition
ChilledCondenser
Waste Solvent
Particle Stream to DiscovIR
Air CooledCondenser
Cyclone
Evaporator
Patent pending: PCT/US2007/025207
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).
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.
At the 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.
Series of Condensers
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
What is Direct Deposition FTIR?
Continuous Polymer Tracks (GPC-IR)Separated Dots from HPLC-IRSeparated Dot Depositing on Disk
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
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
Characterizing Polymer Mixtures byGPC (Size) or IR (Composition)
0
.01
.02
.03
.04
2 4 6 8 10 12 14
GPC: Chromatographic Separation of Components
• Provides size distribution (MWD).• No identification of
polymers additives
IR: Fingerprinting of Chemical Compositions
• Unambiguous identification only practical for single species.• Compounded IR spectra for mixtures.
0
.05
.1
.15
.2
4000 3500 3000 2500 2000 1500 1000
GPC only: 2 or 3 peaks ? IR only: Compounded spectra
A
B?
C
Competitive study of an adhesive: for cost & margin comparison for technical evaluation
Case #1: Deformulate an Adhesive Polymer Mixture: GPC-IR 3D View
8
9
10
11
12
13
14
0
.01
.02
.03
.04
.05
4000 3500 3000 2500 2000 1500 1000
abso
rban
ce
1724
C=O
IR Wavenumber, cm-1
GPC ElutionTime, min
2929
GPC-IR Deformulationof the Adhesive Polymer Mixture
ACB?
Max (Band) Chromatogram at 2929 cm-1
Selected Band Chromatogram at 1724 cm-1
A
B
IR Database Search to Identify Peak A at 10 Min. as EVA Polymer
-CH2
2929
C=O1724
A
GPC-IR to Identify Components C & B by Spectral Subtraction
Component C Paraffin
Component BGlycerol Rosin Ester
A
C
B
CA
B
GPC Confirmation of the Identified Components with Known Stds A, B & C
Case #2: Deformulate Lubricant Additives in SAE 15W-40 Motor Oil
8
9
10
11
12
0
.05
.1
.15
4000 3500 3000 2500 2000 1500 1000
Identification of additives like stabilizers, viscosity modifiers, etc. Stability: ageing & failure analysis
Wavenumber, cm-1
GPC Elution Time(Min. & MW)
Additive X
Additive Y
Low MW mineral oil (~85%) diverted after 12.2 min
Deformulation of Motor OilAdditive X at RT 9.2 Minutes
IR database search: Styrene-Acrylate Copolymer
4000 3500 3000 2500 2000 1500 1000
wavenumber, cm-1
Shell Rotella T Heavy Duty 15W-409.2 minute eluant
Deformulation of Motor Oil Additive Y at RT 12 Minutes
IR database search: Polyisobutenyl Succinimide (PIBS)
4000 3500 3000 2500 2000 1500 1000
wavenumber, cm-1
Shell Rotella T Heavy Duty 15W-4012 minute eluant
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
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
Deformulating the Conductive Ink GPC-IR Chromatogram
Column: 2 x Jordigel DVB Mixed BedMobile Phase: THF at 1.0 ml/minSample Conc.:~5 mg/ml in THFInjection Volume: 60 μl IR Detector Res.: 8 cm-1
ZnSe Disk Temp.: -10°C
Cyclone Temp.: 130°C
Condenser Temp.: 15°CDisk Speed: 12 mm/min
Stacked IR Spectra of Components A, B, C at their MWD Apexes
NH
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)
Commercial IR Database Search for Polymer B (Blue): Polyurethane
Index % Match Compound Name
503 88.13 Spensol L-53 UROTUF L-53 Polyurethane 949 87.51 Polyester Polyol 0305424 87.33 Polycaprolactone944 87.29 Polyester Polyol 0200212 86.86 UCAR Cyracure UVR-6351
NH
OH
Commercial IR Database Search for Component C (Red): Cross-linker
Index % Match Compound Name834 92.47 Desmodur LS-2800, CAS# 93919-05-2, MW 766, Cross-linking Agent3249 65.30 Caffeine; 1,3,7-Trimethylxanthine9302 64.76 Monophenylbutazone615 62.15 Betulinic acid; 3-Hydroxylup-20(29)-en-28-oic acid860 62.05 Spenlite M-27
N
N
N
(CH2)6(H2C)6
O
OO
(CH2)6
HN
NH
HN O
N
O
N
O
N
O
O
O
Reverse-Engineering the Conductive Ink by GPC-IR Deformulation
N
N
N
(CH2)6(H2C)6
O
OO
(CH2)6
HN
NH
HN O
N
O
N
O
N
O
O
O
• C: Desmodur LS-2800• Ketoxime blocked HDI trimer• Latent cross-linking agent
N
N
N
(CH2)6(H2C)6
O
OO
(CH2)6
N
NN C OCO
C
O
N
H
C O
N
H
C O
O
O
N
O
O
H
• De-blocked C cross-linking with Polymer B Chains• Interpenetrating with Polymer A• Lock Ag fillers in place to form conductive circuitry• Super flexibility & elasticity• Superior end-use properties
Curing (150oC / 30 min)
C
B
A
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 …
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
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.
GPC-IR to Characterize Compositional Variations of Copolymers Poly(A-B)
39
high MW low MW
mola
r m
ass
comonomer A
comonomer B
A/B compositionratio
polymer chains
Ab
sorb
ance
AB
GPC Time
IR Spectra
Case #4: GPC-IR to Characterize Composition Drifts of SBR Copolymers
SBS Block
Random
Monomers: S & B
GPC-IR Spectrum Snapshot of Styrene/Butadiene Copolymer
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.
Cove thisThe three bands filled in red arise from the styrene comonomer (1605, 1495, and 698 cm-1)
1605
1495
698
968
GPC-IR Analysis of SBRIR 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).
1495
968
B
S
Compositional Drifts across MWD for Styrene/Butadiene Copolymer
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)
Bulk Average – 10% Styrene
B
S
S/B Ratio
Compositional Drifts across MWD for Styrene/Butadiene Copolymer
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)
Bulk Average – 44% StyreneB
S
S/B Ratio
Compositional Variations for Various SBS Copolymers (Bimodal)
Dotted Curves:MWD
Solid Curves:S/B Ratios
GPC-IR Spectrum of Copovidone Excipient - PVP/VAc Copolymer
Peak 1680 cm-1 from VP comonomer
Peak 1740 cm-1 from VAc comonomer
0
.1
.2
.3
.4
.5
.6
106 104 103 102105Molecular Weight
Copovidone: sample A
30
35
40
45
50 % acetate com
onomer
Comonomer CompositionDistribution
sample B
sample C
0
.1
.2
.3
.4
.5
.6
106 104 103 102105
sample B
sample C
Bulk 40% VAc for All
ma
x. I
R
ab
sorb
an
ce Molecular WeightDistribution
Copovidone PVP/VAc Compositional Drifts from Different Manf. Processes
Copovidone A gave clear tablets while Copovidone C led to cloudy ones.
Case #5: GPC-IR to Characterize Compositions of MMA Copolymers
CH3
CH3
2
=O
C
Co-Monomers: S MAA BA MMA DAAM
17347041605
15361700
1366right peakof doublet
Sample S MAA BA MMA DAAM Ratios
A 5% 12.5% 10% 60% 12.5% A/E, S/EDAAM / E
B 15% 10% 75% Acid/Ester
C 25% 15% 10% 50% A/E, S/E
D (50:50 B/C Mix) 12.5% 15% 10% 62.5%
Acid/EsterS/Ester
1734
Peak Ratios: 704/1734 1700/1734 Total Ester 1734 Base 1536/1734, 1366/1734 E = Total (MMA+BA) 1536/1366 (Ratio Check)
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
DAAM1366
DAAM1536
Sample A: BlackSample B: BlueSample C: VioletSample D: Green
COOH1700
Styrene 1605
Styrene/Ester Ratios across MWD by IR Peak Ratios for MMA/BA/MAA Copolymer
704/1734 Peak Height Ratio, No Styrene
IR Spectrum at Red Marker
IR Spectrum at Blue Marker
Sample B
Styrene/Ester Ratios across MWD by IR Peak Ratios for MMA/BA/MAA/S Copolymer
704/1734 Peak Height Ratio
IR Spectrum at Red Marker
IR Spectrum at Blue Marker
Sample C
Styrene/Ester Ratios across MWD by IR Peak Ratios for Sample D = 50%B+50%C
704/1734 Peak Height Ratio
IR Spectrum at Red Marker
IR Spectrum at Blue Marker
Sample D
Sample B
MMA/BA/MAA
Terpolymer
Sample C
MMA/BA/MAA/S
Tetrapolymer
Sample D
50%B + 50%C
GPC-IR Chromatogram Comparison (B & C MWD Mismatch) of Samples B, C & D
No Styrene
Styrene Level Variation across MWD
Stable Styrene Level
54
Sample S MAA(Acid)
BA(Ester)
MMA(Ester)
DAAM RESULTSRatios across
MWD
A 5% 12.5% 10% 60% 12.5% Stable S/E RatioA/E Small Drift
DAAM/E Small Drift
B 15% 10% 75% S/Ester = 0Acid/Ester Drifting
DAAM/Ester =0
C 25% 15% 10% 50% Stable S/E RatioA/E Small DriftDAAM/Ester =0
D (50:50 B/C Mix) 12.5% 15% 10% 62.5%
S/Ester DriftingAcid/Ester Drifting
DAAM/Ester =0
Summary: Characterizing MMA Copolymers by GPC-IR
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
Case #6: GPC-IR to Analyze HPMCAS Degradation from HME Processing
Unprocessed
Processed at 160C
Processed at 220C
Degradant ?
Polymer Change ?
Degradant ID from HPMCAS (220C) in Hot Melt Extrusion Process
IR Database Search Result: Succinic Acid
HPMCAS Polymer Degradationin Hot Melt Extrusion Process
Functional Group Ratio Changes from High Temp Process (Sample C)
OH
-C=O
Matrix Study: HPMCAS Excipient Stability & Degradation from HME
60
Sample # ExtrusionTemp.
SampleColor
Sample in THF(~0.5%)
DegradantFormed ?
PolymerChange?
Ref. Not Processed
WhitePowder
ClearSolution
None None
A 180 C YellowishPowder
ClearSolution
B 200 C YellowishPowder
Some Residue
? ?
C 220 C BrownishPowder
Some Residue
? ?
Degradant Level Comparison of HPMCAS Samples after HME
Normalized to Additive Level
Additive at 14.1 Min.
Degradant at 14.6 Min.
Sample C: Violet (220C)Sample B: Brown (200C)Sample A: Aqua (180C)Sample R: Blue (Ref.)
Band Chromatograms at 1670 cm-1
Degradant Level Increases with Higher HME Processing Temp.
Ref. A B CSamples:
~190oC
HPMCAS Matrix Study Summary: Degradation & Stability from HME
63
Sample # ExtrusionTemp.
SampleColor
Sample in THF(~0.5%)
DegradantFormed
PolymerChange
Ref. Not Processed
WhitePowder
ClearSolution
None None
A 180 C YellowishPowder
ClearSolution
Little Succinic
Acid
None
B 200 C YellowishPowder
Some Residue
Succinic Acid
C 220 C BrownishPowder
Some Residue
Succinic Accid
HigherOH/C=O
Ratio
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
Figures: Schematic Structures of HPMC-AS Polymeric Excipient
CH3-C=O
HOOC-CH2-CH2-C=O
Case #7: GPC-IR to Analyze PEA/MAA Degradation from HME Process
65
Sample # ExtrusionTemp.
Screw Speed
SampleColor
Sample in THF(~0.5%)
DegradantFormed
?
PolymerChanged
?
S0 Not Processed
White ClearSolution
S1 130 C 250 rpm Off White
ClearSolution
S2 160 C 250 rpm OffWhite
ClearSolution
S3 190 C 250 rpm Brownish Some Residue
? ?
Note: Samples S1-S3 contain 20% plasticizer TEC to assist extrusion process.
IR Spectra of PEA/MAA Samples at Polymer MWD Apex (ET ~9.4 Min.)
66
S0 – Green RefS1 – Violet 130CS2 – Blue 160CS3 – Black 190C
COOEt 1735
COOH 1705
CO-OH
NCE?1805 cm-1
PEA/MAA Crosslinked to Anhydride from COOH at Higher HME Temp
67
COOEt 1735
COOH 1705
S0 – Green RefS1 – Violet 130CS2 – Blue 160CS3 – Black 190C
NCE?1805 cm-1
PEA/MAA Matrix Study Summary: Degradation & Stability from HME
68
Sample # ExtrusionTemp.
Screw Speed
SampleColor
Sample in THF(~0.5%)
DegradantFormed
PolymerChange
S0 Not Processed
White ClearSolution
None None
S1 130 C 250 rpm Off White
ClearSolution
TraceAnhydrides
S2 160 C 250 rpm OffWhite
ClearSolution
Anhydrides Acid/Ester Ratio
Decreased
S3 190 C 250 rpm Brownish Some Residue
Anhydrides Acid/Ester Ratio
Decreased
Common Polymeric Excipients for Hot Melt Extrusion Studied by GPC-IR
69
COCH3
HOOC-CH2-CH2-C=O
NO
O
O
OH
O
O
OH
O
l
m
n
H - (OCH2CH2 )n - OH
HPMCAS ~ 190C
PEA/MAA ~ 160C
Copovidone > 200C
SoluPlus > 200CPEG
Excipient Combinations with Plasticizers and Additives
?
IR Band Identifications of SoluPlus Copolymer
Peak 1642 cm-1 from VCap comonomer
Peak 1738 cm-1 from VAc comonomer
NO
O
O
OH
O
O
OH
O
l
m
n
Group VAc
VCap Note
C=O 1738 cm-1 1642 cm-1 Peak Ratios for Compositional Drifts w/ MWD
Acetyl 1244 cm-1 Internal Ratio Check vs. Peak 1738
CH3 1374 cm-1
Acetyl1244
Methyl1374
VCap
VAc
PEG
SoluPlus Stability: VAc/VCap Ratios Drift Similarly across MWD after HME
71
R – Green Unprocessed ReferenceA – Black Processed at 120C @ 125rpmB – Blue Processed at 120C @ 250rpmC – Brown Processed at 180C @ 125rpmD – Violet Processed at 180C @ 250rpm
All VAc/VCap RatiosWithin Lot-to-LotVariations
GPC-IR Matrix Study Summary: SoluPlus Stability in HME Processing
72
Sample # Temp. (C)
Screw Speed (rpm)
SampleColor
Solution in DMF(~2%)
DegradantFormed
?
PolymerChanged ?
R(Ref.)
Not Processed
WhitePowder
ClearSolution
Not Detected
VAc/VCap Ratio Drift w/
MWD
A 120 125 OffWhite
ClearSolution
Not Detected
Same VAc/VCap Ratio Drift
B 120 250 OffWhite
ClearSolution
Not Detected
Same VAc/VCap Ratio Drift
C 180 125 YellowishWhite
ClearSolution
Not Detected
Same VAc/VCap Ratio Drift
D 180 250 YellowishWhite
ClearSolution
Not Detected
Same VAc/VCap Ratio Drift
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 ……
Summary: GPC-IR to Deformulate Complex Polymer Systems
X? Y? Z?
IR Spectra
IR ID A-B Copolymer C Polymer Additive IR Database Product Name Product # Brand NameSearch & Supplier & Supplier & Supplier
Summary: GPC-IR to Characterize Copolymer Compositions across MWD
A-B C
IR Spectra
Composition Supplier-to-Supplier Built-in Feature/Difference for IDDrifts & Lot-to-Lot Variations Copolymer R&D / Process ControlVariations & Incoming QC for Users
A/B Ratios A
B
Summary: GPC-IR to Characterize Copolymer Degradation from Ageing / Processing
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
A-B C Degradants
A/B Ratios Degradation
DiscovIR-GPC to Characterize Polymer Stability in Lubricant Oils
X3
X4
X1
X2
X0 ID: SEBS
Y0
Ageing @ 170CG0: 0 hrG12: 12 hrG24: 24 hrG36: 36 hrG48: 48 hr
Note: Base oil was diverted at 25 min.
X3
X4
X1
X2
X0 ID: SEBS
Y0
Ageing @ 170CG0: 0 hrG12: 12 hrG24: 24 hrG36: 36 hrG48: 48 hr
DiscovIR-GPC to Characterize Polymer Degradation in Oils
OxidizingEthers (1000-1200 cm-1)Oxiranes (806 cm-1)
X3
X4
X1
X2
X0 ID: SEBS
Y0
Ageing @ 170CG0: 0 hrG12: 12 hrG24: 24 hrG36: 36 hrG48: 48 hr
DiscovIR-GPC to Characterize Polymer Degradation in Oils
OxidizingEthersOxiranes
Oxidative BreakdownCarbonylsOxiranesEthers
80
High MW Low MW GPC Elution
Time
A/B RatioA
B
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) Cross-linking ( Higher MW) Break down ( Lower MW) & Detect low MW degradant
De-Formulate Complex Polymer Mixtures
IR Spectra
Break DownCross Linking
Summary: GPC-IR ApplicationsProfile Polymer Compositions = f (Sizes)
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
Comparison of Max Band (Black)& Selected Band Chromatograms
A
BC
Elution Time (Min.)
Band 1690 cm-1
Band 1510 cm-1
Band 730 cm-1
Max BandDefault At 1730 cm-1
Polymer & Small Molecule Analysis byGPC-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).
Small Molecules Additives Impurities Degradants
Polymers
Polymer Additive AnalysisGPC-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.
SEC-IR to Characterize Compositional Heterogeneity of Acrylate Copolymers
Ref.: Mark Rickard et al, FACSS2011, Dow Chemical Midland Corporate R&D Analytical Sciences
GPC-IR to Characterize Compositional Heterogeneity of Acrylate Copolymers
10721026
11491168
PBMA_reference1PEA_referencePMMA_referencePBA_reference
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
Abs
orba
nce
900 950 1000 1050 1100 1150 1200 1250 1300 1350
Wavenumbers (cm-1)
Monomer Monomer Frequency
Normalization Frequency
EA 1026 (cm-1) 1731 (cm-1)
BMA 1072 (cm-1) 1731 (cm-1)
MMA 1149 (cm-1) 1731 (cm-1)
BA 1168 (cm-1) 1731 (cm-1)
Compositional profiles for each monomer were constructed via intensity ratios at selected IR bands normalized to the ester carbonyl intensity.
Homopolymer FT-IR spectra
PBMA
PEA
PMMA
PBA1072
1026
11491168
PBMA_reference1PEA_referencePMMA_referencePBA_reference
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
Abs
orba
nce
900 950 1000 1050 1100 1150 1200 1250 1300 1350
Wavenumbers (cm-1)
PBMA
PEA
PMMA
PBA1072
1026
11491168
PBMA_reference1PEA_referencePMMA_referencePBA_reference
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
Abs
orba
nce
900 950 1000 1050 1100 1150 1200 1250 1300 1350
Wavenumbers (cm-1)
PBMA
PEA
PMMA
PBA