Post on 15-Apr-2018
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Advanced GPC Technology as a Part of Solving Complex Polymer Problems Scott D. Hanton, Chanell Brown, and Dale Willcox
Intertek Allentown
September 2014
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Acknowledgments
• Intertek
• Sherri Bassner
• Todd McEvoy
• Devon Shankweiler
• Air Products
• Dennis Nagy
• Waters
• Damian Morrison
• Michael O’Leary
• Betsy Baer
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Outline
• Intertek introduction
• Polymer analysis
• Traditional GPC
• High performance SEC
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Extensive Global NetworkE
More than
1,000 laboratories and offices
•FTSE 100 company in the Support Services sector
•Revenues of $3.5 billion in 2013.
More than
120 countries
Approximately
36,000 people
Introduction to Intertek
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Intertek Allentown – Yesterday and Today
• Formerly the corporate analytical group for Air Products and Chemicals • Joined Intertek network in July 2010
• Supported R&D, technical service, process scale-up, and manufacturing troubleshooting globally
• Today • ISO 17025 lab located in Allentown, Pennsylvania USA. Forty-six
technical and administrative staff members.
• Problem-solving and non-standardized testing for multiple industries including Materials (ceramics, polymers, composites), Medical Devices, Pharmaceuticals, Chemicals, Construction Materials and more
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Intertek Allentown Your Problem-Solving Partner
Problem-Solving Teams
Inorganic Analysis
Microscopy, metallurgy, surface science, diffraction,
failure analysis, , particle size
Residue ID, ceramics, polymer
structure, electronic and nano-materials
Titrations, trace metals
System stability, impurity analysis, gases/chemicals
Material Properties
Rheology, thermal analysis/hazards,
sorption
Polymer systems, catalysis, reaction
studies, gas separation
Organic Analysis
Chromatography, MS, NMR,
spectroscopy
Chemical structure identification, degradation
analysis, impurity analysis
Mechanical/ environ. Testing
(Pittsfield)
Extractables and
Leachables (Whitehouse)
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Introduction
• Polymer chemistry continues to be vital
• New products
• New uses
• New research
• Significant challenges presented in polymer analysis
• Multiple monomers
• Solubility
• Complex structures
• Complex formulations
• Require multiple and powerful tools to analyze polymers
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Polymeric Materials
Applications
Physical Properties
Molecular Structure Molecular Weight Distribution
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Polymer structures
• Many different polymer structures have been developed
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Polymer Detective
• What is it?
• What are its properties?
• How does it behave?
• What else is in it?
• Where is it?
• How big is it?
• How much of it is there?
• What is its chemical structure?
• How is it connected?
• What’s on the end?
What? Where? How? Who?
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Polymer Analysis Decision Tree
Identity
FTIR
Raman
CHNOS
SEC
Material Properties
Density
Rheology
DSC
TMA
Sorption
Morphology
SEM
AFM
Components
TGA
XRF
GC
LC
Chemical Structure
NMR
MS
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GPC: “Good” Sample vs. “Bad” Sample
Acrylonitrile Butadiene Styrene (ABS) tubs
Damaged Tub Undamaged Tub
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High Temperature – GPC: “Good” and “Bad” Strap
Sample ID Mn (Daltons) Mw (Daltons) Mp (Daltons) Mz (Daltons) PDI (Mw/Mn)
Bad 6,570 27,100 27,100 54,700 4.1
Good 49,600 172,000 140,000 354,000 3.5
Polypropylene straps
2 3 4 5 6 7 Log MW
Bad Strap
Good Strap
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HT-GPC: “Good” and “Cracked” Lip Balm Squeeze Tubes
Cracked tube
Recent tube Original tube
2 3 5 6 7 4 Log MW
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Amine GPC: Amine and Quaternary Amine Polymers
Obtain useful chromatograms from materials with high amine functionality
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GPC: Monitor Polymer Formation
High Molecular Weight Species
Compare against competitors Polymer formation results in poor performance
Polyamines
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GPC: Monitor Polymer Formation
Polymer Formation
Sample Aged
Sample Air Exposed
Competitor 2
Competitor 1 Sample
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GPC: Trace Determination of Polymer Content
y = 3002.8x - 53039R² = 0.9987
0
500000
1000000
1500000
2000000
2500000
0 100 200 300 400 500 600 700 800
Pe
ak R
esp
on
se (
Are
a C
ou
nt)
Concentration (ppm)
HA Calibration Curve
Series1
Linear (Series1)
Hyaluronic Acid Standard Calibrated from 100 – 800 ppm
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Traditional GPC vs APC
• Conventional GPC
− New Solvent equilibration takes 9 – 48 hours
− Operate columns under low backpressure
− Large system volume lead to loss of resolution
− Typical analysis time 30 – 45 minutes
• Advanced Polymer Chromatography (APC)
+ New solvent equilibration time takes 2 – 4 hours
+ Operate columns under high backpressure
+ Sub 3µm hybrid particle column technology combined with low dispersion result in improvements in resolution
+ Typical analysis time 10 – 15 minutes
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APC: Rapid Analysis of Polycarbonate Urethane
Urgent analyses completed in 22 hours, GPC would have taken 3 days
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APC vs GPC: Polyalkyleneglycol (PAG)
APC GPC
R&D analysis – Improved resolution and speed (15 min vs 35 min)
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APC: Low Mass Surfactants
Improved resolution shows starting alcohol in lowest mass products
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APC: Low Mass Surfactants
Compare ethoxylated surfactants with different end groups and number of EO’s
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APC: Oligomer Content in Polysulfones
Competitive analysis – debunk claim of lower oligomer content
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APC: Compare Silicone Putty Samples
Competitive analysis – compare MWD from different vendors
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APC: EO/PO Degree of Polymerization
R&D synthesis analysis – intended PO10/EO20 and PO55/EO40
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APC: Epoxy Resin Comparison
Regulatory analysis – compare MWD of different epoxy resins
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APC: Verify MWD of PC/ABS Polymer
R&D analysis – measure MWD of polycarbonate/acrylonitrile-butadiene-styrene material
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APC: Reactive Polymer Analysis
R&D analysis – measure MWD of Polymethylhydrogen Siloxanes
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Amine APC: Modified Amine Capped Surfactants
R&D analysis – measure MWD of Reactants and Products
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APC vs GPC: Chromatogram of Hydrocarbon Resin
APC
GPC
APC Mn (Daltons)
Mw (Daltons)
Mz (Daltons)
PDI (Mw/Mn)
APC 2,410 4,920 8,290 2.0 GPC 1,740 3,530 5,740 2.0
4.0
16.0
APC higher due to lower dispersion
Improved resolution
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APC vs GPC: Silicone Surfactant
APC
GPC
Mn (Daltons)
Mw (Daltons)
Mz (Daltons)
PDI (Mw/Mn)
APC 6,610 38,300 92,600 5.8
GPC 5,930 36,600 94,500 6.2
6.0
15.0
Improved resolution
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APC vs GPC: Poloxamer (EO:PO:EO)
APC Mw = 7,500 D
Traditional SEC Mw = 12,000 D
R&D analysis – MWD difference due to resolution or column interaction?
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Future Work on APC
• SEC of materials with more amine functionality
• Understand differences between mixed bed GPC and narrow pore size APC results
• Different mobile phases
• Aqueous
• HFIP
• Interested in modified column sets for more polar samples
• Explore column interactions
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Summary
• SEC
• Solving polymer science problems related to
• Wide range of polymer chemistry
• Wide range of problems
• APC
• Obtain much faster chromatography
• Observe improved resolution
• Useful for a wide range of polymer chemistry
• Interesting research opportunities to expand methods
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Molecular Weight Distribution
• Correlate to the end-use properties of the polymer
• Some properties are listed in table below
Tensile Strength Adhesive Strength Elastomer Relaxation Time
Cure Time Brittleness Elastic Modules
Flex Life Met Viscosity Impact Strength
Hardness Toughness Softening Temperature
Drawability Tear Strength Adhesive Tack
Stress-crack Resistance Coefficient of Friction