Inks, Lubricants, Adhesives, Coatings…

How To Find Your

Competitor’s Recipe!

www.spectra-analysis.com

July 25, 2012

Presenters

Tracy Phillpott Senior Applications Chemist Spectra Analysis Instruments, Inc.

Ming Zhou, PhD Director of Applications Engineering Spectra Analysis Instruments, Inc.

Outline

• Introduction: GPC-IR Hyphenated Technology

• DiscovIR System: Instrumentation & Features

• GPC-IR to De-Formulate Complex Polymer Mixtures

Case #1: De-Formulate a Hot Melt Adhesive

Case #2: De-Formulate a Conductive Ink

Case #3: De-Formulate a UV Curable Coating

Case #4: De-Formulate Polymeric Additives in Lubricant Oil

• Summary

Combination of Single Parameters Tools:

Hyphenated Systems

Separation System and Detection System

• Bundling two analytical techniques to enable the characterization of the polymeric system along two axes Size ( SEC/GPC) for the molecular weight distribution

Composition for the architecture

GPC-IR Hyphenated System:

Principle and Information Output

Infrared Spectroscopy for

Compositional Information

GPC for the Separation of

the Polymers by MW or

Size

GPC-IR Hyphenated System

DiscovIR-GPC

Principle of a GPC-IR Hyphenated System

•Chromatography eluant is

nebulized and stripped of

mobile phase in the Hyphen

•Analytes deposited as a track

on a rotating ZeSn disk.

•Track passes through IR

energy beam of built-in

interferometer.

•A time-ordered set of IR

spectra are captured as a data

file set.

GPC

Hyphen: A Proprietary Desolvation Technology

Cyclone

Evaporator

Thermal

Nebulization

From LC

N2 Addition

Chilled

Condenser

Waste Solvent

Particle Stream to DiscovIR

Air Cooled

Condenser

Cyclone

Evaporator

Patent pending: PCT/US2007/025207

The Thermal Nebulization

•The thin-wall stainless steel capillary tube nebulizer is regulated to

evaporate approximately half the solvent (electric heating).

•Solvent expansion upon conversion to vapor increases the nebulizer

back pressure and create a high-speed jet of micrometer-sized liquid

droplets that contain all the solute.

•Gradients are acceptable as it is a self regulating system (gradient

changes monitored by changes in electrical resistance).

Inside the Cyclone Evaporator

•Centrifugal force holds the

droplets (solute) near the cyclone

wall. Just before the droplet goes

to dryness, its volume to surface

ratio becomes small enough that

it is dragged out of the cavity by

the exiting solvent vapor.

•Evaporative cooling protects the

solute from both evaporation and

degradation by limiting the

maximum solute temperature to

the solvent boiling point. The

solvent boiling point is reduced

by operating the cyclone in a

vacuum.

At the Condensers

• After ejection from the cyclone, solvent vapor is removed by diffusion to, and condensation on, the cooled condenser walls.

• Stokes drag from the nitrogen gas maintains the dried droplets in an aerosol suspension and limits their loss by diffusion to the condenser walls.

• The condenser consists of an air cooled stage followed by a Peltier cooled stage.

• The condensed solvent is collected in a waste bottle.

Series of

Condensers

Proprietary Deposition Technology

• Solid phase deposition for reproducible and higher quality spectra (compare to liquid or gas flow cell) Entire mid IR range

Cryogenically cooled

Under vacuum

No CO2 or H2O interference

IR scan every 0.4 sec

• Transmission IR analysis is done on the solid deposit. Better S/N ratio

Allows for rescan

• Use of ZnSe disk for substrate Disc is large enough for unattended overnight

runs

Easy clean up

• Ten hours worth of chromatographic data

• Auto sampler compatible

GPC

Wavenumber, cm-1

9

10

11

12

13

4000 3500 3000 2500 2000 1500 1000

Elution Time, min

C=O

MW =f(Elution Time)

IR

Spectra

CH2 CH3

C-O

CH2

COPOLYMER A-B

POLYMER C

SMALL MOLECULES

HIGH

MW

LOW

MW

Ab

so

rban

ce

Characterization of Polymers Using GPC-IR

• A chromatogram

reflects the elution

distribution of a

particular chemical

structure.

• Data format is a

time-ordered set of

IR spectra.

• Instrument

software extracts

spectral band

chromatograms

from a data set of

spectra.

Outline

• Introduction: GPC-IR Hyphenated Technology

• DiscovIR System: Instrumentation & Features

• GPC-IR to De-Formulate Complex Polymer Mixtures

Case #1: De-Formulate a Hot Melt Adhesive

Case #2: De-Formulate a Conductive Ink

Case #3: De-Formulate a UV Curable Coating

Case #4: De-Formulate Polymeric Additives in Lubricant Oil

• Summary

Characterizing Polymer Mixtures by

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

polymers

additives

IR: Fingerprinting

of Chemical Compositions

• Unambiguous identification only

practical for single species.

• Compounded IR spectra for mixtures.

0

.05

.1

.15

.2

4000 3500 3000 2500 2000 1500 1000

GPC only: 2 or 3 peaks ? IR only: Compounded spectra

A

B?

C

Competitive study of a hot-melt

adhesive:

for cost and margin

structure comparison.

for technical evaluation.

Case #1: De-Formulate a Hot-Melt Adhesive

Polymer Mixture: GPC-IR Data 3D View

8

9

10

11

12

13

14

0

.01

.02

.03

.04

.05

4000 3500 3000 2500 2000 1500 1000

ab

so

rba

nc

e

1724

C=O IR Wavenumber, cm-1

GPC

Elution

Time, min

2929

GPC-IR De-Formulation

of the Adhesive Polymer Mixture

A

C B?

Max (Band) Chromatogram at 2929 cm-1

Selected Band Chromatogram at 1724 cm-1

A

B

-CH2

2929

C=O

1724

GPC-IR Database Search to Identify Peak A

at 10 minutes as EVA Polymer

A

GPC-IR to Identify Components

C & B by Spectral Subtraction

Component C

Paraffin

Component B Glycerol Rosin Ester

A

C

B

C A

B

GPC Confirmation of the De-Formulated Components

with Known Standards A, B & C

Case #2: De-Formulate a Flexible Conductive Ink

by GPC-IR

Silver ink paste filled with Ag particles (~80% Wt)

• Designed to screen print flexible circuitry

such as membrane switches

• Extremely flexible after curing at 150°C for 30 minutes

• Very conductive even under 20x folding / crease stress tests

(ASTM F1683). 5 times better than the next competitor

• Understand the unique formulation technology

• Deformulate the complex polymer system

De-Formulating the Conductive Ink GPC-IR Chromatogram

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.: -10°C

Cyclone Temp.: 130°C

Condenser Temp.: 15°C

Disk Speed: 12 mm/min

Stacked IR Spectra of Components A, B, C

at Different GPC Times (~ MWD Centers)

NH

Commercial IR Database Search (FDM & Thermo)

for Polymer A (Red): Polyester Suppliers

Index % Match Compound Name Library

434 96.63 Amoco Resin PE-350 Polyester Coatings Technology

450 95.96 Dynapol LH-812 Polyester Coatings Technology

467 95.65 Vitel VPE-222F Polyester Coatings Technology

443 95.06 Dynapol L-411 Coatings Technology

466 94.45 Vitel PE-200 Coatings Technology

Commercial IR Database Search (FDM & Thermo)

for Component B (Blue): Polyurethane Supplier

Index % Match Compound Name

503 88.13 Spensol L-53 UROTUF L-53 Polyurethane

949 87.51 Polyester Polyol 0305

424 87.33 Polycaprolactone

944 87.29 Polyester Polyol 0200

212 86.86 UCAR Cyracure UVR-6351

NH

OH

Commercial IR Database Search (FDM & Thermo)

for Component C (Red): Cross-linker Supplier

Index % Match Compound Name

834 92.47 Desmodur LS-2800, CAS# 93919-05-2, MW 766, Cross-linking Agent

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

Reverse-Engineering the Conductive Ink

by GPC-IR Deformulation

• C: Desmodur LS-2800

• Ketoxime blocked HDI trimer

• Latent cross-linking agent

• De-blocked C cross-linking

with Polymer B Chains

• Interpenetrating with Polymer A

• Lock Ag fillers in place to form

conductive circuitry

• Super flexibility & elasticity

• Superior end-use properties

Curing (150oC / 30 min)

C

B

A

C

Column: Eclipse XDB-C18, 4.6 x150mm

Mobile Phase: A&B at 1.0 ml/min

Solvent A: 0.1% Formic Acid in Water

Solvent B: 0.1% Formic Acid in MeOH

Gradient: Time/%B: 0/1, 30/95, 40/95

Sample Conc.:10 mg/ml in MeOH

Injection Volume: 75 μl

IR Detector Res.: 8 cm-1

Nebulizer Power: 18 watts

ZnSe Disk Temp.: -10°C

Cyclone Temp.: 180°C

Condenser Temp.: 5°C

Disk Speed: 3 mm/min

A

B

C

Case #3: De-Formulate a UV Curable Coating

by HPLC-IR

Commercial IR Database Search

for Component A (Blue)

Index % Match Compound Name Library

707 71.09 Ethyl Acrylate Coatings Technology (Thermo)

724 69.15 Hydroxylpropyl Acrylate Coatings Technology (Thermo)

750 68.43 1,6-Hexanediol Diacrylate Coatings Technology (Thermo)

Commercial IR Database Search

for Component B (Blue)

Index % Match Compound Name Library

754 97.86 Trimethylolpropane Triacrylate Coatings Technology (Thermo)

759 95.98 Dipentaerythritol Triacrylate Coatings Technology (Thermo)

757 95.24 Pentaerythritol Triacrylate Coatings Technology (Thermo)

IR Database Search for Component C (Aqua):

Photomer 6022

Index % Match Compound Name Library

807 94.88 Photomer 6022: Urethane Acrylate Oligmer

Coatings Technology (Thermo)

754 93.56 Trimethylolpropane Triacrylate Coatings Technology (Thermo)

757 93.44 Pentaerythritol Triacrylate Coatings Technology (Thermo)

Case #4: De-Formulate Lubricant Additives

in SAE 15W-40 Motor Oil

8

9

10

11

12

0

.05

.1

.15

4000 3500 3000 2500 2000 1500 1000

Identification of additives like stabilizers,

viscosity modifiers, fungicides, etc.

Stability: ageing & failure analysis

Wavenumber, cm-1

GPC Elution

Time

(Min. & MW)

Additive X

Additive Y

Low MW mineral oil (~85%) diverted after 12.2 min

De-Formulation of Motor Oil

Additive X at RT 9.2 Minutes

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

De-Formulation of Motor Oil

Additive Y at RT 12 Minutes

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

Additive De-Formulation in

Motor Oil Lubricant by GPC-IR

• De-formulated polymeric additives X & Y in motor oil lubricant

• Additive X at retention time 9.2 minutes

Narrow MW distribution ~ average 600K (GPC)

Styrene-Acrylate copolymer (IR database search)

Viscosity Index improver

• Additive Y at retention time 10-12 minutes

Broad MW range: 8-30K (GPC)

Polyisobutenyl Succinimide (PIBS) (IR database search)

Dispersant for metal particles

• Polymer degradation study

Analyze polymer breakdown or cross-linking by GPC

Detect oxidized intermediates by IR

Oil change schedule

GPC-IR to Characterize Polymer Stability in

Lubricant Oils

X3

X4

X1

X2

X0 ID?

Y0

Ageing @ 170C

G0: 0 hr

G12: 12 hr

G24: 24 hr

G36: 36 hr

G48: 48 hr

Note: Base oil was diverted at 25 min.

In-House IR Database Search for Polymeric

Additive X0 (Red): SEB Copolymer

Compositional Changes of Polymeric Additive

X0 X1, X2, X3 & X4 by Oxidation

Ageing @ 170C

G0: 0 hr

G12: 12 hr

G24: 24 hr

G36: 36 hr

G48: 48 hr

Ether

Ox

ira

ne

GPC-IR to Characterize Polymer Degradation in Oils

X3

X4

X1

X2

X0 ID: SEB

Y0

Ageing @ 170C

G0: 0 hr

G12: 12 hr

G24: 24 hr

G36: 36 hr

G48: 48 hr

Oxidizing

Ethers (1000-1200 cm-1)

Oxiranes (806 cm-1)

Polymeric Additive X0 Oxidized to X4 and

Breakdown to Z4

Ageing @ 170C

G0: 0 hr X0

G48: 48 hr X4

dotted line Z4

Ether

Ox

ira

ne

C=O

GPC-IR to Characterize Polymer Degradation in Oils

X3

X4

X1

X2

X0 ID: SEB

Y0

Ageing @ 170C

G0: 0 hr

G12: 12 hr

G24: 24 hr

G36: 36 hr

G48: 48 hr

Oxidizing

Ethers

Oxiranes

Oxidative

Breakdown

Carbonyls

Oxiranes

Ethers

Summary: GPC-IR to De-Formulate Complex

Polymer Mixtures

• GPC-IR is well adapted for the de-formulation of complex polymer systems

Separation of all the components of a mixture (polymer and small molecules)

Detection of each component by IR (solid phase transmission)

Identification by IR database search (commercial & proprietary databases)

• Useful:

For competitive analysis / IP protection

To find specific raw material supplier or qualify a second supplier

For problem solving / trouble shooting / contamination analysis / degradation

• Applicable to coatings, adhesives, inks, sealants, elastomers,

plastics, rubbers, composites, biopolymers …

Summary: GPC-IR to De-Formulate Complex

Polymer Systems

X? Y? Z?

IR Spectra

IR ID A-B Copolymer C Polymer Additive

IR Database Product Name Product # Brand Name

Search & Supplier & Supplier & Supplier

GPC Separation

Summary: GPC-IR to Characterize Compositional /

Structural Variations of Copolymers across MWD

A-B C

IR Spectra

Composition Supplier-to-Supplier Built-in Feature / Difference for ID

Drifts & Lot-to-Lot Variations Copolymer R&D / Process Control

Variations & Incoming QC for Users

A/B

Ratios A

B

Summary: GPC-IR to Characterize Copolymer

Degradation from Ageing / Processing

Degradation Loss of Functional Group A (Reduced A/B Ratios)

Polymer Breakdown ( Lower MW Degradants)

Cross-linking ( Higher MW with New Functional Groups)

Confirm No Degradation / Stability Study

A-B C Degradants

A/B

Ratios Degradation

Application Notes

Deformulating Polymeric Ink

Formula by GPC-IR Technology

Characterization of a Hot-Melt

Adhesive by LC-IR

Lubricants Analysis

Analysis of Polymer Blends by

GPC-FTIR

Polymer Characterization by

Combined Chromatography-

Infrared Spectroscopy (article

published in LC-GC)

www.spectra-analysis.com

Tom Kearney

Vice President of Sales

508-281-6274

tomkearney@spectra-analysis.com

Tracy Phillpott

Senior Applications Chemist

864-751-4834

phillpottt@spectra-analysis.com

Spectra Analysis Instruments, Inc. www.spectra-analysis.com

Ming Zhou, PhD

Director of Applications Engineering

508-281-6276

zhoum@spectra-analysis.com

Comparison of Max Band Chromatogram (Black)

and Selected Band Chromatograms

A

B

C

Elution Time (Min.)

Band 1690 cm-1

Band 1510 cm-1

Band 730 cm-1

Max Band

Default

At 1730 cm-1

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

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

51