lc-ir applications in polymer related industries

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

http://www.spectra-analysis.com/index.htm

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.


http://www.anl.gov/index.html

http://images.google.co.uk/imgres?imgurl=http://www.plant.uoguelph.ca/events/labcamp/images/logo-biorad.jpg&imgrefurl=http://www.plant.uoguelph.ca/events/labcamp/index.html&usg=__dwgKkSWdosOcO4C8F0dJAtkZZZw=&h=130&w=463&sz=53&hl=en&start=2&sig2=YxgS6jEKfE-laLY63BTIQg&tbnid=NkFheOvAf9nCIM:&tbnh=36&tbnw=128&ei=-O-mSb6zEMO9-Aa467nEAg&prev=/images?q=bio-rad&gbv=2&hl=en

http://images.google.co.uk/imgres?imgurl=http://www.milestonedevelopment.com/CPSA/2007/2007sponsors/ionics.gif&imgrefurl=http://www.milestonedevelopment.com/CPSA/2007/sponsor.html&usg=__YJ0rROjn2SC-RM-_iXvDXfDUVDU=&h=352&w=800&sz=48&hl=en&start=8&sig2=sDSlmCxf6WUVkLg_uOqwBQ&tbnid=1rjbXKuzfDXbYM:&tbnh=63&tbnw=143&ei=OvCmSdGUJMS1-AbK-_HQAg&prev=/images?q=ionics&gbv=2&hl=en

http://images.google.co.uk/imgres?imgurl=http://www.biosupplynet.com/suppliers/1168/millipore.gif&imgrefurl=http://www.biosupplynet.com/cfdocs/suppliers/supp_det.cfm?supp_id=1168&usg=__-j1znhSd_Z2CZTZAAXhEBJHtb1k=&h=167&w=225&sz=6&hl=en&start=14&sig2=r1aPQu8BZb7UWkWGbtNJog&tbnid=sJyLfgdKWl9n9M:&tbnh=80&tbnw=108&ei=svCmSZHcHcLQ-AaH5fnbAg&prev=/images?q=millipore+corp&gbv=2&hl=en

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


LC-IR Hyphenated System

LC


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: Direct Deposition &

Data Processing

ZnSe Disk

14


15


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











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


http://upload.wikimedia.org/wikipedia/commons/0/07/Benzene_circle.svg


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




704/1734 Peak Height Ratio



Sample C




704/1734 Peak Height Ratio



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


Study Lot-to-Lot Variations

IR Spectra



37

High MW Low MW GPC

Elution

Time

Ab

so

rban

ce

A/B RatioA

B


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

IR Spectra



38

High MW Low MW GPC

Elution

Time

Ab

so

rban

ce

A/B RatioA

B


Study Lot-to-Lot or Supplier-to-Supplier Variations

Characterize Polymer Degradation from Processing:

Loss of functional group A (Reduced A/B)

IR Spectra



39

High MW Low MW GPC

Elution

Time

Ab

so

rban

ce

A/B RatioA

B




Loss of functional group A (Reduced A/B)

Cross-linking ( Higher MW)

IR Spectra

Cross Linking



40

High MW Low MW GPC

Elution

Time

Ab

so

rban

ce

A/B RatioA

B




Loss of functional group (Reduced A/B)


Break down ( Lower MW) & Detect low MW degradant

IR Spectra

Break Down



41

High MW Low MW GPC

Elution

Time

Ab

so

rban

ce

A/B RatioA

B




Loss of functional group (Reduced A/B)


Break down ( Lower MW) & Detect low MW degradant

De-Formulate Complex Polymer Mixtures

IR Spectra

Break DownCross Linking



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 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


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











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


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

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



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)

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


A

C

B

C

AB


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?



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











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


-(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)


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



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

Branching Levels (Area Ratios) with a GPC-IR Chromatogram


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


Higher Sensitivity than Peak Ratio Method at Low Branching Levels

EP(~40%)

HDPE

EO (~3%)

EO(~2%)

EO(~1%)


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


Blue Trace: No Carboxylates


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


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

Documents

lcir hyphenated systemlc

c transmission ir analysis

webinarlcir applications

gcir product

polymer industries

butadiene comonomer

gpc elution time mwd

comonomer b17