Post on 01-Jul-2015
description
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 Compositions
Proteins Polymer Mixtures
Additive Analysis
LC = 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
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
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
HPLC-IR Operating Conditions for 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 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): TMP Triacrylate
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)
Online IR Library Search from FTIRsearch.com for Peak C (Red) at 26.77’
Correlation search with auto baseline correction ON Overlay view displayed Peak C: Pentaerythritol Triacrylate (Top Match)
IR Database Search for Component D (Aqua): Photomer 6022: Urethane Acrylate
Index % Match Compound Name Library
807 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 ON Overlay view displayed Peak 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 6022 Urethane Acrylate Oligomer
C = Pentaerythritol Triacrylate
EF 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°C
Cyclone Temp.: 130°C
Condenser Temp.: 15°CDisk Speed: 12 mm/min
High MW Low MW
GPC 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 Library
434 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 Name
503 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
O
N
O
N
O
O
O
Reverse-Engineering the Conductive Ink by GPC-IR Deformulation
N
N
N
(CH2)6(H2C)6
O
OO
(CH2)6
HN
NH
HN O
N
O
N
O
N
O
O
O
• C: Desmodur LS-2800• Ketoxime blocked HDI trimer• Latent cross-linking agent
N
N
N
(CH2)6(H2C)6
O
OO
(CH2)6
N
NN C OCO
C
O
N
H
C O
N
H
C O
O
O
N
O
O
H
• 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
Case #3: Deformulate 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 such as
stabilizers, viscosity modifiers, 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
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 Molecules Additives Impurities Degradants
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/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
A-B C Degradants
A/B Ratios Degradation
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High MW Low MW GPC Elution
Time
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)
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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