USOO6642325B2 (12) United States Patent (10) Patent No.: US 6,642,325 B2 Luo et al. (45) Date of Patent: Nov. 4, 2003 (54) SILICAGEL-SUPPORTED CATALYST 4,242.230 A 12/1980 Ueno et al. ................. 252/429 COMPONENT FORETHYLENE (CO) 4,242.231. A 12/1980 Ueno et al. ................. 252/429 POLYMERIZATION, CATALYST 4.293,673 A 10/1981 Hamer et al. ................. 526/88 THEREFROMAND USE OF THE SAME 4,302,565. A 11/1981 Goeke et al. ................. 526/88 4,302,566. A 11/1981 Karol et al. ................ 526/125 (75) Inventors: ang, Beijing (CN);Sk(CN); Keijing Gao,guo 2- E.A.'s1 - 2 : West... alm............. 3. Beijing (CN); Qinfang Zhao, Beijing s: A : .. Hiroyuki et al. ............ S. SN sal,SES." 5,661,097 A 8/1997 Spencer et al. ............. 502/115 t ey s g Huo, 5,744,567 A 4/1998 Hiffer et al. ............ 526/348.6 Ing. 6,200,922 B1 3/2001 Hiffer et al. ............... 502/120 (73) Assignees: China Petroleum & Chemical Corporation, Beijing (CN); Beijing FOREIGN PATENT DOCUMENTS Research Institute of Chemical CN 1230552 10/1999 Industry, Beijing (CN) EP O812861 12/1997 EP O942007 9/1999 (*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. * cited by examiner (21) Appl. No.: 09/935,333 Primary Examiner Ling-Siu Choi (74) Attorney, Agent, or Firm-Ladas & Parry (22) Filed: Aug. 22, 2001 (65) Prior Publication Data (57) ABSTRACT The present invention relates to a Silica gel-Supported cata US 2002/0065378 A1 May 30, 2002 lyst component Suitable for ethylene (co)polymerization, a (30) Foreign Application Priority Data catalyst therefrom and use of the same. The catalyst com ponent according to the present invention is obtained by Aug. 22, 2000 (CN) ........................................ OO123560 A Supporting the reaction product of a titanium compound, a (51) Int. Cl." ................................................... C08F 4/02 halide promoter, a magnesium compound and an electron (52) U.S. Cl. ....................... 526/129; 526/352; 526/348; donor on Silica gel having a larger Specific Surface area. 526/901; 526/143; 526/123.1; 502/103; When the resultant catalyst is used for ethylene 502/115; 502/118; 502/121; 502/125; 502/128 polymerization, especially gas phase fluidized bed (58) Field of Search ................................. 502/103, 115, polymerization, not only the activity is Substantially 502/118, 121, 125, 128; 526/129, 143, enhanced, but also the hydrogen response and the copoly 352, 348,901, 123.1 merizability of ethylene with other alpha-olefins are improved. The catalyst is especially suitable for the fluidized (56) References Cited bed polymerization operated in a condensed State, with high quality LLDPE resins being obtained. U.S. PATENT DOCUMENTS 3.225,023 A 12/1965 Hogan et al. .............. 260/94.9 18 Claims, No Drawings US 6,642,325 B2 1 2 SILICA GEL-SUPPORTED CATALYST response and Superior copolymerizability of ethylene with COMPONENT FORETHYLENE (CO) other alpha-olefins. Especially in the gas phase fluidized bed POLYMERIZATION, CATALYST process operated in a condensed State, which represents an THEREFROMAND USE OF THE SAME advanced process currently, the catalyst according to the present invention shows a good balance among various properties. FIELD OF THE INVENTION The object of the present invention is to provide a highly active Silica gel-Supported catalyst component Suitable for The present invention relates to a Silica gel-Supported ethylene (co)polymerization, which has overcome the dis catalyst component Suitable for ethylene (co) advantages associated with the prior Silica gel-Supported polymerization, a catalyst therefrom and its use in ethylene titanium based catalyst, Such as low activity and the like. (co)polymerization, in particular in a gas phase fluidizedbed Another object of the present invention is to provide a proceSS operated in a condensed State. catalyst for ethylene (co)polymerization. BACKGROUND OF THE INVENTION Still another object of the present invention is to provide 15 the use of the catalyst in accordance with the present It is well known that microspherical Silica gels (having an invention for olefin (co)polymerization. average particle size of 10 to 100 microns) has been widely In its one aspect, the present invention provides a highly applied in catalysts for olefin polymerization as the carrier, active Silica gel-Supported catalyst component Suitable for especially in catalysts for olefin polymerization by a gas ethylene (co)polymerization which is a titanium-containing phase process, and Silica gels which have been used cur active component Supported on a porous inert carrier material, comprising the reaction product of at least one rently include SYLOPOL 948, SYLOPOL 955 and XPO titanium compound, at least one magnesium compound, at 2402 manufactured and marketed by Grace Corporation, least one halide promoter, and at least one electron donor, USA and SD490 manufactured and marketed by Crosfield wherein Said porous inert carrier material is spherical or Corporation, typically having a specific Surface area of about Spheroidal Silica gel having an average particle size of 10 to 300 ml/g or even less. When applied for supporting 25 100 microns, a specific surface area of 300 to 1000 m/g, a catalysts, the amount of the active components Supported on pore Volume of 2.0 to 5.0 ml/g and an average pore diameter these Silica gels are limited and thus the improvements in of 5 to 45 nanometers. catalytic activity are limited. For example, U.S. Pat. Nos. In its Second aspect, the present invention provides a 4.293,673, 4,302,565, 4,302,566 and 4,303,771 disclose a catalyst comprising the Supported catalyst component in Series of catalysts Suitable for ethylene polymerization by a accordance with the present invention. gas phase fluidized bed process, in which the above men In its third aspect, the present invention relates to the use tioned Silica gels are used as the carrier. Up to now, most of Such commercially available catalysts are obtained by Sup of the catalyst in accordance with the present invention for porting a magnesium compound, a titanium compound and olefin (co)polymerization. an electron donor onto SYLOPOL 955 silica gel and when 35 DETAILED DESCRIPTION OF THE they are used for ethylene polymerization by a gas phase INVENTION fluidized bed process, the catalytic activity is typically about The catalyst component in accordance with the present 3500 g PE/g Cat; however, when they are used in a gas phase invention is obtained by impregnating a carrier material with fluidized bed proceSS operated in a condensed State, the the reaction product of at least one titanium compound, at catalytic activity is Substantially lowered due to the short 40 least one magnesium compound and at least one electron ening of the residence time of the catalysts, thereby leading donor compound So as to Support the reaction product onto to an increase in the ash content of the resultant ethylene the carrier material. It should be particularly noted that the polymers, which in turn deteriorates the quality of ethylene carrier material is Selected among Spherical or spheroidal polymers. Therefore, enhancing the activity of Such catalysts Silica gels having a larger Specific Surface area, with dehy is one of the key factors for the improvement in the quality 45 drated Silica gels being preferred. The hydroxyl content on of the ethylene polymers. If, however, only the Specific the Surface is typically adjusted by controlling the conditions Surface area of Silica gel is increased, on one hand, the for heat-activating Silica gels Preferably, Silica gels have an activity of the catalysts when used for olefin polymerization average particle Size of 10 to 100 microns, more preferably is enhanced to Some extent; on the other hand, the pore size 20 to 80 microns, most preferably 30 to 60 microns; a of Silica gel is decreased due to the increase in its specific 50 specific surface area of 300 to 1000 m/g, more preferably Surface area, thus other properties Such as hydrogen 400 to 800 m/g, most preferably 600 to 800 m/g; a pore response, copolymerizability of ethylene with other alpha volume of 1.0 to 6.0 ml/g, more preferably 2.0 to 5.0 ml/g; olefins and the like decrease dramatically (cf. U.S. Pat. No. and an average pore diameter of 5 to 45 nanometers, more 3,225,023). Therefore, taking the balance among various preferably 10 to 35 nanometers. properties into account, the currently commercialized Silica 55 In the catalyst component as mentioned above, at least gel carrier materials for ethylene polymerization by a gas one halide promoter is also added. The halide promoter is a phase process is typically controlled to have a specific class of compounds represented by general formula F-R' surface area of about 300 m /g. IRX3) wherein F represents a functional group which is SUMMARY OF THE INVENTION chemically reactive with the organoaluminium compound, 60 the titanium compound or hydroxyl groups on Silica gels, After eXtensive and repetitive investigation, the present Such as an aldehyde group, an acyl group, a hydroxyl group, inventors have found that by employing Silica gels having a an amino group, an ester group and the like; R' represents larger Specific Surface area and Supporting thereon a mag a divalent C-C aliphatic or aromatic group which is nesium compound, a titanium compound and an electron attached to the functional group F; R represents hydrogen, donor compound, as well as a halide promoter, the resultant 65 unsubstituted or halogen-Substituted C-C alkyl, C-C, catalyst has not only a largely enhanced activity when used cycloalkyl or Co-Co aromatic groups, b is 0, 1 or 2, and X for olefin polymerization, but also excellent hydrogen is F, Cl or Br.