lc-ir applications in polymer related industries
DESCRIPTION
LC-IR Application Overview for Polymer Related Industries with Many Case Studies: characterize copolymer compositions across MWD and de-formulate complex polymer mixturesTRANSCRIPT
LC-IR Applications in Polymer Industries:
Characterizing Copolymer Compositions &
De-Formulating Complex Polymer Mixtures
Ming Zhou, PhD
Director of Applications Engineering
July 29, 2011
1
Webinar
OUTLINE
Introduction: LC-IR Technology & System
LC-IR Applications: Case Studies
Characterize Copolymer Compositions across MWD:
SBR, SEBS, PMMA/BA/MAA/S/DAAM
Polymer Blend Ratio Analysis across MWD: EVA/PBMA
Polymer Additive Analysis by HPLC-IR: AO, PDMS
De-Formulate Complex Polymer Mixtures: Adhesive
Polyolefin Branching Analysis by High Temp GPC-IR
Polymer Degradation Analysis: PEG2
December 2009 3
2004: Founded with Substantial Commercial
Experience in FTIR, LC-MS, GC
2005 & 2006: Developed LC-IR Technology (Patent Protected)
2008: Received R&D Magazine‟s „Top 100‟ Product Award.
2009: Received Massachusetts Life Science Center‟s Award & Certification.
2007-2009: Sales to „Top Tier‟ Customers: Polymers, Forensics,
& National Labs.
2009-Present: Focused Application Development in Polymer Industries
The Company
257 Simarano Drive
Marlborough, MA 01752
DiscovIR Users
Dow Chemical Polymers
Du Pont Polymers
WR Grace Polymers
SABIC Polymers
Afton Chemical Polymers
Nissan (Japan) Polymers
China Mining Univ. Polymers
Novartis / Ciba Vision Polymer (Pharma)
Merck Polymer (Pharma)
Johnson & Johnson Polymer (Pharma)
Lawrence Livermore National Lab Trace Analysis
Oak Ridge National Laboratory Environmental
Naval Research Laboratory Organics
US Army Aberdeen Proving Ground Forensics
State Police: PA, VT, AL, LA, MD ... Forensics
Scientific Excellence
5
Sid Bourne, PhD
Co-founder
Chief Scientist
Developed the first GC-IR product
while at the Argonne National
Laboratory.
Developed the “Tracer” at Bio-Rad.
Founded Bourne Scientific, Inc and
the “Detective”.
University of Minnesota, PhD.
Organic Chemistry.
William W. Carson, PE
Co-founder
V P Engineering
Over $1b revenue generated by
products covered by his 19 US patents
and 75 corresponding patents.
Registered Professional Engineer.
VP RD&E at Waters
Developed 150CGPC, LC-MS, etc.
Massachusetts Institute of Technology,
MS Mechanical Engineering.
Hyphenated Technologies & Major
Applications
Liquid Chromatography
Mass
SpectroscopyInfra Red
Spectroscopy
Separation
Applications Small Molecules Copolymer Compositions
Proteins Polymer Mixtures
Additive Analysis
Detection &
Data Analysis
LC-MS LC-IR
8
LC-IR Hyphenated System
HPLC
or GPC
Hyphen
Desolvation
Deposition
Microscopic FTIR
System Control
Data Processing
How Does It Work?
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
10-0.3 mm/min
Unattended overnight runs
The yellow ZnSe disk is under
vacuum without moisture or
CO2 interference
Disk Temp: -140C ~ 100C
Transmission IR analysis is
done on the solid deposit.
Re-usable after solvent
cleaning
11
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 HPLC Solvents, Gradients & Volatile Buffers
• e.g. Water, ACN, Methanol, THF, DMSO …
All GPC/SEC Solvents: e.g. THF, TCB, HFIP, Chloroform, DMF
High Quality Solid Phase Transmission IR Spectra
Fully Automated Operation: No More Manual Fractionation
Multi-Sample Processing: 10 Hr ZnSe Disk Time
GPC-IR to Characterize Compositional
Variations of Copolymers Poly(A-B)
16
high MW low MW
mol
ar m
ass
comonomer A
comonomer B
A/B compositionratio
polymer chains
Ab
so
rba
nc
e
Bulk 50% (NMR,
Benchtop FTIR)
GPC Time
GPC-IR to Characterize Compositional
Variations of Copolymers Poly(A-B)
17
high MW low MW
mol
ar m
ass
comonomer A
comonomer B
A/B compositionratio
polymer chains
Ab
so
rba
nc
e
AB
GPC Time
IR Spectra
OUTLINE
Introduction: LC-IR Technology & System
LC-IR Applications: Case Studies
Characterize Copolymer Compositions across MWD:
SBR, SEBS, PMMA/BA/MAA/S/DAAM
Polymer Blend Ratio Analysis across MWD: EVA/PBMA
Polymer Additive Analysis by HPLC-IR: AO, PDMS
De-Formulate Complex Polymer Mixtures: Adhesive
Polyolefin Branching Analysis by High Temp GPC-IR
Polymer Degradation Analysis: PEG18
Styrene-Butadiene Copolymer Structures
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
LC-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
GPC-IR Spectrum Snapshot & Peak
ID for SEBS Block Copolymers
-(CH2-CH)k-(CH2-CH2)m-(CH2-CH)n-(CH2-CH)l –
S E B S
CH2-CH3
S1
1493
S2
700
BB2
2924
BB1
1465
B
1379
BB = Backbone
SEBS Ratio Overlay w/ MWD
BB1/BB2 (Flat), B/BB1, S1/BB1, S2/BB1
Characterize MMA Copolymers by GPC-IR
Identify IR Peaks of the Co-Monomers
CH3
CH3
2
=O
C
Co-Monomers: S MAA BA MMA DAAM
1734
704
1605
15361700
1366
right peak
of doublet
Sample S MAS BA MMA DAAM
A 5% 12.5% 10% 60% 12.5%
B 15% 10% 75%
C 25% 15% 10% 50%
D (50:50
B/C Mix) 12.5% 15% 10% 62.5%
1734
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 MAS 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
Total (MMA+BA) 1536/1366 (Ratio Check)
IR Spectrum Comparison (1800-1300cm-1) of
All 4 Samples at 23.2 Min. Elution Time
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
IR Spectrum Comparison (1350-650cm-1) of
Samples B/C/D at 23.2 Min. Elution Time
Styrene
704
Sample B: Blue
Sample C: Violet
Sample D: Green
Styrene/Ester Ratio Variation across MWD
(Elution Time) by IR Peak Ratios
704/1734 Peak Height Ratio, No Styrene
IR Spectrum at Red Marker
IR Spectrum at Blue Marker
Sample B
Styrene/Ester Ratio Variation across MWD
(Elution Time) by IR Peak Ratios
704/1734 Peak Height Ratio
IR Spectrum at Red Marker
IR Spectrum at Blue Marker
Sample C
Styrene/Ester Ratio Variation across MWD
(Elution Time) by IR Peak Ratios
704/1734 Peak Height Ratio
IR Spectrum at Red Marker
IR Spectrum at Blue Marker
Sample D
Sample B
Sample C
Sample D
GPC-IR Chromatogram Comparison (B/C
MWD Mismatch) of Samples B/C/D
34
Sample S MAS
(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
35
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)
IR Spectra
Summary: GPC-IR ApplicationsProfile Polymer Compositions = f (Sizes)
36
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 Variations
IR Spectra
Summary: GPC-IR ApplicationsProfile Polymer Compositions = f (Sizes)
37
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 Supplier-to-Supplier Variations (2nd Source)
IR Spectra
Summary: GPC-IR ApplicationsProfile Polymer Compositions = f (Sizes)
38
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 A (Reduced A/B)
IR Spectra
Summary: GPC-IR ApplicationsProfile Polymer Compositions = f (Sizes)
39
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 A (Reduced A/B)
Cross-linking ( Higher MW)
IR Spectra
Cross Linking
Summary: GPC-IR ApplicationsProfile Polymer Compositions = f (Sizes)
40
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
IR Spectra
Break Down
Summary: GPC-IR ApplicationsProfile Polymer Compositions = f (Sizes)
41
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)
OUTLINE
Introduction: LC-IR Technology & System
LC-IR Applications: Case Studies
Characterize Copolymer Compositions across MWD:
SBR, SEBS, PMMA/BA/MAA/S/DAAM
Polymer Blend Ratio Analysis across MWD: EVA/PBMA
Polymer Additive Analysis by HPLC-IR: AO, PDMS
De-Formulate Complex Polymer Mixtures: Adhesive
Polyolefin Branching Analysis by High Temp GPC-IR
Polymer Degradation Analysis: PEG42
Polymer Blend Ratio Analysis by
GPC-IR for EVA / PBMA Mixture
IR spectral bands of EVA & PBMA are closely overlapped.
The 1152 and 2852 cm-1 bands selected for minimal convolution.
EVA / PBMA Polymer Blend
Chromatograms at Different IR Bands
Maximum Peak Chromatogram
Functional Group Chromatograms
(Molecular Weight Distribution)
Rela
tive
Ab
so
rban
ce
Polymer Blend EVA/PBMA Ratios with
MWD Determined by IR Peak Ratios
(Molecular Weight Distribution)
Calibration Curve: Y = 1.6162 X-0.2149 by Flow Injection Method w/o LC Separation
Y is EVA/PBMA Mass Ratio, X is Peak Ratio Abs(2852)/Abs(1152)
y = 1.6162x - 0.2149
0
0.5
1
1.5
2
2.5
3
3.5
4
0 0.5 1 1.5 2 2.5
absEVA(2852)/absPBMA(1152)
mE
VA
/mP
BM
A
OUTLINE
Introduction: LC-IR Technology & System
LC-IR Applications: Case Studies
Characterize Copolymer Compositions across MWD:
SBR, SEBS, PMMA/BA/MAA/S/DAAM
Polymer Blend Ratio Analysis across MWD: EVA/PBMA
Polymer Additive Analysis by HPLC-IR: AO, PDMS
De-Formulate Complex Polymer Mixtures: Adhesive
Polyolefin Branching Analysis by High Temp GPC-IR
Polymer Degradation Analysis: PEG46
Polymer Additive Analysis
Additives improve polymer performance in small quantities.
Many types of additives: antioxidants, UV stabilizers, etc
Basic ASTM additive analysis techniques:
1) Separate additives from bulk polymer samples and
also from solids such as fillers.
2) Fractionate extract to obtain separate components.
Typically by HPLC or SEC.
3) Identify/quantify the individual components by MS, IR,
NMR.
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
51
• 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 byGPC-IR for ABS Plastic w/o 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
Polymer Additive Analysis
GPC-IR for ABS Plastic w/o 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.
OUTLINE
Introduction: LC-IR Technology & System
LC-IR Applications: Case Studies
Characterize Copolymer Compositions across MWD:
SBR, SEBS, PMMA/BA/MAA/S/DAAM
Polymer Blend Ratio Analysis across MWD: EVA/PBMA
Polymer Additive Analysis by HPLC-IR: AO, PDMS
De-Formulate Complex Polymer Mixtures: Adhesive
Polyolefin Branching Analysis by High Temp GPC-IR
Polymer Degradation Analysis: PEG54
De-Formulation Analysis
of Polymer Mixture (A & B)
56
GPC Elution Time, Min
Abs. Band Chromatogram
at 1705 cm-1 Specific
for Polymer ABand Chromatogram
at 1734 cm-1 Specific
for Polymer B
Peak Chromatogram at 2929 cm-1 (CH2 Backbone of AB Mixture)
GPC-IR De-Formulation
of An Adhesive Polymer Mixture
A
Cat 2929 cm-1 B?
CH2
2929C=O
1724
GPC-IR Database Search to Identify
the Component A at 10 Min. as EVA
A
GPC-IR to Identify Components
C & B by Spectral Subtraction
Component C
Paraffin
Component B
De-Formulation of Motor Oil Lubricant
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 Diverted after 12.2 min
Wavenumber, cm-1
Elution
Time
(Min. & MW)
De-Formulation of Motor Oil Lubricant
Additive #1 @ 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 #2 @ 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
Lubricant De-Formulation of
Motor Oil with GPC-IR
De-formulate Polymeric Additives in Motor Oil Lubricant
Additive #1 @ 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 #2 @ Retention Time 10-12 Min
• Broad MW Range: 8-30K (GPC)
• Polyisobutenyl Succinimide (PIBS) (IR Database Search)
• A Dispersant
• Small Comonomer Compositional Drift
[dimethyl (1367 cm-1) / imide (1700 cm-1)] Ratio Change < 10%
Polymer Degradation Study – Oil Change Schedule
Search for Suppliers?
De-Formulation Analysis
LC-IR Application Scope
65
Combine Polymer Analysis and Additive Analysis
• Profile Polymer Blends with MWD – Database Searchable
• Analyze Copolymer Compositional Drift with MWD
• Analyze Additives – Database Searchable
Competitive Analysis
IP Protection
Problem Solving
Trouble Shooting
Contamination Analysis
OUTLINE
Introduction: LC-IR Technology & System
LC-IR Applications: Case Studies
Characterize Copolymer Compositions across MWD:
SBR, SEBS, PMMA/BA/MAA/S/DAAM
Polymer Blend Ratio Analysis across MWD: EVA/PBMA
Polymer Additive Analysis by HPLC-IR: AO, PDMS
De-Formulate Complex Polymer Mixtures: Adhesive
Polyolefin Branching Analysis by High Temp GPC-IR
Polymer Degradation Analysis: PEG66
High Temperature GPC-IR Test
Conditions for SCB Analysis
67
GPC: Waters 150C
Solvent : TCB
Temperature: 145C
Column: Jordi DVB Mix Bed 25cm x 1cm Size 5 mm
Flow Rate: 1 ml/min
Sample: 2.5 mg/ml with 200ppm Irganox 1010
Injection Volume: 100 ml
Transfer Line Temperature: 150C
DiscovIR-LC Conditions:
• Cyclone Temperature: 375C
• Chamber Vacuum: 2 Torr
• Disk Speed: 3 mm/min (Standard)
0.3 mm/min (Slower for thicker deposition)
(Better Sensitivity in IR Fingerprint Region)
High Temp GPC-IR Removes
TCB Solvent for SCB Analysis
DiscovIR-LC Removes TCB Completely and Gives Clean IR Spectrum (Blue).
Polyethylene Sample with & without TCB Solvent
Flow Cell
Window
High Temp GPC-IR Spectra for
Polyolefin Branching Analysis
Ethylene-Propylene Copolymer (40% PP), Solvent TCB @ 150C
Polyolefin Branching Analysis by
GPC-IR for EP Copolymer
Copolymer Compositional Drift ~ CH3 Branching ~ Peak Ratio A1378/A1468
GPC-IR Chromatogram of EP Copolymer Overlaid with Peak Ratio Abs1378/Abs1468
(Molecular Weight Distribution)
-(CH2-CH2)m-(CH2-CH)n-
CH3
HT GPC-IR Spectra of
Ethylene-Hexene Copolymers
Butyl Branching ~ Peak Ratio A1378/A1368-(CH-CH2)m-(CH2-CH2)n-
CH2CH2CH2-CH3
Butyl Branching Analysis of
Ethylene-Hexene Copolymers
Butyl Branching Numbers per 1000 Backbone Carbons with Elution Time (MWD)
(Molecular Weight Distribution)
N butyls/1000 c
10
12
14
16
18
20
22
24
26
8 9 10 11 12 13 14 15
elution time, min
N b
uty
ls/1
000 c
-(CH-CH2)m-(CH2-CH2)n-
CH2CH2CH2-CH3
Area Ratio = Area (2940-3100cm-1) / Area (2940-2800cm-1)
Polyolefin Short Chain Branching
Analysis by Chemometrics
GPC-IR Chromatograms Overlaid with Area Ratios of EP Copolymer
(Molecular Weight Distribution)
Area Ratio = Area (Peak 1375 cm-1) / Area (Peak 1465 cm-1)
Branching Levels (Area Ratios) with a GPC-IR Chromatogram
(Molecular Weight Distribution)
GPC-IR Branching Analysis of
Dow ENGAGE® Polyolefins
-(CH-CH2)m-(CH2-CH2)n-
CH2CH2CH2CH2CH2-CH3Ethylene-Octene: 8100, 8200
8401, 8540
Area Ratio = Area (2940-3100cm-1) / Area (2940-2800cm-1)
GPC-IR Branching Analysis of
Ethylene-Octene Copolymers
GPC-IR Chromatograms Overlaid with Area Ratios
(Molecular Weight Distribution)
Higher Sensitivity than Peak Ratio Method at Low Branching Levels
EP(~40%)
HDPE
EO (~3%)
EO(~2%)
EO(~1%)
OUTLINE
Introduction: LC-IR Technology & System
LC-IR Applications: Case Studies
Characterize Copolymer Compositions across MWD:
SBR, SEBS, PMMA/BA/MAA/S/DAAM
Polymer Blend Ratio Analysis across MWD: EVA/PBMA
Polymer Additive Analysis by HPLC-IR: AO, PDMS
De-Formulate Complex Polymer Mixtures: Adhesive
Polyolefin Branching Analysis by High Temp GPC-IR
Polymer Degradation Analysis: PEG76
Forced Degradation Study of PEG Pharmaceutical Excipient
Reverse-Phase HPLC-IR with H2O/ACN; PEG-1000 before Degradation
AU Scale for all traces
1116 cm-1 band chromatogram
1607 cm-1 band chromatogram
Blue Trace: No Carboxylates
1719 cm-1 band chromatogram
Red Trace: No Aldehydes
-(O-CH2-CH2)n-
Degradation Intermediates Detected by
HPLC-IR from Degraded PEG
Three Chromatographic displays generated from one time ordered set of FTIR Spectra
PEG-1000 Sample Air Bubbled Overnight at 55C
IR Identification of Degraded Intermediates
(Aldehydes & Carboxylates)
11.45 minutes
4.93 minutes
1.50 minutes
Na+ or K+ Cation
Carboxylate Salt
1607
Aldehyde
1719
Typical IR Spectra of PEG in Black
Proposed Mechanism of PEG Oxidation
Supported by HPLC-IR Data
Series of Aldehydes
Series of Carboxylates
LC-IR Application Summary
LC-IR Applications: Model Cases
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)
De-Formulate Complex Polymer Mixtures:
PolyX + Poly(A-B) + Add.
PolyX + PolyY + Poly(A-B-C) + Add‟s
81
SUMMARY
DiscovIR-LC is a Powerful Tool for Polymers, Additives & Materials Analysis
Characterize Copolymer Compositional Variations across MWD
Analyze Polymer Additives / Degradants / Impurities
De-Formulate Complex Polymer Mixtures
Polyolefin Copolymer Branching Analysis by High Temp GPC-IR
Characterize Polymer Changes: Modification or Degradation
Process Control & Optimization
For Plastics, Rubbers, Films, Fibers, Foams, Composites & Biopolymers
For Polymer Analysis of Coating, Adhesive, Sealant & Elastomer
For General Analytical Capability: Trouble Shooting
82