De-Formulating Complex Polymer Mixtures
by GPC-IR Hyphenated Technology
Ming Zhou, PhD
Director of Applications Engineering
Spectra Analysis Instruments, Inc.
Marlborough, MA
Contact: [email protected]
American Coatings Conference
May 7, 2012
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
Liquid Chromatography
Mass
SpectroscopyInfra Red
Spectroscopy
Separation
Detection &
Data Analysis
LC-MS LC-IR
Hyphenated Technologies &
Major Applications
Applications Small Molecules Copolymer Compositions
Proteins Polymer Mixtures
Additive Analysis
LC = GPC or HPLC
LC-IR Hyphenated System
GPC
or HPLC
Hyphen
Desolvation
Deposition
Microscopic FTIR
System Control
Data Processing
How is the Solvent Removed?
Cyclone
EvaporatorThermal Nebulization
From LC
N2 Addition
Chilled
Condenser
Waste Solvent
Particle Stream to DiscovIR
Air Cooled
Condenser
Cyclone
Evaporator
Patent pending: PCT/US2007/025207
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 transparent8
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 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
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
Case #1: De-Formulate an Adhesive
GPC (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 species.
• Additives not identified.
IR: Fingerprinting
of Chemical Compositions
• Unambiguous identification only
practical for single species.
• Compounded IR spectra for mixtures
• Composition drift not determined.
0
.05
.1
.15
.2
4000 3500 3000 2500 2000 1500 1000
Hot-melt adhesive (Mixture)
GPC only: 2 or 3 peaks ?
Hot-melt adhesive (Mixture)
IR only: Compounded spectra
A
B?
C
8
9
10
11
12
13
14
0
.01
.02
.03
.04
.05
4000 3500 3000 2500 2000 1500 1000
GPC
Elution
Time, min
IR Wavenumber, cm-1
ab
so
rba
nc
e
GPC-IR Data 3D View: De-Formulate
the Adhesive Polymer Mixture
1724
GPC-IR De-Formulation
of the Adhesive Polymer Mixture
A
CB?
IR Band Chromatogram at 1724 cm-1
IR Max (Band) Chromatogram at 2929 cm-1
CH2
2929C=O
1724
GPC-IR Database Search to Identify
Peak A at 10 Min. as EVA Polymer
A
GPC-IR to Identify Components
C & B by Spectral Subtraction
Component C
Paraffin
Component B
A
C
B
C
AB
GPC Confirmation of the De-Formulated
Components with Known Stds A, B & C
Case #2: To De-Formulate Lubricant
Additives in Motor Oil: GPC-IR 3D View
8
9
10
11
12
0
.05
.1
.15
4000 3500 3000 2500 2000 1500 1000
SAE 15W-40 Heavy Duty Oil in THF
Low MW Mineral Oil (~85%) Diverted after 12.2 min
Wavenumber, cm-1
Elution
Time
(Min. & MW)
Additive X
Additive Y
De-Formulation of Motor Oil
Additive X @ RT 9.2 Min
IR Database Search: Styrene-Acrylate Copolymer
4000 3500 3000 2500 2000 1500 1000
wavenumber, cm-1
Shell Rotella T Heavy Duty 15W-40
9.2 minute eluant
Lubricant De-Formulation of
Motor Oil Additive Y @ RT 12 Min
IR database Search: Polyisobutenyl Succinimide (PIBS)
4000 3500 3000 2500 2000 1500 1000
wavenumber, cm-1
Shell Rotella T Heavy Duty 15W-40
12 minute eluant
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
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
De-Formulating the Conductive Ink GPC-IR Chromatogram Using 2 x GPC Columns
B
C
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
Stacked IR Spectra of Components A, B, C
at Different GPC Times (~ MWD Centers)
Comparison of Max Band Chromatogram
(Black) & Selected Band Chromatograms
A
B
C
Elution Time (Min.)
Band 1690 cm-1
Band 1510 cm-1
Band 730 cm-1
Max Band
Default
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
In-House Database Match of Polymer A
(Red Spectrum) with Flex Resin (Blue Std)
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
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
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
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
Summary: GPC-IR to De-Formulate
Complex Polymer Mixtures
35
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 !
William Carson
Tracy Phillpott
Tom Kearney
Frederic Prulliere
George Giansanti
Thank YOU !36
Acknowledgment
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
Copolymerization Process Control: Poly(A-B-C)37
Polymer Additive AnalysisHPLC (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
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
Additive Analysis
LC-IR Application Scope
41
• 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
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).
Small Molecules
Additives
Impurities
Degradants
Polymers
Identification
Compositional
Variations
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.
Hyphenated Techniques to Characterize
Copolymers Poly(A-B)
44
high MW low MW
mol
ar m
ass
comonomer A
comonomer B
A/B compositionratio
polymer chains
Ab
so
rba
nce
SEC Time
GPC/SEC
Composition
Analysis:IR
NMR
MS
HPLC
Hyphenated (Coupling) Techniques
LC—NMR: Fractionation (Batching)
LC-MS: for Low MW Portion
2D LC: HPLC x SEC; IPC x SEC
GPC-IR
GPC-IR to Characterize Compositional
Variations of Copolymers Poly(A-B)
45
high MW low MW
mol
ar m
ass
comonomer A
comonomer B
A/B compositionratio
polymer chains
Ab
so
rba
nce
AB
GPC Time
IR Spectra
46
High MW Low MW GPC
Elution
Time
Ab
so
rban
ce
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 to Characterize MMA Copolymers by
IR Peak Ratios of Co-Monomer Contributions
CH3
CH3
2
=O
C
Co-Monomers: S MAA BA MMA DAAM
1734
704
1605
15361700
1366
right peak
of doublet
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
B/C Mix) 12.5% 15% 10% 62.5%
Acid/Ester
S/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
DAAM
1366
DAAM
1536
Sample A: Black
Sample B: Blue
Sample C: Violet
Sample D: Green
COOH
1700
Styrene
1605
49
Sample S MAA
(Acid)
BA
(Ester)
MMA
(Ester)
DAAM RESULTS
Ratios across
MWD
A 5% 12.5% 10% 60% 12.5% Stable S/E Ratio
A/E Small DriftDAAM/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
B/C Mix) 12.5% 15% 10% 62.5%
S/Ester Drifting
Acid/Ester Drifting
DAAM/Ester =0
Summary: Characterizing MMA
Copolymers by GPC-IR
0
.1
.2
.3
.4
.5
.6
106 104 103 102105Molecular Weight
Copovidone: sample A
30
35
40
45
50
% a
ceta
te c
om
onom
er
Comonomer Composition
Distribution
sample B
sample C
0
.1
.2
.3
.4
.5
.6
106 104 103 102105
sample B
sample C
Bulk 40% VAc
ma
x. IR
ab
so
rba
nce Molecular Weight
Distribution
Copovidone PVP/VAc Compositional
Drifts from Different Manf. Processes
Copovidone A gave clear tablets while Copovidone C led to cloudy ones.
