Presenter: Shouliang Nie Supervisor: Prof. Costas Tzoganakis. Department of Chemical Engineering University of Waterloo IPR Symposium 1

Transcription

1 R H E O LO G I C A L P R O P E R T I E S O F TA I LO R - M A D E M E TA L LO C E N E A N D Z I E G L E R - N AT TA B A S E D C O N T R O L L E D R H E O LO GY P O LY P R O P Y L E N E S Presenter: Shouliang Nie Supervisor: Prof. Costas Tzoganakis Department of Chemical Engineering University of Waterloo 15 IPR Symposium 1

2 Introduction 1. Z i e g l e r - N a t t a, m e t a l l o c e n e b a s e d p o l y p r o p y l e n e ( Z N - P P a n d m P P ). O r i g i n o f C o n t r o l l e d R h e o l o g y P o l y p r o p y l e n e s ( C R P P ) ZN-PP: broad MWD; high MW and viscosity. Random scission by peroxide CRPP: narrower MWD; Controlled rheological properties. 3.Purpose of this study Rheometer Rheological properties ZN-PP mpp CRPP technique CRPPs with same MW/MFR Extruder Extrusion behavior Introduction

3 Modelling study of CRPP 1. M o d e l l i n g p r o c e s s P Pn ] ln1 * m [ * n [ dw / d(log M )] 3 ( [ Pn ] 3) Pn ] *exp( 1 dt) [ CRPP reaction kinetics Discrete GPC output of polypropylenes. M o d e l l i n g r e s u l t s f o r C R P P s From ZN-PP From mpp PDI down to the most probable distribution, From ZN-PP: MW ; PDI lowered sharply. From mpp: MW, however, PDI keeps ca.. We can make CRPPs with tailor-made MW and MWD from different origins. Modelling study of CRPP 3

4 Experimental study of CRPP MFR,(g/1min) 1. Raw Materials & Equipment: Original PPs: Peroxide: Batch Mixer: 1 C*3min. MW/MFR of CRPPs : Evolution of MW η = *Mw 3.49 ω M w monitored by η η (18 C, Pa*s) from PPC target Evolution of MFR Rotational rheometer Lupreox11 conc.(ppm) CRPP series to find peroxide level for target MW 6 4 MFR tester Experimental study of CRPP from PPC target Lupreox11 conc.(ppm) CRPP series to find peroxide level for target MFR 4

5 Extrusion study of CRPPs and their rheological characters Pressure drop (psi) Thermocouples Melt temp P Rheocord 9 Rheomix5 Zone1 Zone Zone3 Melt Pressure Zone4 Zone5 Water Bath α L 4. Extrusion set-up for CRPPs D=.315" (.89mm) Drawing of the extrusion die D=.315, L/D=9 18 Pressure dorp during extrusion of PPD at different die temperature Extrusion speed / shear rate 15 1 On-set zone of melt fracture C 16 C 18 C C ẏ app (s -1 ) Development of melt-fracture with extrusion rate of the extrudate Extrusion study of CRPPs 5

6 Pressure drop (psi) MFR,(g/1min) 18 Extrusion pressure drop of CRPPs with same MW 1, CRPPs with the similar zero-shear viscosity 15 η A88 Pressure drop (psi) onset of melt-fracture PPD A88 B1 C39 η* (Pas) B1 C39 PPD A88 fit B1 fit C39 fit PPD fit strength of shear-thinning ẏapp ẏ (s (s-1) ) Extrusion pressure drop of CRPPs with same MFR ω (rad*s -1 ) target MFR 3 Origin PPs A48 CRPPs with similar MFR PPD as target C19 B4 9 PPD A48 PPB PPC 6 B4 C19 1 PPA ẏapp ẏ (s-1) app (s ) Extrusion study of CRPPs and their rheological characters PP Sample 6

7 Acknowledgements Prof. Costas Tzoganakis Dr. Yasaman Amintowlieh Dr. Shuihan Zhu Dr. Xiaochuan Wang (NOVA Chemicals) Acknowledgements 7

8 Mixing torque(m.g) Supporting data1: CRPP production Production of CRPP Polypropylene Peroxide Polypropylene: Ingenia ground grades MFR: 13.5 g/1min (3C*.16kg) Peroxide: Luperox 11, SIGMA-ALDRICH (L11),,5-Bis(tert-butylperoxy)-,5-dimethyl hexane (DHBP). t 13.5s. HAAKE Rhoemix 3 inner mixer 1 Mixing of 8rpm in HAAKE mixer add L11 Load PP Time (min) Mixing recipe of CRPPs: Sample L11/ppm Acetone,ml Liquid add A1 5 directly A 1 directly A3 15 directly A4 directly B4 directly C4 pre-mix Mixing condiction: Temp: 1C Roter speed: 8rpm Reaction time: 3min 8

9 Supporting data: Reaction kinetics of CRPP Reaction kinetics of peroxide-induced CRPP Initiation: Kd I R Chain scission (β-scission): Pn + R K 1 P r + P n-r + R Transfer: Pn + P r K P r + P s + P n-s Thermal degradation: Pn K 3 P r + P n-r Termination: Pn + P r K 4 P n + P r C. Tzoganakis, J. Vlachopoulos, and A.E. Hamielec, Polym. Eng. Sci., 8, 17 (1988). B. Krause, M.Stephan,S.Volkland,D.Voigt, L.Haubler,H.Dorschner, J.App.Polym.Sci.,Vol.99,6 65(6) 9

10 dw/d(logm) Supporting data3: Model for CRPP process 3 ( [ Pn ] 3) [ Pn ] *exp( 1 dt) Model Quantitation of GPC data P [ Pn ] ln1 * m * n [ dw / d(log M )] fk [ I ] m d 1 P 1 n * 3 n 1 [ P n ] [ I] [ I] exp( k dt) d [dw/d(logm)] ordinate data in the normalized differential GPC curve R. LEW, D. SUWANDA, and S. T. BALKE, J. of App. Polym. Sci., Vol. 35, (1988) dt m ρ P reaction time increment molecular weight of monomer polymer density [P n ] concentration of polymer chain n chain length [I] initiator concentration Kd decomposition rate constant of the initiator f initiator efficiency S. T. BALKE, D. SUWANDA, and R. LEW, J. of Polym. Sci.: Part C, Vol. 5, (1987) GPC output Differencial GPC Curve d(logm) dw/d(logm) 3 logm 4 i logm5 i logm 1

11 η (Pa*s) Supporting data4: CRPPs series with same MW/MFR 1. CRPPs series production for similar MW (η ) * * The MW level of CRPPs was characterized by the zero-shear viscosity η. Prediction procedure of the peroxide concentrations for CRPPs from PPA/PPB/PPC are: 88/1/39 respectively 1 1 Denpendence of η on Mw y = 7E-16x R² =.9997 A Mw vs n C 1 D B 1 E Mw(g/mol) 11

12 η* (Pas) MFR,(g/1min). CRPPs series production for similar MFR 8 7 MFR,(g/1min) from PPA Lupreox11 conc.(ppm) Prediction procedure of the peroxide concentrations for CRPPs from PPA/PPB/PPC are: 48/4/19 respectively 1, CRPPs with the similar MFR A48 B4 C19 PPD , ω (rad*s -1 ) from PPC Lupreox11 conc.(ppm) 1