How To Figure out Your Competitor’s Formula ? Deformulating Complex Polymer Systems

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: [email protected]
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
Separation
Detection &
Data Analysis
Applications
LC-IR
LiquidChromatography
Chromatography
Liquid
Mass
Spectroscopy
Small Molecules
Proteins
InfraRed
Red
Infra
Spectroscopy
Spectroscopy
Copolymer Compositions
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 for
Compositional Information
Principle of a LC-IR Coupled
System
LC
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 System
System Control
Data Processing
Deposition
Microscopic FTIR
Hyphen
Desolvation
HPLC
or GPC
Schematic View of LC-IR System
GPC
or
HPLC
Hyphen: A Proprietary Desolvation
Technology
N2 Addition
Thermal
From LC
Nebulization
Cyclone
Evaporator
Cyclone
Evaporator
Air Cooled
Condenser
Chilled
Condenser
Particle Stream to DiscovIR
Patent
pending:
PCT/US2007/
025207
Waste Solvent
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 micrometersized 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
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: 75l
 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
707
% Match
71.09
724
750
69.15
68.43
Compound Name
Ethyl Acrylate
Hydroxylpropyl Acrylate
1,6-Hexanediol Diacrylate
Library
Coatings Technology (Thermo)
Coatings Technology (Thermo)
Coatings Technology (Thermo)
Commercial IR Database Search for
Component B (Blue): TMP Triacrylate
Index
754
759
757
% Match
97.86
95.98
95.24
Compound Name
Trimethylolpropane Triacrylate
Dipentaerythritol Triacrylate
Pentaerythritol Triacrylate
Library
Coatings Technology (Thermo)
Coatings Technology (Thermo)
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
NH
Index
807
% Match
94.88
754
757
93.56
93.44
Compound Name
Photomer 6022:
Urethane Acrylate Oligmer,
Hexafunctional Aromatic
Trimethylolpropane Triacrylate
Pentaerythritol Triacrylate
Library
Coatings Technology (Thermo)
Coatings Technology (Thermo)
Coatings Technology (Thermo)
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
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 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 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
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
434
450
467
443
466
% Match
96.63
95.96
95.65
95.06
94.45
Compound Name
Amoco Resin PE-350 Polyester
Dynapol LH-812 Polyester
Vitel VPE-222F
Polyester
Dynapol L-411
Vitel PE-200
Library
Coatings Technology
Coatings Technology
Coatings Technology
Coatings Technology
Coatings Technology
(Thermo)
(Thermo)
(Thermo)
(Thermo)
(Thermo)
Commercial IR Database Search
for Polymer B (Blue): Polyurethane
NH
OH
Index
503
949
424
944
212
% Match
88.13
87.51
87.33
87.29
86.86
Compound Name
Spensol L-53  UROTUF L-53
Polyester Polyol 0305
Polycaprolactone
Polyester Polyol 0200
UCAR Cyracure UVR-6351
Polyurethane
Commercial IR Database Search
for Component C (Red): Cross-linker
O
O
O
N
N
O
HN
(H2C)6
N
O
N
H
(CH2)6
N
N
O
O
(CH2)6
O
HN
N
O
Index
834
3249
9302
615
860
% Match
92.47
65.30
64.76
62.15
62.05
Compound Name
Desmodur LS-2800, CAS# 93919-05-2, MW 766, Cross-linking Agent
Caffeine; 1,3,7-Trimethylxanthine
Monophenylbutazone
Betulinic acid; 3-Hydroxylup-20(29)-en-28-oic acid
Spenlite M-27
Reverse-Engineering the Conductive
Ink by GPC-IR Deformulation
• C: Desmodur LS-2800
• Ketoxime blocked HDI trimer
• Latent cross-linking agent
C
Curing (150oC / 30 min)
B
A
• 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
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
9
8
3500
3000
2500
2000
Wavenumber, cm-1
Low MW mineral oil (~85%) diverted after 12.2 min
1500
1000
GPC
Elution
Time
(Min. & MW)
Deformulation of Motor Oil
Additive X at RT 9.2 Minutes
Shell Rotella T Heavy Duty 15W-40
9.2 minute eluant
4000
3500
3000
2500
2000
1500
1000
wavenumber, cm-1
In-House IR database search: Styrene-Acrylate Copolymer
Deformulation of Motor Oil
Additive Y at RT 12 Minutes
Shell Rotella T Heavy Duty 15W-40
12 minute eluant
4000
3500
3000
2500
2000
1500
1000
wavenumber, cm-1
In-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:
C
A
D
B
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 torr
Condenser (single) temp. 10ºC,
Cyclone temperature: 200ºC
Additive Identification by HPLC-IR
In-House Database Search Results
A
B
D
C
Polymer Additive Analysis
by 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
Y
X
Y
X
Z
Z
Additive Analysis
LC-IR Application Scope
•
•
•
•
•
•
•
•
•
•
•
•
•
•
•
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
41
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?
High MW
IR ID
IR Database
Search
Z?
Low MW
A-B Copolymer
Product Name
& Supplier
C Polymer
Product #
& Supplier
Additive
Brand Name
& 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 ChromatographyInfrared Spectroscopy (article
published in LCGC)
www.spectra-analysis.com
DiscovIR Users
 Dow Chemical
 Du Pont
 BASF
 WR Grace
 SABIC
 Afton Chemical
 Nissan (Japan)
 China Mining Univ.
 Novartis
 Merck
 Johnson & Johnson
 Shire Pharma
 Lawrence Livermore National Lab
 Oak Ridge National Laboratory
 Naval Research Laboratory
 US Army Aberdeen Proving Ground
 Canada Border Control
 State Police: Forensic Labs
AL, LA, VT, PA, MD, VA, GA ......
Polymers
Polymers
Polymers
Polymers
Polymers
Polymers
Polymers
Polymers
Polymer (Pharma)
Polymer (Pharma)
Polymer (Pharma)
Polymer (Pharma)
Trace Analysis
Environmental
Organics
Forensics
Forensics
Forensics
Contact Information
Ming Zhou, PhD
Director of Applications Engineering
508-281-6276
[email protected]
Tracy Phillpott
Senior Applications Chemist
864-751-4834
[email protected]
Rita Barbagallo
Technical Sales Representative
864-751-4833
[email protected]
www.spectra-analysis.com
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 Step
GPC-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 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
Max Band
Default
At 1730 cm-1
Band 1690 cm-1
Band 1510 cm-1
A
B
Band 730 cm-1
C
Elution Time (Min.)
Summary: GPC-IR to Characterize
Copolymer Compositions across MWD
A-B
Composition
Drifts &
Variations
Supplier-to-Supplier
Lot-to-Lot Variations
B
IR Spectra
A/B
Ratios
A
C
Built-in Feature/Difference for ID
Copolymer R&D / Process Control
& Incoming QC for Users
Summary: GPC-IR to Characterize Copolymer
Degradation from Ageing / Processing
A/B
Ratios
Degradation
A-B
Degradation
C
Degradants
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
A/B Ratio
High MW
Break Down
A
IR Spectra B
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)
 Cross-linking ( Higher MW)
 Break down ( Lower MW) & Detect low MW degradant
 De-Formulate Complex Polymer Mixtures
54
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