PRACTICAL TRIALS OF THE WATERS ACQUITY APC SYSTEM

Transcription

1 PRACTICAL TRIALS OF THE WATERS ACQUITY APC SYSTEM Christian Wold, Elena Uliyanchenko, SABIC; Innovative Plastics, Bergen op Zoom, The Netherlands Any brands, products or services of other companies referenced in this document are the trademarks, service marks and/or trade names of their respective holders.

2 AGENDA Introduction to SABIC Introduction to the WATERS ACQUITY APC and ACQUITY APC Columns Testing Protocols at SABIC; Innovative Plastics Application to Polycarbonate, Polybuteneterphthalate, Polyetherimide, Polybutylene terphthalate Application of high speed runs Long term system robustness Conclusions No. 1

3 SABIC IN NUMBERS 1976, our beginning 2 nd largest global diversified chemical company* 88 th largest public company in the world* 90 B$ total assets 50 B$ annual revenue 40,000 employees 40 countries 6 Strategic Business Units 62 world-class plants worldwide 1 Corporate Research & Innovation Center 17 Technology and Application Centres 150 new products each year 8,000 global patents * Forbes 2012 No. 2

4 INNOVATIVE PLASTICS IN THE ENGINEERING THERMOPLASTICS INDUSTRY High Price Performance PI PPSU EXTEM (PI) ULTEM (PEI) LEXAN (PC) NORYL (PPO) CYCOLOY (PC/ABS) GELOY (ASA) CYCOLAC (ABS) PEEK LCP HTN XENOY (PBT/PC) VALOX (PBT) Nylon High performance polymers Engineering polymers and blends Low Polystyrene Polyvinyl chloride Polyethylene Polypropylene Bulk polymers AMORPHOUS CRYSTALLINE Family Clarity, colorability, impact strength Chemical resistance, flow, electrical properties SABIC and brands marked with are trademarks of SABIC or its subsidiaries or affiliates. No. 3

5 ACQUITY APC Size Exclusion System Designed for UPLC Ultra high pressures on sub 3um particles High resolution, fast separations Previously SEC was not suitable for UPLC conditions as SDVB packing materials were restricted to lower operating pressures Technology relies on new robust BEH particles that have been developed first for UPLC and translated to SEC The ACQUITY APC has also been designed to operate under SEC conditions with a variety of common solvents No. 4

6 TESTING REGIME AT SABIC Polymers: Polycarbonate, polyetherimide, polyphenylene oxide, polybutylene terphthalate, homopolymers, oligomers Systems: Standard SEC with styrene di-vinylbenzene single bed column 4.6mmx250mm, standard eluent conditions, detection UV ACQUITY APC system equipped with UPLC SEC columns of varying pore sizes (450, 200,125,45Å) and lengths, detection UV Aim: - Prove that new technology provides similar data to legacy systems - Highlight benefits of using new technology - Proof of column/system robustness - Make recommendation for future use of system 2D chromatography No. 5

7 HOMOPOLYMER TESTING No. 6

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9 POLYCARBONATE GPC APC polymer Mw (Da) Mn (Da) Pd Mw (Da) Mn (Da) Pd PC n= F-test Mn and Mw, p>0.05 no significant differences T-test Mn and Mw, p<<0.05 significantly different However the actual difference of Mw or Mn is only 1 or two monomer units so in reality we can work with these numbers No. 8

10 POLYPHENYLENE OXIDE 3000 Comparison PPO Absorbance Retentie tijd (min) GPC APC No. 9

11 GPC APC polymer Mw (Da) Mn (Da) Pd Mw (Da) Mn (Da) Pd PPO n= F-test Mn and Mw, p>0.05 no significant differences T-test Mn and Mw, p<<0.05 significantly different Lower Mn for APC probably adsorption PPO (contains some amine end-groups, its tricky even for GPC) Data still o.k for comparative work No. 10

12 POLYBUTYLENE TERPTHALATE 600 Comparison PBT absorbance GPC Retentie tijd (min) APC No. 11

13 GPC APC polymer Mw (Da) Mn (Da) Pd Mw (Da) Mn (Da) Pd PBT n= F-test Mn and Mw, p>0.05 no significant differences T-test Mn and Mw, p<<0.05 significantly different PBT acid end-groups likely adsorption on the column, however measured in different eluents (5% vs 10% HFIP in 1% EtOH in CHCL 3 ) Experimentation found that modifiers e.g. alcohol, formic acid and higher temperatures help No. 12

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15 GPC APC polymer Mw (Da) Mn (Da) Pd Mw (Da) Mn (Da) Pd PEI (n=5) F-test Mn and Mw, p>0.05 no significant differences T-test Mn and Mw, p<<0.05 significantly different Absolute difference low and still useful No. 14

16 CONCLUSIONS OF HOMO-POLYMER TESTING APC is very comparable to GPC w.r.t short term variation in results (F-test) For all polymers APC gives significantly different results for Mw and Mn (T-test) Polymers with polar functionality (especially amine or acid end-groups) may exhibit adsorption behavior on the APC silica based packing material Method development using different modifiers and analysis temperature can help in reducing these effects NO SHOW STOPPERS No. 15

17 OLIGOMER TESTING No. 16

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19 OLIGOMER SEPERATIONS Comparison of oligomer profile in whole sample Normalized Absorbance APC GPC Retention time (min) No. 18

20 OLIGOMER SEPERATIONS Absorbance standard oligomer samples (synthetic) flowmarker Retentie tijd (min) Plate Height (mm) Van Deemter plot Uopt Uopt Linear velocity of mobile phase (mm/s) APC GPC No. 19

21 THE NEED FOR SPEED No. 20

22 COMPREHENSIVE 2DLC POLYMER ANALYSIS Composition Molecular Weight No. 21

23 SPEEDING UP THE UPLC SEPERATION Normal analysis Fast analysis Average Average polymer Mn (Da) Mw (Da) Pd Polymer Mn (Da) Mw (Da) Pd PC PC PEI PEI PPO PPO PBT PBT Normal APC analysis Fast APC analyse Detector signaal Retention time (min) 3 columns 450, 200, cmx4.6mm, 1ml/min Detector signaal Retention tiime (min) 2 columns 450, cmx4.6mm, 2ml/min No. 22

24 THE FUTURE HPLC chemical composition based separation APC in second dimension Higher resolution 2D chromatography for polymers No. 23

25 NOTE ON APPLICATION ROBUSTNESS Boxplot of Mw (Da), Mn (Da) Recorded on Polycarbonate Sample Over 3 months (n=9) Data Mw (Da) Mn (Da) Solvents previously run DCM CHCL3 + DBA CHCL3 + HFIP 100% HFIP CHCL3 + HFIP, DCM CHCL3 + HFIP +TFA CHCL3 + DBA, CHCL3 + HFIP CHCL3 + DBA CHCL3 + HFIP RSD ~5% No. 24

26 CONCLUSIONS The new system opens up some interesting possibilities for R&D SEC High resolution oligomer analysis is possible For 2D analysis the new column technology is extremely interesting Faster analysis will allow greater slices and resolution along with lower solvent consumption compared to existing fast SEC columns Short term precision comparable with legacy SEC The columns are flexible and robust with regard to switching applications and solvents Results for polymers with polar end-groups may differ compared to standard SEC QA applications normally require greater long term precision and this must be assessed case by case No. 25

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