(19) TZZ _496¥_T (11) EP 2 174 963 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C08F 210/00 (2006.01) C08F 4/642 (2006.01) 27.02.2013 Bulletin 2013/09 C07F 17/00 (2006.01) C08F 10/00 (2006.01) C08F 4/6592 (2006.01) (21) Application number: 09016141.5 (22) Date of filing: 08.09.1999 (54) Metallocene catalysts for olefin polymerization and methog of polymerizing olefins using the metallocene catalysts Metallocenkatalysatoren zur Olefinpolymerisation und Verfahren zur Polymerisation von Olefinen unter Verwendung dieser Metallocenkatalysatoren Catalyseurs métallocènes pour la polymérisation d’oléfines et méthode de polymérisation d’oléfines, utilisant ces catalyseurs (84) Designated Contracting States: • Yoon, Keun-Byoung CH DE FR GB IT LI SE Chungcheungnam-do 356-870 (KR) • Jung, Won-Cheol (30) Priority: 13.10.1998 KR 19980042729 Chungcheungnam-do 356-870 (KR) (43) Date of publication of application: (74) Representative: Hering, Hartmut 14.04.2010 Bulletin 2010/15 Patentanwälte Berendt, Leyh & Hering (62) Document number(s) of the earlier application(s) in Innere Wiener Strasse 20 accordance with Art. 76 EPC: 81667 München (DE) 02028085.5 / 1 302 482 99117715.5 / 0 994 132 (56) References cited: • CHEMICAL ABSTRACTS, vol. 127, no. 12, 22 (73) Proprietor: Samsung General Chemicals Co., Ltd. September 1997 (1997-09-22), Columbus, Ohio, Seosan-shi, US; abstract no.: 162245, HINO, TAKAHIRO ET Chungcheongnam-do 356-870 (KR) AL: "Metallocene catalyst for olefin polymerization and production of polyolefins", (72) Inventors: XP002126590 & JP 9 176221 A (SUMITOMO •Lyu,Yi- Yeol CHEMICAL CO., LTD., JAPAN) 8 July 1997 Chungcheungnam-do 356-870 (KR) (1997-07-08) • Chang, Seok Chungcheungnam-do 356-870 (KR) Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 174 963 B1 Printed by Jouve, 75001 PARIS (FR) EP 2 174 963 B1 Description [0001] The present invention relates to new metallocene catalysts for use in preparation of olefin polymers or co-pol- ymers. More specifically, the present invention relates to methods of preparing the metallocene catalysts and methods 5 of preparing olefin polymers such as mono-polymers of ethylene or α-olefin, ethylene/α-olefin co-polymers, propylene/ α-olefin co-polymers, etc. using the metallocene catalysts. [0002] Metallocene catalysts have high activities and are capable of preparing resin with enhanced physical properties in comparison with the resin polymerized by using Ziegler-Natta catalysts. The metallocene catalysts are compounds of Group IV transition metals of the Periodic Table such as titanium, zirconium, hafnium, etc., and have a coordinated 10 structure with a metal compound and ligands composed of one or two groups of cyclopentadienyl, indenyl, fluorenyl or their derivatives. The metallocene catalysts are usually employed with a co- catalyst. And the co-catalyst is normally an alkylaluminoxane such as methylaluminoxane prepared by reacting an alkylaluminium compound with H2O, unlike the co-catalyst employed with the Ziegler-Natta catalysts. [0003] U.S. Patent No. 3,740,384 discloses a process for polymerization of monoolefins by contacting the olefin with 15 a catalyst composition containing an organometallic zirconium complex selected from hydrocarbyl complexes of zirco- nium in which the valence or coordination requirements of the metal are satisfied by alkyl, alkenyl, or arylalkyl groups which may be partially replaced by other monovalent ligands, using the catalyst composition of 1,1,3,3-tetraphenylsi- loxane-1,3-diol. The organometallic zirconium compounds contain allyl, ethylbenzyl, methylene or naphthyl ligands. [0004] The JP 9 176 221 A discloses a method for providing olefin polymerisation catalysts and using the same. The 20 catalysts comprising a transition metal, cyclopentadienyl rings which are optionally bridged with dihydroxyphenylene, diaminolkylene and disulfidoalkylene as bridging groups. The O-, N- and S- containing bridging groups are selected from the elements to groups 15 and 16 of the periodic table of elements. [0005] EP Publication No. 423 872 A2 discloses a reaction product (for example, Cp2ZrR2, R=alkyl or halogen) of a silicon of siloxane diol and a dicyclopentadienyl zirconium as a catalyst for ethylene polymerization. 25 [0006] The inventors of the present invention have discovered that the metallocene catalyst prepared by reacting a diol (or diamine, alkyl dimagnesium halide, aryl dimagnesium halide) compound with a cyclopentadienyl zirconium halide has a higher activity in preparation of olefin polymers than conventional catalysts, and that the metallocene catalysts are capable of using less amount of a co-catalyst such as an alkylaluminoxane than conventional catalysts when they are employed in preparation of olefin polymers. 30 [0007] Accordingly, the present inventors have developed new metallocene catalysts for use in preparation of olefin polymers, and methods of preparing the metallocene catalysts and methods of preparing olefin polymers such as mo- no-polymers of ethylene or α-olefin, ethylene/α-olefin co-polymers, propylene/α-olefin co-polymers, etc using the met- allocene catalysts. [0008] An object of the present invention is to provide metallocene catalysts having a high activity to prepare polyolefins 35 with enhanced physical properties in comparison with the polyolefins prepared by using Ziegler-Natta catalysts. Another object of the present invention is to provide metallocene catalysts which are capable of using less amount of a co- catalyst such as an alkylaluminoxane than conventional catalysts when they are employed in preparation of olefin polymers. [0009] A further object of the present invention is to provide a method of preparing the metallocene catalysts according to the present invention. 40 [0010] A further object of the present invention is to provide a method of preparing olefin polymers such as mono-pol- ymers of ethylene or α-olefin, ethylene/α-olefin co-polymers, propylene/α. -olefin co- polymers, etc using the metallocene catalysts. [0011] Other objects and advantages of this invention will be apparent from the ensuing disclosure and appended claims. 45 [0012] The new metallocene catalysts according to the present invention are prepared by reacting a metallocene compound with a compound having at least two functional groups. The metallocene compound is a transition metal compound, which is coordinated with a main ligand such as cyclopentadienyl group, and an ancillary ligand. The functional groups in the compound are selected from the group consisting of a hydroxyl group, an alkyl or aryl magnesium halide, a thiol group, a primary amine group, a secondary amine group, a primary phosphorous group, a secondary phosphorous 50 group. [0013] The metallocene catalysts of the present invention can be also prepared by reacting a metallocene compound with the dianion compound produced by reacting an alkali metal compound with a compound having those functional groups. [0014] The metallocene catalysts according to the present invention have a structure in which an ancillary ligand of a 55 metallocene compound is bonded to the functional groups of a compound having at least two functional groups. A structure of the metallocene catalysts can be varied with the type of a metallocene compound and a compound having at least two functional groups, and the molar ratio of each reactant. [0015] The metallocene catalysts are employed with a co-catalyst for olefin polymerization. The co-catalyst is an 2 EP 2 174 963 B1 organometallic compound, or a mixture of non-coordinated Lewis acid and alkylaluminium as it is well known in the art. [0016] The metallocene catalysts according to the present invention are prepared by reacting a metallocene compound with a compound having at least two functional groups. The metallocene catalyst is a transition metal compound, which is coordinated with a main ligand such as cyclopentadienyl group and an ancillary ligand. The functional groups in the 5 compound having at least two functional groups are selected from the group consisting of a hydroxyl group, an alkyl or aryl magnesium halide, a thiol group, a primary amine group, a secondary amine group, a primary phosphorous group, a secondary phosphorous group. The metallocene catalysts of the present invention can be also prepared by reacting a metallocene compound with a dianion compound produced by reacting an alkali metal compound with a compound having those functional groups. 10 [0017] The metallocene catalysts according to the present invention have a structure in which an ancillary ligand of a metallocene compound is bonded to the functional groups of a compound having at least two functional groups. A structure of the metallocene catalysts can be varied with the type of a metallocene compound and a compound having at least two functional groups, and the molar ratio of each reactant. [0018] The metallocene catalysts are employed with a co-catalyst for olefin polymerization. The co-catalyst is an 15 organometallic compound, or a mixture of non-coordinated Lewis acid and alkylaluminium, which is well known in the art. The organometallic