How To Figure out Your Competitor’s Formula ?

Tracy Phillpott, Sr. Apps Chemist

Dr. Ming Zhou, Director of Apps Engineering

Spectra Analysis Instruments Inc., Marlborough, MA

Contact: ZhouM@Spectra-Analysis.com1

Webinar – Oct. 23, 2012

Deformulating Complex Polymer Systems by LC-IR Coupled Technology

OUTLINE

2

Introduction: LC-IR Coupled Technology

DiscovIR System: Instrumentation & Features

LC-IR to Deformulate Complex Polymer Systems

Case #1: HPLC-IR to Deformulate a UV Curable Coating

Case #2: GPC-IR to Deformulate a Conductive Ink

Case #3: To Deformulate Additives in Lubricant Oil & Others

Summary

Q & A

Coupled Technologies &Major Applications

Liquid ChromatographyLiquid Chromatography

MassSpectroscopy

Infra RedSpectroscopy

Infra RedSpectroscopy

Separation

Applications Small Molecules Copolymer CompositionsProteins Polymer Mixtures

Additive AnalysisLC = GPC / SEC or HPLC

Detection &Data Analysis

LC-MS LC-IR

GPC-IR Coupled Technology for Polymers: Principle & Information Output

Infrared Spectroscopy for Compositional Information

GPC Separation of the Polymers by MW or Size

Principle of a LC-IR Coupled 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.

LC

DiscovIR-LC

LC-IR Coupled System

HPLCor GPC

HyphenDesolvation

DepositionMicroscopic FTIR

System ControlData Processing

Schematic View of LC-IR System

GPC orHPLC

Hyphen: A Proprietary Desolvation Technology

CycloneEvaporator

Thermal

NebulizationFrom LC

N2 Addition

ChilledCondenser

Waste Solvent

Particle Stream to DiscovIR

Air CooledCondenser

CycloneEvaporator

Patent pending: PCT/US2007/025207

Desolvation Stage #1: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).

Desolvation Stage #2: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.

ZnSe Sample Disk

Rotate at tunable speed 10-0.3 mm/min

Unattended overnight runs/10h The yellow ZnSe disk is under

vacuum with NO moisture or CO2 interference

Disk Temp: - 50C ~ 100C Transmission IR analysis is

done on the solid deposit. Re-usable after solvent

cleaning Mid-IR transparent

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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 GPC/SEC Solvents: e.g. THF, TCB, HFIP, Chloroform, DMF

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

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OUTLINE

16

Introduction: LC-IR Coupled Technology

DiscovIR System: Instrumentation & Features

LC-IR to Deformulate Complex Polymer Systems

Case #1: HPLC-IR to Deformulate a UV Curable Coating

Case #2: GPC-IR to Deformulate a Conductive Ink

Case #3: To Deformulate Additives in Lubricant Oil & Others

Summary

Q & A

Case #1: De-Formulate a UV Curable Coating by HPLC-IR

HPLC-IR Operating Conditionsfor the Coating Deformulation

LC System Settings: Agilent 1200• HPLC Column: Eclipse XDB-C18, 4.6 x150mm• Mobile Phase: A & B at 1.0 ml/min Flow Rate• Solvent A: Water with 0.1% Formic Acid• Solvent B: Methanol with 0.1% Formic Acid• Gradient: B% linear ramp from 1%-95% in 0-30’, hold at 95%B in 30-40’.• Injection Volume: 75l

IR Detection: DiscovIR-LC®

• Cyclone Temperature: 180oC• Condenser Temperature: 5oC• ZnSe Disk Temperature: -10oC• Disk Speed: 3 mm/min

Sample Preparation• 100 mg of the coating sample was dissolved in 10 ml methanol and

the solution was filtered through 0.45 m PTFE filter before HPLC injection. The sample concentration was ~ 10 mg/ml (1.0%).

Commercial IR Database Search for Component A (Blue): Ethyl Acrylate

Index % Match Compound Name Library707 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): TMP Triacrylate

Index % Match Compound Name Library754 97.86 Trimethylolpropane Triacrylate Coatings Technology (Thermo)759 95.98 Dipentaerythritol Triacrylate Coatings Technology (Thermo)757 95.24 Pentaerythritol Triacrylate Coatings Technology (Thermo)

Online IR Library Search from FTIRsearch.com for Peak C (Red) at 26.77’

Correlation search with auto baseline correction ONOverlay view displayedPeak C: Pentaerythritol Triacrylate (Top Match)

IR Database Search for Component D (Aqua): Photomer 6022: Urethane Acrylate

Index % Match Compound Name Library807 94.88 Photomer 6022:

Urethane Acrylate Oligmer, Hexafunctional Aromatic

Coatings Technology (Thermo)

754 93.56 Trimethylolpropane Triacrylate Coatings Technology (Thermo)757 93.44 Pentaerythritol Triacrylate Coatings Technology (Thermo)

NH

Online IR Library Search from FTIRsearch.com for Peak E (Red) at 29.51’

Correlation search with auto baseline correction ONOverlay view displayedPeak E: Photomer 6022 (Urethane Acrylate) as the Top Match

Online IR Library Search from FTIRsearch.com for Peak F (Red) at 30.50’

Peak F: Photomer 6022 (Urethane Acrylate) as the Top Match

A = Ethyl Acrylate

B = TMP Triacrylate

D = Photomer 6022Urethane Acrylate

Oligomer

C = PentaerythritolTriacrylate

E F G

Deformulation Results of the UV Curable Coating by HPLC-IR

Degradation Study of PEG-1000 Pharmaceutical Excipient

Reverse-Phase HPLC-IR with H2O/ACN; PEG-1000 before Degradation

1116 cm-1 Max Band Chromatogram

Case #2: Deformulate 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

Deformulating the Conductive Ink GPC-IR Chromatogram

Column: 2 x Jordigel DVB Mixed BedMobile Phase: THF at 1.0 ml/minSample Conc.:~5 mg/ml in THFInjection Volume: 60 μl IR Detector Res.: 8 cm-1

ZnSe Disk Temp.: -10°CCyclone Temp.: 130°CCondenser Temp.: 15°CDisk Speed: 12 mm/min

High MW Low MWGPC Elution Time

Stacked IR Spectra of Components A, B, C at their MWD Apexes

NH

Commercial IR Database Search for Polymer A (Red): Polyester

Index % Match Compound Name Library434 96.63 Amoco Resin PE-350 Polyester Coatings Technology (Thermo)450 95.96 Dynapol LH-812 Polyester Coatings Technology (Thermo)467 95.65 Vitel VPE-222F Polyester Coatings Technology (Thermo)443 95.06 Dynapol L-411 Coatings Technology (Thermo)466 94.45 Vitel PE-200 Coatings Technology (Thermo)

Commercial IR Database Search for Polymer B (Blue): Polyurethane

Index % Match Compound Name503 88.13 Spensol L-53 UROTUF L-53 Polyurethane 949 87.51 Polyester Polyol 0305424 87.33 Polycaprolactone944 87.29 Polyester Polyol 0200212 86.86 UCAR Cyracure UVR-6351

NH

OH

Commercial IR Database Search for Component C (Red): Cross-linker

Index % Match Compound Name834 92.47 Desmodur LS-2800, CAS# 93919-05-2, MW 766, Cross-linking Agent3249 65.30 Caffeine; 1,3,7-Trimethylxanthine9302 64.76 Monophenylbutazone615 62.15 Betulinic acid; 3-Hydroxylup-20(29)-en-28-oic acid860 62.05 Spenlite M-27

N

N

N(CH2)6(H2C)6

O

OO

(CH2)6

HN

NH

HN O

N

ON

O

N

O

O

O

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 formconductive circuitry

• Super flexibility & elasticity• Superior end-use properties

Curing (150oC / 30 min)

C

B

A

Case #3: Deformulate Lubricant Additives in SAE 15W-40 Motor Oil

8

9

10

11

12

3500 3000 2500 2000 1500 1000

Identification of additives such as stabilizers, viscosity modifiers, etc.

Stability: ageing & failure analysis

Wavenumber, cm-1

GPCElution

Time(Min. & MW)

Additive X

Additive Y

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

Deformulation of Motor OilAdditive X at RT 9.2 Minutes

In-House IR database search: Styrene-Acrylate Copolymer

 

4000 3500 3000 2500 2000 1500 1000

wavenumber, cm-1

Shell Rotella T Heavy Duty 15W-409.2 minute eluant

Deformulation of Motor Oil Additive Y at RT 12 Minutes

In-House IR database search: Polyisobutenyl Succinimide (PIBS)

 

4000 3500 3000 2500 2000 1500 1000

wavenumber, cm-1

Shell Rotella T Heavy Duty 15W-4012 minute eluant

Additive Deformulation 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 or degradants by IR Oil change schedule

Polymer Additive AnalysisHPLC-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. -110ºC, Pressure Chamber: 6.58 torrCondenser (single) temp. 10ºC, Cyclone temperature: 200ºC

AB

D

C

Additive Identification by HPLC-IRIn-House Database Search Results

A

C

B

D

Polymer Additive Analysisby GPEC-IR for PDMS in THF/H2O

PolyDiMethyl Siloxane is Difficult to be Detected by UV or RI.IR is an Universal Detector for Organics

X

Y

Z Z

Y

X

Additive AnalysisLC-IR Application Scope

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• 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

OUTLINE

42

Introduction: LC-IR Coupled Technology

DiscovIR System: Instrumentation & Features

LC-IR to Deformulate Complex Polymer Systems

Case #1: HPLC-IR to Deformulate a UV Curable Coating

Case #2: GPC-IR to Deformulate a Conductive Ink

Case #3: To Deformulate Additives in Lubricant Oil & Others

Summary

Q & A

Summary: LC-IR to Deformulate Complex Polymer Mixtures

• LC-IR is well suited to deformulate 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

For problem solving / trouble shooting / contamination analysis

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

plastics, rubbers, composites, biopolymers …

Summary: GPC-IR to Deformulate Complex Polymer Systems

X? Y? Z?

IR Spectra

IR ID A-B Copolymer C Polymer Additive IR Database Product Name Product # Brand NameSearch & Supplier & Supplier & Supplier

High MW Low MW

Application Notes Available

Deformulating UV Coating System by LC-IR Technology

Deformulating Polymeric Ink Formula by GPC-IR Technology

Lubricants Analysis Characterization of a Hot-Melt

Adhesive by LC-IR Analysis of Polymer Blends by

GPC-FTIR Polymer Characterization by

Combined Chromatography-Infrared Spectroscopy (article published in LCGC)

www.spectra-analysis.com

DiscovIR Users Dow Chemical Polymers Du Pont Polymers BASF Polymers WR Grace Polymers SABIC Polymers Afton Chemical Polymers Nissan (Japan) Polymers China Mining Univ. Polymers Novartis Polymer (Pharma) Merck Polymer (Pharma) Johnson & Johnson Polymer (Pharma) Shire Pharma Polymer (Pharma) Lawrence Livermore National Lab Trace Analysis Oak Ridge National Laboratory Environmental Naval Research Laboratory Organics US Army Aberdeen Proving Ground Forensics Canada Border Control Forensics State Police: Forensic Labs Forensics

AL, LA, VT, PA, MD, VA, GA ......

Rita Barbagallo

Technical Sales Representative

864-751-4833

barbagallor@spectra-analysis.com

Tracy Phillpott

Senior Applications Chemist

864-751-4834

phillpottt@spectra-analysis.com

Contact Information Ming Zhou, PhD

Director of Applications Engineering

508-281-6276

zhoum@spectra-analysis.com

www.spectra-analysis.com

OUTLINE

48

Introduction: LC-IR Coupled Technology

DiscovIR System: Instrumentation & Features

LC-IR to Deformulate Complex Polymer Systems

Case #1: HPLC-IR to Deformulate a UV Curable Coating

Case #2: GPC-IR to Deformulate a Conductive Ink

Case #3: To Deformulate Additives in Lubricant Oil & Others

Summary

Q & A

Polymer & Small Molecule Analysis byGPC-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 in Green).

Small MoleculesAdditivesImpuritiesDegradants

Polymers

Polymer Additive AnalysisGPC-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.

Comparison of Max Band (Black)& Selected Band Chromatograms

A

BC

Elution Time (Min.)

Band 1690 cm-1

Band 1510 cm-1

Band 730 cm-1

Max BandDefault At 1730 cm-1

Summary: GPC-IR to Characterize Copolymer Compositions across MWD

A-B C

IR Spectra

Composition Supplier-to-Supplier Built-in Feature/Difference for IDDrifts & Lot-to-Lot Variations Copolymer R&D / Process ControlVariations & Incoming QC for Users

A/BRatios 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

A-B C Degradants

A/BRatios Degradation

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High MW Low MW GPCElution Time

A/B Ratio AB

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 SpectraBreak DownCross Linking

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

Summary: GPC-IR Applications in Polymer-Related Industries

DiscovIR-LC is a Powerful Tool for Polymers, Additives & Materials Analysis

Deformulate complex polymer mixtures: identify polymer components

Characterize copolymer composition variations across MWD

Characterize polymer changes: degradation or modification

Useful:

For competitive analysis / IP protection

To find specific raw material supplier or qualify a second supplier

For new copolymer R&D and process scale-up

To characterize polymer degradation: ageing study, failure analysis

For problem solving / trouble shooting as general analytical capability

Applicable to Coatings, Adhesives, Inks, Sealants, Elastomers,

Plastics, Rubbers, Composites, Biopolymers ……

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

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