Full Text:   <1130>

CLC number: O632.12

On-line Access: 

Received: 2002-12-16

Revision Accepted: 2003-01-05

Crosschecked: 0000-00-00

Cited: 1

Clicked: 3313

Citations:  Bibtex RefMan EndNote GB/T7714

-   Go to

Article info.
1. Reference List
Open peer comments

Journal of Zhejiang University SCIENCE A 2003 Vol.4 No.2 P.121~130

http://doi.org/10.1631/jzus.2003.0121


Ethene/norbornene copolymerization by [Me2Si(3-tertBuCp)(NtertBu)]TiCl2/MAO-catalyst


Author(s):  TRAN Phu-Dennis, KAMINSKY Walter

Affiliation(s):  Institute of Technical and Macromolecular Chemistry, University of Hamburg, Germany

Corresponding email(s):   Phu-Dennis.Tran@chemie.uni-hamburg.de, kaminsky@chemie.uni-hamburg.de

Key Words:  Polymerization, Ethene/norbornene copolymers, Constrained geometry catalyst, Temperature effects


Share this article to: More

TRAN Phu-Dennis, KAMINSKY Walter. Ethene/norbornene copolymerization by [Me2Si(3-tertBuCp)(NtertBu)]TiCl2/MAO-catalyst[J]. Journal of Zhejiang University Science A, 2003, 4(2): 121~130.

@article{title="Ethene/norbornene copolymerization by [Me2Si(3-tertBuCp)(NtertBu)]TiCl2/MAO-catalyst",
author="TRAN Phu-Dennis, KAMINSKY Walter",
journal="Journal of Zhejiang University Science A",
volume="4",
number="2",
pages="121~130",
year="2003",
publisher="Zhejiang University Press & Springer",
doi="10.1631/jzus.2003.0121"
}

%0 Journal Article
%T Ethene/norbornene copolymerization by [Me2Si(3-tertBuCp)(NtertBu)]TiCl2/MAO-catalyst
%A TRAN Phu-Dennis
%A KAMINSKY Walter
%J Journal of Zhejiang University SCIENCE A
%V 4
%N 2
%P 121~130
%@ 1869-1951
%D 2003
%I Zhejiang University Press & Springer
%DOI 10.1631/jzus.2003.0121

TY - JOUR
T1 - Ethene/norbornene copolymerization by [Me2Si(3-tertBuCp)(NtertBu)]TiCl2/MAO-catalyst
A1 - TRAN Phu-Dennis
A1 - KAMINSKY Walter
J0 - Journal of Zhejiang University Science A
VL - 4
IS - 2
SP - 121
EP - 130
%@ 1869-1951
Y1 - 2003
PB - Zhejiang University Press & Springer
ER -
DOI - 10.1631/jzus.2003.0121


Abstract: 
Ethene/norbornene copolymerization by the catalyst system [Me2Si(3-tertBuCp)(NtertBu)]TiCl2/MAO was investigated in detail at 30°C, 60°C, and 90°C. A mass flow controller was used in this work to obtain kinetic data and investigate temperature's effects on activity, norbornene incorporation, copolymerization parameter, microstructure, glass transition temperature, and molar masses were described. High copolymerization values rE and high alternation are determined. The number of isotactic alternating sequences is much higher than that of the syndiotactic alternating sequences.

Darkslateblue:Affiliate; Royal Blue:Author; Turquoise:Article

Reference

[1]Altamura, P. and Grassi, A., 2001. Crystalline Alternating Sequences identified in ethylene-co-norbornene polymers produced by the (η5-C2B9H11)Zr(NEt2)2(NHEt2)-AliBu3 catalyst. Macromolecules, 34:9197-9200.

[2]Arndt, M. and Beulich, I., 1998. C1-symmetric metallocenes for olefin polymerisation, 1: Catalytic performance of [Me2C(3-tertBuCp)(Flu)]ZrCl2 in ethene/norbornene copolymerisation. Macromol. Chem. Phys., 199: 1221-1232.

[3]Arndt-Rosenau, M. and Beulich, I., 1999. Microstructure of Ethene/Norbornene Copolymers. Macromolecules, 32(22): 7335-7343.

[4]Bergström, C. H. and Seppala, J. V., 1997. Effects of polymerization conditions when making norbornene-ethylene copolymers using the metallocene catalyst ethylene bis (indenyl) zirconium dichloride and MAO to obtain high glass transition temperatures. J. Appl. Polym. Sci., 63:1063-1070.

[5]Beulich, I., 1999. Copolymerisation von Ethen und sterisch anspruchsvollen Olefinen durch Metallocen-Katalysatoren. Dissertation, University Hamburg, Germany.

[6]Brekner, M. J., Osan, F., Rohrmann, J. and Antberg, M., 1992. Process for the preparation of chemically homogeneous cycloolefin copolymers. Patent US 5 324 801.

[7]Canich, J. A. M., 1997. Monocyclopentadienyl metal compounds for ethylene-alpha-olefin-copolymer production catalysts. Patent US 5 631 126.

[8]Cherdron, H., Brekner, M. J. and Osan, F., 1994. Cycloolefin-Copolymere: Eine neue Klasse transparenter Thermoplaste. Angew. Makromol. Chem., 223: 121-133.

[9]Ewen, J. A., Elder, M. J., Jones, R. L., Haspeslagh, L., Atwood, J. L., Bott, S. G. and Robinson, K., 1991. Metallocene/polypropylene structural relationships: implications on polymerization and stereochemical control mechanisms. Makromol. Chem. Macromol. Symp., 48/49:253-295.

[10]Forsyth, J., Pereña, J.M., Benavente, R., Pérez, E., Tritto, I., Boggioni, L. and Brintzinger, H.H., 2001. Influence of the polymer microstructure on the thermal properties of cycloolefin copolymers with high norbornene contents. Macromol. Chem. Phys., 202(5):614-620.

[11]Goodall, B. L. and Lester, H. McI, 2001. Method for the preparation of copolymers of ethene/norbornene-type monomers with cationic palladium catalysts. Patent US 6 265 506.

[12]Harrington, B. A. and Crowther, D. J., 1998. Stereoregular, alternating ethylene-norbornene copolymers from monocyclopentadienyl catalysts activated with non-coordinating discrete anions. J. Mol. Catal. A: Chem., 128: 79-84.

[13]Jansen, J. C., Mendichi, R., Locatelli, P. and Tritto, I., 2001. Evidence of the quasi-living character of the ansa-Zirconocene/MAO-catalyzed copolymerization of ethylene and norbornene. Macromol. Rapid Commun., 22:1394-1398.

[14]Kaminsky, W. and Spiehl, R., 1989. Copolymerization of cycloalkenes with ethylene in presence of chiral zirconocene catalyst. Makromol. Chem., 19:515.

[15]Kaminsky, W., Arndt, M. and Bark, A., 1991. New results of the polymerization of olefins with metallocene/aluminoxane-catalysts. Polym. Prep., 1:467.

[16]Kaminsky, W. and Noll, A., 1993. Copolymerization of Norbornene and Ethene with Homogeneous Zirconocenes/Methylaluminoxane Catalysts. Polymer Bulletin, 31:175.

[17]Kiesewetter, J. and Kaminsky, W., 2002. Ethene/Norbornene copolymerization with Palladium(II) α-Diimine catalysts from ligand screening to discrete catalysts species. Chem. Eur. J., accepted.

[18]Lamonte, R. R. and McNally, D., 2001. Cyclic olefin copolymers. Advanced Materials & Process.

[19]Landolt-Börnstein, 1976. Zahlenwerte und Funktionen aus Physik Chemie Astronomie Geophysik Technik, Springer, Berlin, 6th edition, Part 4, C2: p.121.

[20]Laserov, H., Mönkkönen and Pakkanen, T. T., 1998. Influence of batch reaction conditions on norbornene/ethylene copolymers made using C2v- and Cs-symmetric metallocene/MAO. Macromol. Chem. Phys., 199:1939-1942.

[21]McKnight, A. L. and Waymouth, R. M., 1999. Ethylene/Norbornene Copolymerizations with Titanium CpA Catalysts. Macromolecules, 32:2816-2825.

[22]Rische, T., Waddon, A.J., Dickinson, L. C. and MacKnight, W. J., 1998. Microstructure and Morphology of Cycloolefin Copolymers. Macromolecules, 31:1871-1874.

[23]Ruchatz, D. and Fink, G., 1998. Ethene-Norbornene Copolymerization Using Homogeneous Metallocene and Half-Sandwich Catalysts: Kinetics & Relationship between Catalyst Structure & Polymer Structure. Macromolecules, 31:4669-4686.

[24]Thorshaug, K., Mendichi, R., Boggioni, L., Tritto, I., Trinkle, S., Friedrich, C. and Mülhaupt, R., 2002. Poly(ethene-co-norbornene) obtained with a constrained geometry catalyst. A study of reaction kinetics and copolymer properties. Macromolecules, 35(8):2903-2911.

[25]Tran, Phu-Dennis, 1999. Ethen/Norbornen-Copolymerisation durch Metallocenkatalysatoren. Diploma thesis, University Hamburg, Germany.

[26]Tritto, I., Marestin, C., Boggioni, L., Zetta, L., Provasoli, A. and Ferro, D. R., 2000. Ethylene-norbornene copolymer microstructure. Assessment and advances based on assignments of 13C NMR Spectra. Macromolecules, 33:8931-8944.

[27]Tritto, I., Marestin, C., Boggioni, L., Sacchi, M. C., Brintzinger, H.H. and Ferro, D. R., 2001. Stereoregular and Stereoirregular Alternating Ethylene-Norbornene Copolymers. Macromolecules, 34(17):5770-5777.

[28]Yoshida, Y., Saito, J., Mitani, M., Takagi, Y., Matsui, S., Ishii, S., Nakano, T., Kashiwa, N. and Fujita, T., 2002. Living ethylene/norbornene copolymerization catalyzed by titanium complexes having two pyrrolide-imine chelate ligands. Chem. Commun., 0(12): 1298-1299.

[29]Wang, Q., Weng, J., Fan, Z. and Feng, L., 1997. Influence of mixed aluminoxane systems on ethylene-norbornene copolymerization catalyzed by metallocene. Macromol. Rapid Commun., 18:1101-1107.

[30]Wendt, R. A., Mynott, R., Hauschild, K., Ruchatz, D. and Fink, G., 1999. 13C NMR studies of ethene-norbornene copolymers: assigment of sequence distributions using 13C-enriched monomers and determination of the copolymerization parameters. Macromol. Chem. Phys., 200:1340-1350.

Open peer comments: Debate/Discuss/Question/Opinion

<1>

Please provide your name, email address and a comment





Journal of Zhejiang University-SCIENCE, 38 Zheda Road, Hangzhou 310027, China
Tel: +86-571-87952783; E-mail: cjzhang@zju.edu.cn
Copyright © 2000 - Journal of Zhejiang University-SCIENCE