Advanced GPC Technology as a Part of Solving Complex Polymer Problems

Transcription

1 Advanced GPC Technology as a Part of Solving Complex Polymer Problems Scott D. Hanton, Chanell Brown, and Dale Willcox Intertek Allentown September

2 Acknowledgments Intertek Sherri Bassner Todd McEvoy Devon Shankweiler Air Products Dennis Nagy Waters Damian Morrison Michael O Leary Betsy Baer 2

3 Outline Intertek introduction Polymer analysis Traditional GPC High performance SEC 3

4 Extensive Introduction Global to Intertek NetworkE More than 1,000 laboratories and offices Approximately 36,000 people More than 120 countries FTSE 100 company in the Support Services sector Revenues of $3.5 billion in

5 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 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 5

6 Intertek Allentown Your Problem-Solving Partner Problem-Solving Teams Inorganic Analysis Material Properties Organic Analysis Mechanical/ environ. Testing (Pittsfield) Microscopy, metallurgy, surface science, diffraction, failure analysis,, particle size Titrations, trace metals Rheology, thermal analysis/hazards, sorption Chromatography, MS, NMR, spectroscopy Extractables and Leachables (Whitehouse) Residue ID, ceramics, polymer structure, electronic and nano-materials System stability, impurity analysis, gases/chemicals Polymer systems, catalysis, reaction studies, gas separation Chemical structure identification, degradation analysis, impurity analysis 6

7 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 7

8 Polymeric Materials Applications Physical Properties Molecular Structure Molecular Weight Distribution 8

9 Polymer structures Many different polymer structures have been developed 9

10 Polymer Detective What is it? What are its properties? How does it behave? What? Where? How? Who? 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? 10

11 Polymer Analysis Decision Tree Identity Material Properties Morphology Components Chemical Structure FTIR Density SEM TGA NMR Raman Rheology AFM XRF MS CHNOS DSC GC SEC TMA LC Sorption 11

12 Traditional GPC Problem-solving through molecular size measurements 12

13 GPC: Characterize MWD of Acrylates R&D Acrylate Polymers 13

14 GPC: Good Sample vs. Bad Sample Acrylonitrile Butadiene Styrene (ABS) tubs Damaged Tub Undamaged Tub 14

15 GPC: Good Sample vs. Bad Sample Damaged Tub Undamaged Tub

16 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, Good 49, , , , Bad Strap Polypropylene straps Good Strap Log MW 16

17 HT-GPC: Good and Cracked Lip Balm Squeeze Tubes Original tube Recent tube Cracked tube Log MW

18 Amine GPC: Amine and Quaternary Amine Polymers Obtain useful chromatograms from materials with high amine functionality 18

19 Amine GPC: Polymerization Process Epoxy- Amines Beginning End Log MW

20 GPC: Monitor Polymer Formation Compare against competitors Polyamines Polymer formation results in poor performance High Molecular Weight Species 20

21 GPC: Monitor Polymer Formation Polymer Formation Sample Air Exposed Sample Aged Sample Competitor 1 Competitor 2 21

22 GPC: Trace Determination of Polymer Content Hyaluronic Acid Standard Calibrated from ppm HA Calibration Curve y = x R² = Peak Response (Area Count) Series1 Linear (Series1) Concentration (ppm) 23

23 High Performance SEC Waters Advanced Polymer Chromatography (APC) 24

24 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 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 minutes 25

25 APC: Rapid Analysis of Polycarbonate Urethane Urgent analyses completed in 22 hours, GPC would have taken 3 days 26

26 APC vs GPC: Polyalkyleneglycol (PAG) R&D analysis Improved resolution and speed (15 min vs 35 min) APC GPC 27

27 APC: Low Mass Surfactants Improved resolution shows starting alcohol in lowest mass products 28

28 APC: Low Mass Surfactants Compare ethoxylated surfactants with different end groups and number of EO s 29

29 APC: Oligomer Content in Polysulfones Competitive analysis debunk claim of lower oligomer content 30

30 APC: Compare Silicone Putty Samples Competitive analysis compare MWD from different vendors 31

31 APC: EO/PO Degree of Polymerization R&D synthesis analysis intended PO10/EO20 and PO55/EO40 32

32 APC: Epoxy Resin Comparison Regulatory analysis compare MWD of different epoxy resins 33

33 APC: Verify MWD of PC/ABS Polymer R&D analysis measure MWD of polycarbonate/acrylonitrile-butadiene-styrene material 34

34 APC: Oil Additives R&D analysis measure MWD of additives directly from oil 35

35 APC: Reactive Polymer Analysis R&D analysis measure MWD of Polymethylhydrogen Siloxanes 36

36 Amine APC: Modified Amine Capped Surfactants R&D analysis measure MWD of Reactants and Products 37

37 APC vs GPC: Chromatogram of Hydrocarbon Resin APC APC Improved resolution Mn (Daltons) Mw (Daltons) Mz (Daltons) PDI (Mw/Mn) APC 2,410 4,920 8, GPC 1,740 3,530 5, APC higher due to lower dispersion GPC

38 APC vs GPC: Silicone Surfactant Mn (Daltons) Mw (Daltons) Mz (Daltons) PDI (Mw/Mn) APC APC 6,610 38,300 92, GPC 5,930 36,600 94, Improved resolution 6.0 GPC

39 APC vs GPC: Poloxamer (EO:PO:EO) R&D analysis MWD difference due to resolution or column interaction? APC Mw = 7,500 D Traditional SEC Mw = 12,000 D 40

40 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 41

41 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 42

42 Valued Quality. Delivered. 43

43 Back Up 44

44 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 45

45 Chromatogram of Glycol Sample APC vs. GPC APC Mn (Daltons) Mw (Daltons) Mz (Daltons) PDI (Mw/Mn) APC 24,600 37,400 44, GPC 24,000 35,500 42, GPC 46