De-Formulating Complex Polymer Mixtures

by GPC-IR Hyphenated Technology

Ming Zhou, PhD

Director of Applications Engineering

Spectra Analysis Instruments, Inc.

Marlborough, MA

Contact: ZhouM@Spectra-Analysis.com1

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

GPC-IR Hyphenated System

GPC

LC-IR Hyphenated System

GPC

or HPLC

Hyphen

Desolvation

Deposition

Microscopic FTIR

System Control

Data Processing

Schematic View of LC-IR System

GPC

or

HPLC

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

Direct Deposition IR in Action

10

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

GPC-IR: Direct Deposition &

Data Processing

ZnSe Disk

12

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

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

Additive Identification by HPLC-FTIR

Database Searchable

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.