PEG 1000 base, typically 20 – 25 monomer units, Stegosaurus, reverse phase Note arrow pointing to where we found the oxidation products. Compounds of interest buried in the noise of chromatogram.
Figure. GPC-IR application summary to characterize poly (A-B) copolymers and to de-formulate polymer mixtures.
Webinar: How to Figure Out Your Competitors Formula by LC-IR Deformulation
Webinar – Oct. 23, 2012 How To Figure out Your Competitor’s Formula ?Deformulating Complex Polymer Systems by LC-IR Coupled Technology Tracy Phillpott, Sr. Apps Chemist Dr. Ming Zhou, Director of Apps Engineering Spectra Analysis Instruments Inc., Marlborough, MA Contact: ZhouM@Spectra-Analysis.com 1
OUTLINE 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 2
Coupled Technologies & Major Applications LC-MS LC-IRSeparation Liquid Chromatography Liquid ChromatographyDetection & Mass Infra Red Infra Red Spectroscopy Spectroscopy SpectroscopyData AnalysisApplications Small Molecules Copolymer Compositions Proteins Polymer Mixtures Additive Analysis LC = GPC / SEC or HPLC
GPC-IR Coupled Technology for Polymers: Principle & Information Output GPC Separation of the Polymers by MW or Size Infrared Spectroscopy forCompositional Information
Principle of a LC-IR Coupled SystemLC DiscovIR-LC •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-IR Coupled SystemSystem Control Deposition Hyphen HPLCData Processing Microscopic FTIR Desolvation or GPC
Hyphen: A Proprietary Desolvation Technology N2 Addition Cyclone Thermal Cyclone EvaporatorFrom LC Evaporator Nebulization Air Cooled Condenser Chilled Condenser Particle Stream to DiscovIR Patent pending: Waste Solvent PCT/US2007/ 025207
Desolvation Stage #1: The Thermal Nebulization The thin-wall stainless steel capillary tube nebulizer is regulated toevaporate approximately half the solvent (electric heating). Solvent expansion upon conversion to vapor increases thenebulizer 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 (gradientchanges monitored by changes in electrical resistance).
Desolvation Stage #2: Inside the Cyclone Evaporator Centrifugal force holds the droplets (solute) near the cyclone wall. Just beforethe droplet goes to dryness, its volume to surface ratio becomes small enough thatit is dragged out of the cavity by the exiting solvent vapor. Evaporative cooling protects the solute from both evaporation and degradationby limiting the maximum solute temperature to the solvent boiling point. The solventboiling 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 11
What is Direct Deposition FTIR?Separated Dot Depositing on Disk Separated Dots from HPLC-IR Continuous Polymer Tracks (GPC-IR)
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 14
OUTLINE 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 16
Case #1: De-Formulate a UV Curable Coating by HPLC-IR
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: 75µl 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 µm PTFE filter before HPLC injection. The sample concentration was ~ 10 mg/ml (1.0%).
Commercial IR Database Search for Component A (Blue): Ethyl AcrylateIndex % 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 TriacrylateIndex % 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 NHIndex % Match Compound Name Library807 94.88 Photomer 6022: Coatings Technology (Thermo) Urethane Acrylate Oligmer, Hexafunctional Aromatic754 93.56 Trimethylolpropane Triacrylate Coatings Technology (Thermo)757 93.44 Pentaerythritol Triacrylate Coatings Technology (Thermo)
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
Deformulation Results of the UV Curable Coating by HPLC-IR A = Ethyl Acrylate B = TMP Triacrylate C = Pentaerythritol Triacrylate D = Photomer 6022 Urethane Acrylate Oligomer E FG
Degradation Study of PEG-1000 Pharmaceutical ExcipientReverse-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-IRSilver 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 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/minHigh MW Low MW GPC Elution Time
Stacked IR Spectra of Components A, B, C at their MWD ApexesNH
Commercial IR Database Search for Polymer A (Red): PolyesterIndex % 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 NH OHIndex % Match Compound Name503 88.13 Spensol L-53 UROTUF L-53 Polyurethane949 87.51 Polyester Polyol 0305424 87.33 Polycaprolactone944 87.29 Polyester Polyol 0200212 86.86 UCAR Cyracure UVR-6351
Commercial IR Database Search for Component C (Red): Cross-linkerIndex % 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
Reverse-Engineering the Conductive Ink by GPC-IR Deformulation • C: Desmodur LS-2800C • Ketoxime blocked HDI trimer • Latent cross-linking agent Curing (150oC / 30 min)B • De-blocked C cross-linking with Polymer B Chains • Interpenetrating with Polymer AA • Lock Ag fillers in place to form conductive circuitry • Super flexibility & elasticity • Superior end-use properties
Case #3: Deformulate Lubricant Additives in SAE 15W-40 Motor Oil Identiﬁcation of additives such as stabilizers, viscosity modifiers, etc. Stability: ageing & failure analysis Additive Y 12 11 Additive X 10 GPC Elution 9 Time 8 (Min. & MW) 3500 3000 2500 2000 1500 1000 Wavenumber, cm-1Low MW mineral oil (~85%) diverted after 12.2 min
Deformulation of Motor Oil Additive X at RT 9.2 MinutesIn-House IR database search: Styrene-Acrylate Copolymer
Deformulation of Motor Oil Additive Y at RT 12 MinutesIn-House IR database search: Polyisobutenyl Succinimide (PIBS)
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 Analysis HPLC-IR of Polymer Extract HPLC Conditions: Columns: guard+ Eclipse C18 50mm x 46mm 5um C Mobile phase: Grad. 75-100% AcN (5min)-100%AcN(5min) in Water, 1ml/min DA DiscovIR Conditions: B Nebulizer 2.2W, Carrier gas 400cc, Disk Speed 3mm/min, Disk Temp. -110ºC, Pressure Chamber: 6.58 torr Condenser (single) temp. 10ºC, Cyclone temperature: 200ºC
Additive Identification by HPLC-IR In-House Database Search ResultsA B DC
Polymer Additive Analysis by GPEC-IR for PDMS in THF/H2OPolyDiMethyl Siloxane is Difficult to be Detected by UV or RI. IR is an Universal Detector for Organics Y X Y X Z Z
OUTLINE 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 42
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 IR Spectra X? Y? Z? High MW Low MWIR ID A-B Copolymer C Polymer AdditiveIR Database Product Name Product # Brand NameSearch & Supplier & Supplier & Supplier
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 ......
OUTLINE 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 48
Polymer & Small Molecule Analysis by GPC-IR for ABS Plastic w/ No Extraction StepGPC-IR Chromatogram (Blue) for ABS Sample and Ratio Plot of Nitrile/Styrene (2240 cm-1/1495 cm-1 in Green). Polymers Small Molecules Additives Impurities Degradants
Polymer Additive Analysis GPC-IR for ABS Plastic w/ No Extraction StepIR spectra at different elution times across the low MW peak of the SECanalysis of ABS. Spectra indicate presence of multiple components.
Comparison of Max Band (Black) & Selected Band Chromatograms Band 1690 cm-1Max Band Band 1510 cm-1DefaultAt 1730 cm-1 A Band 730 cm-1 B C Elution Time (Min.)
Summary: GPC-IR to Characterize Copolymer Compositions across MWD IR Spectra B A/B Ratios A A-B CComposition Supplier-to-Supplier Built-in Feature/Difference for IDDrifts & Lot-to-Lot Variations Copolymer R&D / Process ControlVariations & Incoming QC for Users
Summary: GPC-IR to Characterize Copolymer Degradation from Ageing / Processing A/B Ratios Degradation A-B C DegradantsDegradation 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
Summary: GPC-IR Applications Profile Polymer Compositions = f (Sizes) Cross Linking Break Down IR Spectra B A A/B Ratio High MW Low MW GPC Elution Time 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) 54 Cross-linking ( Higher MW) Break down ( Lower MW) & Detect low MW degradant De-Formulate Complex Polymer Mixtures
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 56