Deformulating Complex Polymer Mixtures By GPC-IR Technology
description
Transcript of Deformulating Complex Polymer Mixtures By GPC-IR Technology
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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
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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
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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
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LC-IR Hyphenated System
GPC
or HPLC
Hyphen
Desolvation
Deposition
Microscopic FTIR
System Control
Data Processing
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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
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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
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What is Direct Deposition FTIR?
Continuous Polymer Tracks (GPC-IR)Separated Dots from HPLC-IRSeparated Dot Depositing on Disk
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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
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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
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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
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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
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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
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CH2
2929C=O
1724
GPC-IR Database Search to Identify
Peak A at 10 Min. as EVA Polymer
A
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GPC-IR to Identify Components
C & B by Spectral Subtraction
Component C
Paraffin
Component B
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A
C
B
C
AB
GPC Confirmation of the De-Formulated
Components with Known Stds A, B & C
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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
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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
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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
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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
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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
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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
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Stacked IR Spectra of Components A, B, C
at Different GPC Times (~ MWD Centers)
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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
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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
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In-House Database Match of Polymer A
(Red Spectrum) with Flex Resin (Blue Std)
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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
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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
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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
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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
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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 !
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William Carson
Tracy Phillpott
Tom Kearney
Frederic Prulliere
George Giansanti
Thank YOU !36
Acknowledgment
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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
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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
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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
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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
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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
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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.
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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
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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
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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)
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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)
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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
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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
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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.