Supported Metallocene Catalyst for Long Chain Branched Polypropylene

Transcription

1 2017 SPE international Polyolefins Conference Houston, TX Japan Polypropylene Corporation Feb 27 th, 2017 Supported Metallocene Catalyst for Long Chain Branched Polypropylene Iku Kouzai Japan Polypropylene Corporation

2 Content 1. Objective 2. Clay-Mineral Supported Metallocene Catalyst 3. Requirements and Catalyst Architecture 4. Selective In-Situ Synthesis of Active Macromer 5. Macromer Incorporation 6. Launched LCB-PP WAYMAX TM 7. Conclusion

3 Objective of This Study Post reactor modification of PP to LCB-PP Irradiation of electron beam Reaction with peroxide and diene Radical reaction Problems/concerns relating to radical reaction Gel Direct synthesis from propylene Coloring In situ Catalyst for LCB-PP Macromer Japan Polypropylene Corporation

4 Clay-Mineral Supported Met Catalyst Our catalyst is very unique because we use clay minerals instead of MAO. JPP Catalyst Clay minerals Chemical and Physical treatment Granulation Common Catalyst SiO2 Support MAO Activator R R Cl Zr Cl Support- Activator Modified Support R High performance Metallocene Complex R Cl Zr Cl Metallocene Complex JPP Met Cat Common catalyst Easy handling Non-flammable Solid(insoluble) Clay minerals versus MAO Flammable Soluble Difficult to handle

5 Site Architecture Activation reactions Active sites Zr Cl Cl AlR3 alkylation Zr R R Clay minerals Zr + cationization - R stabilization (Stabilization of activated complex) Basic site (Cationization of alkylated complex) Acid site Only strong acid sites can transform a complex into the active species. (Function) Structure O Si, Al A Al, Mg OH A Interlayer Cation (Increase of effective acid sites) Interlayer cation - Defects of lattice (corresponding to chemical composition) - Acidity

6 Active Site Preparation on Clay-Minerals Tetrahedral layer Octahedral layer Tetrahedral layer Acid site Amorphous SiO 2 Montmorillonite (MMT) Acid treatment ( Al extraction ) AFM Metallocene M M M Propylene M M M M M M M Activated metallocene Polypropylene Active sites are concentrated on the border part. TEM Ref) T. Tayano et al., J. Mol. Catal. A: Chem., 420, 228 (2016) Japan Polypropylene Corporation

7 Requirements and Catalyst Architecture Requirements 1. Selective synthesis of active vinyl macromer 2. Effective incorporation of synthesized macromer 3. Overall MFR control for extrusion foaming application Architecture Active acid site on boarder Activated clay mineral Rigid framework & cationization Complex-A for macromer synthesis High vinyl-specificity Good stereo-specificity Complex-A Complex-B Neighboring Complex-B for copolymerization High Mw High comonomer incorporation Japan Polypropylene Corporation

8 JPP Proprietary Metallocene Complex Various platform of metallocene complex Bridged bis Cp 1) Me Bridged at sub-ring 2) 2-Furyl-indenyl 3) Ph Bis 7memberd-ring 4) Ph Me Me 2 Si Me Me Me ZrCl 2 Ph Me 2 Si ZrCl 2 O Me 2 Si ZrCl 2 Me O Ph Ph Me 2 Si ZrCl 2 Ph Tm=162 ºC, Mw=134,000 (MAO, 30 ºC) Tm=159 ºC, Mw=61,200 (MAO, 40 ºC) Tm= 159 ºC, Mw= 733,000 (MAO, 30 ºC) Tm=156 ºC, Mw=166,000 (MAO, 70 ºC) 1) Mise, et al. Chem. Lett. 1989, ) Kato, et al. In Metalorganic Catalysts for Synthesis and Polymerization; Kaminsky, W., Ed.; 1999; p192. 3) Ushioda, et al. In Proceedings of Polypropylene 2002, Zurich, ) Iwama, et at. Organometallics 2004, 23, Found effective framework for macromer synthesis

9 Indispensable Selective β-elimination PE H PP Met β-elimination Me Me n Me Met H + n Active α-olefin STD β-elimination Me Me n Me STD H + Me Me Me n Inactive vinylidene Complex-A β-me-extraction n Complex-A Me + H Me Me n Active α-olefin Japan Polypropylene Corporation

10 Microstructure of PP Obtained by Complex β-elimination after regular 1-2 insertion Unsaturated & saturated terminals relating to β-me extraction Complex A-1 A-2 A-3 Stereo/Regio [mol%] mm Unsaturated terminal [unit/1,000unit] 1-Propenyl Vinylidene 1-Butenyl i-butenyl 1,2 1,2 2,1 1,3 β-h β-me extraction β-h extraction β-h extraction Rearrangement Saturated terminal [unit/1,000unit] i-butyl n-propyl n-butyl β-me β-h β-me 1,2 insertion 1,2 insertion 1,3 + others Et β-me 2,1 + others Note: Complex was supported on STD MMT-support and used for bulk polymerization. Japan Polypropylene Corporation

11 Macromer Incorporation Catalyst preparation Complex-A + Complex-B + Activator Influence of activator Activated montmorillonite MAO-SiO 2 LCB in high Mw chains No LCB Structure control LCB content is controllable by complex mixing ratio.

12 Branching Evaluation GPC MALLS RI Viscometer GPC, RI, Viscometer:Waters Alliance GPCV2000 MALLS:Wyatt Technology Dawn-E Solvent:1,2,4-trichlorobenzene Temperature:140 C MALLS Viscometer Absolute Mw, Turning radius Intrinsic viscosity [η] gg = ηη bbbbbbbbbbb ηη llllllllllll at same MW Linear LCB g = 1 g < 1

13 Influence of Activator Only activated clay-mineral shows high compatibility to the LCB system. Complex-A & -B supported on activated montmorillonite High Mw chains have LCB. Favorable supporting state Complex-A & -B supported on MAO-SiO 2 No LCB Unfavorable supporting state

14 Plausible Model of Supporting State Montmorillonite MAO-SiO 2 Complex-A Complex-B LCB site

15 Polymer Structure Control LCB content is easily adjustable by preparation recipe. Note: LCB content was determined by 13 C-NMR. Japan Polypropylene Corporation

16 Launched LCB-PP WAYMAX TM MFR MS MFX series Grade MFR dg/min MS g Grade EX series MFR dg/min MS g Low High MFX EX MFX EX High Low MFX3 9 6 EX Note) not for specification

17 WAYMAX TM Melt Strength 25 MFX8 Melt Strength / g EX8000 EX6000 MFX6 5 Linear PP EX4000 MFX MFR / dg/min MFX: High melt strength EX : Adjusted melt strength for some application

18 WAYMAX TM Strain Hardening Elongational Viscosity (Pa s) 1.0E E E E+04 ARES Rheometer 180 C, 0.1sec -1 WAYMAX Linear PP MFX8 (MFR=1) MFX6 (MFR=3) MFX3 (8MFR) Strain Hardening 1.0E Time (sec)

19 Extrusion Foaming Extrusion Foaming Process Flat Die Annular Die Expansion ratio up to 3 more than 5 Closed cell Open cell Cell structure Good thermal insulation, cushioning and thermoforming Good sound absorption, water absorption

20 Extrusion Foaming with Flat Die Sample Non-foamed skin layer: A Layer structure Equipment: 65mmφ single screw EXT with flat die WAYMAX TM EX4000 (Foamed core layer: B) NOVATEC TM BC3BRF A/B/A multi layered (thickness ratio: 3/96/3% ) Blowing Agent CO 2 CBA Hydrocerol CF40E-J (0.5wt%) Average thickness / mm Expansion ratio / times Closed cell cont. / vol.% TD-ND Cross section view 0.5 mm

21 Extrusion Foaming with Annular Die Sample Layer Structure Equipment: 65mmφ single screw EXT with annular die WAYMAX TM MFX6 EX6000 Single layer Blowing Agent C 4 H 10 C 4 H 10 Average Thickness / mm Expansion ratio / Closed cell cont. / vol.% TD-ND Cross section view 0.5 mm

22 Conclusion Established effective catalyst system for direct synthesis of LCB-PP from propylene Selective β-me extraction achieved by specific complex framework Clear difference of compatibility to LCB system between clay-minerals and MAO-SiO2 Launched LCB-PP WAYMAX TM based on the catalyst system

23 Thank you for your attention. Japan Polypropylene Corporation

24 AFM Analysis of Acid-Treated MMT Raw material MMT (montmorillonite) 1.4 nm 500 nm MMT treated with sulfuric acid at 90 C 5h 1.0 nm 1.5 nm 410 nm

25 Slightly Polymerized Model Catalyst* 1) TEM analysis Wide view EFTEM* 2) analysis Zero-loss image Close view Fibril-like Carbon map Brighter parts are rich in carbon. * 1) Non-granulated MMT-supported metallocene catalyst was contacted with a small amount of propylene. * 2) Energy filtered transmission electron microscope Japan Polypropylene Corporation