LC-IR Applications In Polymer Related Industries

Webinar

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

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: PEG 2

The Company
257 Simarano Drive
Marlborough, MA 01752

 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
December 2009 3

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
Sid Bourne, PhD William W. Carson, PE
Co-founder Co-founder
Chief Scientist V P Engineering

Developed the first GC-IR product  Over $1b revenue generated by
while at the Argonne National products covered by his 19 US patents
Laboratory. and 75 corresponding patents.
Developed the “Tracer” at Bio-Rad.  Registered Professional Engineer.
Founded Bourne Scientific, Inc and  VP RD&E at Waters
the “Detective”.  Developed 150CGPC, LC-MS, etc.
University of Minnesota, PhD.  Massachusetts Institute of Technology,
Organic Chemistry. MS Mechanical Engineering.

5

Hyphenated Technologies & Major
Applications
LC-MS LC-IR

Separation Liquid Chromatography

Detection & Mass Infra Red
Data Analysis Spectroscopy Spectroscopy

Applications Small Molecules Copolymer Compositions
Proteins Polymer Mixtures
Additive Analysis

LC-IR Hyphenated System

System Control Deposition Hyphen HPLC
Data Processing Microscopic FTIR Desolvation or GPC8

How is the Solvent Removed?
N2 Addition
Cyclone
From LC Cyclone Evaporator
Evaporator
Thermal Nebulization

Air Cooled
Condenser

Patent pending:
PCT/US2007/025207

Chilled
Condenser

Particle Stream to DiscovIR

Waste Solvent

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?

Separated Dot Depositing on Disk Separated Dots from HPLC-IR Continuous Polymer Tracks (GPC-IR)

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: Direct Deposition &
Data Processing

ZnSe Disk

14

GPC-IR to Characterize Compositional
Variations of Copolymers Poly(A-B)

Absorbance

A/B composition
molar mass

ratio
Bulk 50% (NMR,
Benchtop FTIR)

high MW low MW GPC Time

polymer chains

comonomer A
comonomer B
16

GPC-IR to Characterize Compositional
Variations of Copolymers Poly(A-B)

IR Spectra

A
B
Absorbance

A/B composition
molar mass

ratio

high MW low MW GPC Time

polymer chains

comonomer A
comonomer B
17

OUTLINE








Styrene-Butadiene Copolymer
Structures
Monomers: S & B

Random

SBS Block

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.

LC-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

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)

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)

GPC-IR Spectrum Snapshot & Peak
ID for SEBS Block Copolymers

BB2
CH2-CH3
2924
-(CH2-CH)k-(CH2-CH2)m-(CH2-CH)n-(CH2-CH)l –

BB = Backbone S E B S

BB1
1465 S2
B 700
S1 1379
1493

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

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%
Co-Monomers: S MAA BA MMA DAAM
CH3

C
=O 1734
1700 1536
704 1734
1605

2
1366
right peak
CH3
of doublet

GPC-IR to Characterize MMA Copolymers by
IR Peak Ratios of Co-Monomer Contributions
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 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

2
1366
right peak
CH3
of doublet

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
Sample A: Black
Sample B: Blue
Sample C: Violet
Sample D: Green

COOH
1700
DAAM
Styrene 1366
1605 DAAM
1536

IR Spectrum Comparison (1350-650cm-1) of
Samples B/C/D at 23.2 Min. Elution Time

Sample B: Blue
Sample C: Violet
Sample D: Green

Styrene
704

Styrene/Ester Ratio Variation across MWD
(Elution Time) by IR Peak Ratios

704/1734 Peak Height Ratio, No Styrene Sample B

IR Spectrum at Red Marker

IR Spectrum at Blue Marker


704/1734 Peak Height Ratio Sample C




704/1734 Peak Height Ratio Sample D



GPC-IR Chromatogram Comparison (B/C
MWD Mismatch) of Samples B/C/D

Sample B

Sample C

Sample D

Summary: Characterizing MMA
Copolymers by GPC-IR
Sample S MAS 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
34

Summary: GPC-IR Applications
Profile Polymer Compositions = f (Sizes)

IR Spectra B A
A/B Ratio
Absorbance

High MW Low MW GPC
Elution
Time

 Map out Copolymer Compositions (A/B Ratio) across MWD (Sizes)

35


IR Spectra B A
A/B Ratio
Absorbance

High MW Low MW GPC
Elution
Time

 Study Lot-to-Lot Variations

36


IR Spectra B A
A/B Ratio
Absorbance

High MW Low MW GPC
Elution
Time

 Study Supplier-to-Supplier Variations (2nd Source)

37


IR Spectra B A
A/B Ratio
Absorbance

High MW Low MW GPC
Elution
Time

 Study Lot-to-Lot or Supplier-to-Supplier Variations
 Characterize Polymer Degradation from Processing:
 Loss of functional group A (Reduced A/B)
38

Cross Linking
IR Spectra B A
A/B Ratio
Absorbance

High MW Low MW GPC
Elution
Time

 Loss of functional group A (Reduced A/B)
39
 Cross-linking ( Higher MW)

Break Down
IR Spectra B A
A/B Ratio
Absorbance

High MW Low MW GPC
Elution
Time

 Loss of functional group (Reduced A/B)
40
 Break down ( Lower MW) & Detect low MW degradant

Cross Linking Break Down
IR Spectra B A
A/B Ratio
Absorbance

High MW Low MW GPC
Elution
Time

 Loss of functional group (Reduced A/B)
41
 Break down ( Lower MW) & Detect low MW degradant
 De-Formulate Complex Polymer Mixtures

OUTLINE








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
Relative Absorbance

Chromatogram

Functional Group
Chromatograms

(Molecular Weight Distribution)

Polymer Blend EVA/PBMA Ratios with
MWD Determined by IR Peak Ratios

4

3.5
mEVA/mPBMA

y = 1.6162x - 0.2149
3

2.5

2

1.5

1

0.5

0
0 0.5 1 1.5 2 2.5

absEVA(2852)/absPBMA(1152)


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)

OUTLINE








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.

HPLC (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

Additive Identification by HPLC-FTIR
Database Searchable

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

• 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

51

Polymer & Small Molecule Analysis by
GPC-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).

Polymers Small Molecules
Additives
Impurities
Degradants

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








De-Formulation Analysis
of Polymer Mixture (A & B)

55

of Polymer Mixture (A & B)
Peak Chromatogram at 2929 cm-1 (CH2 Backbone of AB Mixture)

Abs. Band Chromatogram
at 1705 cm-1 Specific
for Polymer A
Band Chromatogram
at 1734 cm-1 Specific
for Polymer B

GPC Elution Time, Min
56

GPC-IR De-Formulation
of An Adhesive Polymer Mixture

C
B?
at 2929 cm-1
A

GPC-IR Database Search to Identify
the Component A at 10 Min. as EVA

CH2 A
2929
C=O
1724

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

SAE 15W-40 Heavy Duty Oil in THF

Low MW Mineral Oil Diverted after 12.2 min

12

11

10
Elution
9 Time
8 (Min. & MW)
3500 3000 2500 2000 1500 1000

Wavenumber, cm-1

De-Formulation of Motor Oil Lubricant
Additive #1 @ RT 9.2 Min

Shell Rotella T Heavy Duty 15W-40
9.2 minute eluant

4000 3500 3000 2500 2000 1500 1000
wavenumber, cm-1

IR Database Search: Styrene-Acrylate Copolymer

Lubricant De-Formulation of Motor Oil
Additive #2 @ RT 12 Min

Shell Rotella T Heavy Duty 15W-40
12 minute eluant

4000 3500 3000 2500 2000 1500 1000
wavenumber, cm-1

IR database Search: Polyisobutenyl Succinimide (PIBS)

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?

LC-IR Application Scope

 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

65

OUTLINE








High Temperature GPC-IR Test
Conditions for SCB Analysis

 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)

67

High Temp GPC-IR Removes
TCB Solvent for SCB Analysis
Polyethylene Sample with & without TCB Solvent

Flow Cell
Window

DiscovIR-LC Removes TCB Completely and Gives Clean IR Spectrum (Blue).

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
GPC-IR Chromatogram of EP Copolymer Overlaid with Peak Ratio Abs1378/Abs1468

CH3

-(CH2-CH2)m-(CH2-CH)n-


Copolymer Compositional Drift ~ CH3 Branching ~ Peak Ratio A1378/A1468

HT GPC-IR Spectra of
Ethylene-Hexene Copolymers

CH2CH2CH2-CH3
Butyl Branching ~ Peak Ratio A1378/A1368
-(CH-CH2)m-(CH2-CH2)n-

Butyl Branching Analysis of
Ethylene-Hexene Copolymers
N butyls/1000 c
26

24

22

20
N butyls/1000 c

18

16
CH2CH2CH2-CH3
14
12

10
8 9 10 11 12 13 14 15
elution time, min


Butyl Branching Numbers per 1000 Backbone Carbons with Elution Time (MWD)

Polyolefin Short Chain Branching
Analysis by Chemometrics
GPC-IR Chromatograms Overlaid with Area Ratios of EP Copolymer


Area Ratio = Area (2940-3100cm-1) / Area (2940-2800cm-1)

GPC-IR Branching Analysis of
Dow ENGAGE® Polyolefins
Branching Levels (Area Ratios) with a GPC-IR Chromatogram

Ethylene-Octene: 8100, 8200 CH2CH2CH2CH2CH2-CH3
8401, 8540

Area Ratio = Area (Peak 1375 cm-1) / Area (Peak 1465 cm-1)

GPC-IR Branching Analysis of
Ethylene-Octene Copolymers
GPC-IR Chromatograms Overlaid with Area Ratios

EP(~40%)

EO (~3%)
EO(~2%)
EO(~1%)
HDPE

Area Ratio = Area (2940-3100cm-1) / Area (2940-2800cm-1)
Higher Sensitivity than Peak Ratio Method at Low Branching Levels

OUTLINE








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

-(O-CH2-CH2)n-
Blue Trace: No Carboxylates

Red Trace: No Aldehydes

Degradation Intermediates Detected by
HPLC-IR from Degraded PEG
PEG-1000 Sample Air Bubbled Overnight at 55C

Three Chromatographic displays
generated from one time ordered set of
FTIR Spectra

IR Identification of Degraded Intermediates
(Aldehydes & Carboxylates)

Typical IR Spectra of PEG in Black

Na+ or K+ Cation
Aldehyde Carboxylate Salt
1719 1607

11.45 minutes

4.93 minutes

1.50 minutes

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

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

LC-IR Applications In Polymer Related Industries

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