Sk(CN); Guo EA's West Alm 3

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. US 6,642,325 B2 3 4 When F represents a hydroxyl group, Said promoter is a (2) adding the heat-activated Silica gel into a lower alkane class of halogenated alcohol, Specific compound being 2.2, Solvent, followed by addition of an alkyl aluminum 2-trichloroethanol (ClCCH-OH), 2,2-dichloroethanol compound, and then reacting the mixture for a period (CICHCH-OH), 2-chloroethanol (CICHCH-OH), 1,1- of time, followed by evaporating the Solvent and dimethyl-2,2,2-trichloroethanol (ClCC(CH), OH), drying, thereby obtaining a Solid powder, 4-chlorobutanol (ClCHCHCHCH-OH), para (3) dissolving the titanium compound and the magnesium chlorophenol, iso-chlorophenol, ortho-chlorophenol, compound into the electron donor compound to prepare 2-chlorocyclohexanol and the like, with 2,2,2- a mother liquor, wherein the titanium compound is trichloroethanol, 2,2-dichloroethanol, 2-chloroethanol and 1,1-dimethyl-2,2,2-trichloroethanol being preferred. added into the electron donor compound before or after 1O the addition of the magnesium compound, or both the When F represents an acyl group, Said promoter is a class titanium compound and the magnesium compound are of halogenated acyl halide, Suitable examples of Such com added Simultaneously, pounds being trichloroacetyl chloride, dichloroacetyl chloride, chloroacetyl chloride, o-chlorobenzoyl chloride (4) adding the carrier material activated in step (2) into the and 2-chlorocyclohexyl carbonyl chloride, with trichloro mother liquor from Step (3) and reacting them for a acetyl chloride, dichloroacetyl chloride and chloroacetyl 15 period of time, followed by drying to remove exceSS chloride being preferred. Solvent, i.e. the electron donor compound, with its In the catalyst component as mentioned above, the mag residual content being controlled to be in the range of nesium compound, the electron donor compound and the 10 percent by weight to 21 percent by weight, thereby titanium compound have been described in U.S. Pat. No. obtaining a Solid material; 4,302,565, which is incorporated herein by reference. (5) Suspending the Solid material from Step (4) in a lower In the titanium-containing catalyst component as men alkane Solvent and then reducing with one or more tioned above, the magnesium compound, the electron donor alkyl aluminum compounds, followed by drying, compound and the halide promoter are used in amounts of thereby obtaining the final catalyst component. 0.5 to 50 moles, preferably 1.5 to 5 moles; 0.5 to 50 moles, The lower alkane Solvents used in step (2) and step (5) can preferably 1 to 10 moles; 0.5 to 50 moles, preferably 1 to 10 25 be C-C alkanes, preferably Cs and C alkanes, Such as moles, per mole of the titanium compound, respectively. isopentane, pentane, hexane and the like. In the catalyst component in accordance with the present The alkyl aluminum compounds which can be used in invention, preferable titanium compounds are those repre Step (2) and step (5) are preferably those represented by Sented by the following general formulae: general formula AlRX, wherein R' can be same or different and represents C-C alkyl groups, X represents a Ti(OR), X, or TIX halogen, m is an integer of 1 to 3. Preferable alkyl alu wherein R is C-C aliphatic hydrocarbyl, X is F, Cl, Br or minium compounds are Alets, Al(n-CH), AlBt-Cl, and combinations thereof and n is an integer of 1 to 4. Suitable the like. examples are Selected from the group consisting of titanium It should be particularly noted that the halide promoter in tetrachloride, titanium trichloride, titanium tetrabromide, 35 accordance with the present invention can be incorporated titanium tetraiodide, titanium tetrabutoxide, titanium into the catalyst component by any effective manner. For tetraethoxide, triethoxy titanium chloride, diethoxy titanium example, an excellent promotion effect can be achieved by dichloride, ethoxy titanium trichloride and mixtures thereof, adopting one of the following methods: i) adding during the with titanium tetrachloride, ethoxy titanium trichloride and treatment of the carrier material in Step (2), ii) adding during titanium trichloride being preferred. 40 Step (4) for Supporting the catalyst complex from Step (3) The magnesium compound which can be used is prefer onto the carrier material and iii) adding during the reduction ably those represented by general formula MgX, wherein X of the catalyst in Step (5). is Cl, Br, I or combinations thereof. Specific examples can The present invention also relates to a catalyst for ethyl be magnesium dichloride, magnesium dibromide, magne ene (co)polymerization, which is a reaction product of the sium diiodide, with magnesium dichloride being perferred. 45 above titanium-containing catalyst component and an alkyl The electron donor (ED) compound which can be used is aluminum compound, wherein the alkyl aluminum com preferably Selected from the group consisting of alkyl esters pound used is represented by the general formula AlR", in of aliphatic or aromatic carboxylic acids, aliphatic ethers, which R" can be same or different and represents Cls alkyl cyclic ethers and Saturated aliphatic ketones. Among them, groups, one or two of which can be replaced by chlorine. alkyl esters of C-C Saturated aliphatic carboxylic acids, 50 Preferable alkyl aluminum compounds are Alets, Al(iso alkyl esters of C7-Cs aromatic carboxylic acids, C-C, Bu), Al(n-CH), Al(n-CH7), Alt2Cl and the like. The aliphatic ethers, C-C cyclic ethers, C-C Saturated ali alkyl aluminum compounds can be used alone or in a phatic ketones are preferred. Most preferably are methyl mixture of two or more of them. formate, ethyl acetate, butyl acetate, diethyl ether, dihexyl The catalyst according to the present invention is Suitable ether, tetrahydrofuran (THF), acetone and methyl isobutyl 55 for ethylene homopolymerization and copolymerization of ketone. These electron donor compounds can be used alone ethylene and C-olefins, with the C-olefins being propylene, or in a mixture of two or more of them. butene, pentene, hexene, 4-methylpentene-1, octene, and the The catalyst component in accordance with the present like. The polymerization reaction can be carried out by a invention is prepared by firstly dissolving the titanium Slurry process, a gas phase process or a Solution process. The compound and the magnesium compound into the electron 60 catalyst according to the present invention is more Suitable donor compound to form a mother liquor and then impreg for gas phase fluidized bed polymerization, especially for nating a Silica gel carrier having a larger Specific Surface area gas phase fluidized bed process operated in a condensed with the mother liquor, preferably by a process comprising State. The polymerization temperature can be ranged from the Steps of: 50° C. to 100° C. (1) activating the Silica gel carrier material in a conven 65 It should be particularly noted that by using Silica gel tional manner, preferably dehydrating at a temperature having a larger Specific Surface area, the titanium content in of 600° C. for 4 hours; the catalyst component is Substantially enhanced while good US 6,642,325 B2 S 6 particulate property of the catalyst is guaranteed, which hexane (1.5 mmol) with the molar ratio of Al(n-CH)/ provides the basis for enhancing the activity of the resultant THF being 0.20, after the completion of addition, the catalyst. At the same time, by fixing the halide promoter mixture is reacted for half an hour and then dried by carrying a functional group on the Surface of Silica gel by Sweeping with highly pure nitrogen, thereby obtaining chemical reaction, the properties of polymers produced by Slightly yellow, Solid powdery catalyst component. The using the resultant catalyst do not deteriorate due to the catalyst component contains 1.16 percent by weight of Ti, increase in the Specific Surface area of the carrier, and both 1.83 percent by weight of Mg, 4.37 percent by weight of Al the hydrogen response of the catalyst and copolymerizability and 13.23 percent by weight of Cl and has a specific Surface of ethylene with other alpha-olefins are improved. area of 364 m/g and a pore volume of 2.4 ml/g, as measured Therefore, the disadvantages associated with the conven by mercury intrusion (Apparatus: AUTOPORE 9410, tional Silica gel-Supported catalysts when used in a gas phase MICROMERITICS, USA). fluidized bed process operated in a condensed State, i.e., low Slurry homopolymerization of ethylene. The slurry poly catalytic activity, high ash content and low polymer quality, merization is carried out in a 2 liter Stainless Steel autoclave. are overcome. The catalyst according to the present inven The conditions are as follows: the catalyst component, 50 tion is especially Suitable for gas phase fluidized bed proceSS 15 mg; H/CH=0.28/0.75 MPa; 1 ml of a solution of Alet in operated in a condensed State to produce high quality hexane (1 mmol/ml); hexane, 1 liter; 80° C.; 2 hours. The LLDPE resins. polymerization results are listed in Table 1. Gas phase copolymerization of ethylene and butene: The EXAMPLES polymerization is carried out in a p 150 mm fluidized bed for The catalyst according to the present invention is gas phase polymerization of ethylene, in the presence of 0.2 described in more details by the following examples, but the g catalyst, 5 mmol Alet and 600g polyethylene powders as catalyst System according to the present invention is not dispersant, under the following polymerization conditions: limited to them. total pressure, 1.7 MPa, temperature, 88 C.; composition of The physical parameters involved are measured by the the mixed gas (percent by volume): H=12.35, CH=59.47, 25 1-CH=14.57, N=13.61; 4 hours. The polymerization following Standard procedures: results are listed in Table 2. Specific Surface Area, Pore Volume and Average Pore Diameter: Mercury Intrusion (AUTOPORE 9410, Example 2 MICROMERITICS, USA) The catalyst component is prepared in a Same manner as Melt Index (MI); ASTM D-1238(2.16 kg) that in Example 1 except that (1) 1.3 ml ClCCOCl is used Melt Flow Index (FI): ASTM D-1238(21.6 kg) instead of 1.1 ml ClCCH-OH to treat the silica gel; (2) the Apparent Density (BD): ASTM D-1895 powder obtained in Step (4) contains 15.7 percent by weight Density (D): ASTM D-1505 of THF, and (3) Ti content in the resultant catalyst compo nent is 1.29 percent by weight. Example 1 35 The resultant catalyst is evaluated in the slurry polymer Preparation of Catalyst Component: ization in a same manner as that in Example 1 and the (1) 12 g of spherical silica gel (GRACE silica, SMRH49 polymerization results are listed in Table 1. 3039 available from Grace Corporation, USA; average par ticle size=55 microns, specific Surface area=717 m/g, pore Example 3 Volume=4.6 ml/g and average pore diameter=25.7 40 The catalyst component is prepared in a Same manner as nanometers) is weighed and then activated at a temperature that in Example 1 except that (1) 1.16 g TiCl2(AA grade) is of 600 C. for 4 hours. used in place of 0.64 ml TiCl, during the preparation of the (2) Under nitrogen, to a flask equipped with a stirrer and catalyst mother liquor; (2) the powder obtained in Step (4) containing isopentane (100 ml) as Solvent are added 10 g the contains 17.7 percent by weight of THF, and (3) Ticontent heat-activated Silica from Step (1) and 5.6 ml of a Solution 45 of Alet in hexane (1 mmol/ml). The mixture is reacted at a in the resultant catalyst component is 1.14 percent by temperature of 20-30 C. for half an hour, followed by slow weight. drop addition of 1.1 ml ClCCH-OH. After the completion The resultant catalyst is evaluated in the slurry polymer of addition, the mixture is reacted for half an hour and then ization in a same manner as that in Example 1 and the is dried by Sweeping with highly pure nitrogen, thereby 50 polymerization results are listed in Table 1. obtaining flowable powders. Example 4 (3) To another flask equipped with a stirrer are added 1.74 g MgCl2, 0.64 ml TiCl, and 174 ml tetrahydrofuran. The The catalyst component is prepared in a Same manner as mixture is heated under stirring to reflux for 5 hours, thereby that in Example 1 except that (1) 1.16 g TiCl2(AA grade) is obtaining a catalyst mother liquor. 55 used in place of 0.64 ml TiCl, during the preparation of the (4) The silica treated in step (2) is mixed with the catalyst catalyst mother liquor; (2) 1.3 ml of ClCCOCl is used mother liquor from step (3). The mixture is stirred under instead of 1.1 ml ClCCH-OH to treat the silica gel; (3) the refluxing for 1 hour, followed by drying by Sweeping with powder obtained in Step (4) contains 17.2 percent by weight highly pure nitrogen, thereby obtaining flowable, pale yel of THF, and (4) Ti content in the resultant catalyst compo low Solid powders containing 16.0 percent by weight of 60 nent is 1.07 percent by weight. THF. The resultant catalyst is evaluated in the slurry polymer (5) The product from step (4) is prereduced in 100 ml ization in a same manner as that in Example 1 and the isopentane at room temperature by first drop adding 7.2 ml polymerization results are listed in Table 1. of a solution of AlEtCl in hexane (2.21 mmol) with the Comparative Example 1 molar ratio of Alt-Cl/THF being 0.45, after the completion 65 of addition, the mixture is reacted for half an hour, followed The catalyst component is prepared in a Same manner as by drop adding 4.8 ml of a Solution of Al(n-CH) in that in Example 1 except that (1) no ClCCH-OH is used to US 6,642,325 B2 7 8 treat the Silica gel; (2) the powder obtained in Step (4) The resultant catalyst is evaluated in the slurry polymer contains 19.1 percent by weight of THF, and (3) Ticontent ization in a same manner as that in Example 1 and the in the resultant catalyst component is 1.36 percent by polymerization results are listed in Table 1. weight. The resultant catalyst is evaluated in the Slurry polymer Example 5 ization in a same manner as that in Example 1 and the The catalyst component is prepared in a Same manner as polymerization results are listed in Table 1. that in Example 1 except that (1) 1.16 g TiCl2(AA grade) is Comparative Example 2 used in place of 0.64 ml TiCl, during the preparation of the 1O catalyst mother liquor; (2) ClCCH-OH is used in an amount The catalyst component is prepared in a Same manner as of 175 ml instead of 1.1 ml to treat the silica gel; (3) the that in Example 1 except that (1) no ClCCH-OH is used to powder obtained in Step (4) contains 13.7 percent by weight treat the silica gel; (2) 1.169 of TiCl(AA grade) is used in of THF, and (4) Ti content=1.36 percent by weight, Mg place of 0.64 ml TiCl, during the preparation of the catalyst content=2.65 percent by weight, Al content=3.33 percent by mother liquor; (3) the powder obtained in Step (4) contains weight and Cl content=14.23 percent by weight. 17.2 percent by weight of THF, and (4) Ti content in the 15 resultant catalyst component is 1.26 percent by weight. The resultant catalyst is evaluated in the slurry polymer The resultant catalyst is evaluated in the Slurry polymer ization in a same manner as that in Example 1 and the ization in a same manner as that in Example 1 and the polymerization results are listed in Table 1. polymerization results are listed in Table 1. Gas phase copolymerization of ethylene and butene: The polymerization is carried out in a p 150 mm fluidized bed for Comparative Example 3 gas phase polymerization of ethylene, in the presence of 0.2 The catalyst component is prepared in a Same manner as g catalyst, 5 mmol Alets and 600g polyethylene powders as that in Example 1 except that (1) SYLOPOL 948 silica gel dispersant, under the following polymerization conditions: (manufactured by Grace Corporation, USA, average particle 25 total pressure, 1.7 MPa, temperature, 88 C.; composition of size=50 microns, specific Surface area=295 m/g, pore the mixed gas (percent by volume): H=15.05, CH=65.60, Volume =1.7 ml/g and average pore diameter=23.3 1-CH=13.73, N2=5.62; 4 hours. The polymerization nanometers) is used instead of the Silica gel used in Example results are listed in Table 2. 1, with its amount being unchanged and no ClCCH-OH is used to treat the silica gel; (2) 1.19 of MgCl, 0.4 ml of TiCl Example 6 and 100 ml THF are used during the preparation of the catalyst mother liquor; (3) the powder obtained in Step (4) The catalyst component is prepared in a Same manner as contains 13.5 percent by weight of THF, and (4) Ticontent that in Example 1 except that (1) 1.16 g TiCl(AA grade) is in the resultant catalyst component is 0.9 percent by weight. used in place of 0.64 ml TiCl, during the preparation of the catalyst mother liquor; (2) 1.1 ml of ClCCOCl is used The resultant catalyst component has a specific Surface 35 instead of 1.1 ml of ClCCH-OH to treat the silica gel; (3) area of 230 m/g and a pore volume of 1.8 ml/g, as measured the powder obtained in step (4) contains 14.2 percent by by mercury intrusion (Apparatus: AUTOPORE 9410, weight of THF, and (4) Ti content=1.37 percent by weight, MICROMERITICS, USA). Mg content=2.63 percent by weight, Al content=2.61 per The resultant catalyst is evaluated in the Slurry polymer cent by weight and Cl content=12.36 percent by weight. ization in a same manner as that in Example 1 and the 40 polymerization results are listed in Table 1. The resultant catalyst is evaluated in the slurry polymer ization in a same manner as that in Example 1 and the Comparative Example 4 polymerization results are listed in Table 1. The catalyst component is prepared in a Same manner as Gas phase copolymerization of ethylene and butene: The that in Example 1 except that (1) SYLOPOL 948 silica gel 45 polymerization is carried out in a p 150 mm fluidized bed for is used instead of the Silica gel used in Example 1, with its gas phase polymerization of ethylene, in the presence of 0.2 amount being unchanged and no ClCCH-OH is used to g catalyst, 5 mmol Alets and 600g polyethylene powders as treat the silica gel; (2) 1.1 g of MgCl, 0.73 g of TiCl, and dispersant, under the following polymerization conditions: 100 ml THF are used during the preparation of the catalyst total pressure, 1.7 MPa, temperature, 88 C.; composition of mother liquor, (3) the powder obtained in step (4) contains 50 the mixed gas (percent by volume): H=8.49, CH=75.93, 14.2 percent by weight of THF, and (4) Ti content in the 1-CH=5.74, N=9.85; 4 hours. The polymerization results resultant catalyst component is 0.95 percent by weight. are listed in Table 2.

TABLE 1. Evaluation of catalysts Activity Activity MI FI Fine gPEI (10-)g BD g/10 g/10 MF Particle size distribution of PE (mesh Powder Catalyst Ti% g Cat PE/g Ti g/cm min min R <2O 20-40 40-65 65-80 80-100 100-140 140-200 -200 >8O Ex. 1 1.26 6667 52.9 O.35 0.53 15.92 3O.O 89.8 9.6 0.4 O.O1 O.O6 O.OS O.04 O.O6 O.2 Ex. 2 1.29 6160 47.8 0.34 0.53 16.44 31.0 86.1 10.6 1.4 0.5 O.3 0.4 0.4 O.3 1.4 Ex. 3 1.14 4955 43.5 O.37 O.S2 17.2O 33.1 74.9 2O.9 2.3 O.7 0.4 O.6 0.4 O.3 1.7 Ex. 4 1.07 4649 43.4 O.38 0.52 15.3O 29.4 61.3 28.9 4.0 1.6 1.O 1.3 1.2 O.7 4.2 Ex. 5 1.26 6450 51.2 O.32 0.55 16.O 29.1. 85.3 12.9 1.O O.2 O.2 O.2 O.2 O.2 O.8 Ex. 6 1.10 28OO 25.5 O.35 0.26 7.9 30.4 63.8 32.1 2.2 0.5 0.4 0.4 0.4 O.2 1.4 US 6,642,325 B2

TABLE 1-continued Evaluation of catalysts Activity Activity MI FI Fine gPEI (10-)g BD g/10 g/10 MF Particle size distribution of PE (mesh Powder Catalyst Ti% g Cat PE/g Ti g/cm min min R <20 20–40 40–65 65–80 80-100 100-140 140-200 >200 >80 Comp. 1.36 3946 29.0 O.32 O.18 5.41. 30.1 73.5 22.9 1.8 0.4 O.2 O.2 O.2 O.8 1.4 Ex. 1 Comp. 1.26 2402 19.1 O.37 O.2O 6.78 33.9 34.7 54.4 4.7 1.4 O.9 1.2 1.5 1.3 4.9 Ex. 2 Comp. O.90 12OO 13.3 O.32 O.51 15.4 30.2 12.1 60.1 24.O 1.9 0.5 0.5 O.6 O.3 1.9 Ex. 3 Comp. 0.95 1160 12.2 0.38 0.52 16.3 31.3 11.4 61.6 22.5 1.5 O.7 O.8 O.8 O.7 3.0 Ex. 4

TABLE 2 Evaluation for gas phase fluidized bed(D150) polymerization of catalysts Activity MI FI Fine g PE, BD g/10 g/10 D Particle Size Distribution of PE (mesh Powder Catalyst g Cat g/cm min min MFR g/ml <2O 20-40 40-65 65-80 80-100 100-140 140-200 200 >60 Ex. 1 395O O.33 7.5 225.3 29.96 O.9247 57.6 38.2 3.2 0.5 O.3 O.2 O.O O.O 0.5 Ex. 5 591O O.30 8.6 254.O 29.46 O.9281 57.3 33.9 5.4 1.6 O.9 O6 O.3 O.O 1.8 Ex. 6 616O O.31 14 41.54 29.89 O.93O9 73.1 22.6 2.9 O.8 O.3 O.2 O.1 O.O O.6

It can be seen from Table 1 and Table 2 that by using silica increased from 1200 g PE/g Cat to 6667 g PE/g Cat, with M1 gel having a larger Specific Surface area in place of being essentially the same; by comparing Example 2 and SYLOPOL 948 silica gel, the Supporting ratio of the catalyst Comparative Example 3, it can be seen that the activity of component onto the silica gel is increased from 28% to 38%, the catalyst is increased from 1200 g PE/g Cat to 6160 g thereby Substantially enhancing the titanium content of the PE/g Cat, with M1 being essentially the same. When resultant catalyst, which provides the basis for enhancing the 35 ClCCH-OH is used as the halide promoter, by comparing activity of the resultant catalyst. At the same time, the good Example 3 and Comparative Example 4, it can be seen that particle morphology of the catalyst is maintained. If no the activity of the catalyst is increased from 1160 g PE/g Cat halide promoters such as ClCCH-OH, ClCCOCl and the to 4955 g PE/g Cat, with M1 being the same; when like are used during the preparation of the catalyst and only ClCCOCl is used as the halide promoter, by comparing a Silica gel having a larger Specific Surface area is used in 40 Example 4 and Comparative Example 4, it can be seen that place of SYLOPOL 948 silica gel, the activity of the the activity of the catalyst is increased from 1160 g PE/g Cat resultant catalyst is largely enhanced and however, the to 4649 g PE/g Cat, with M1 being the same. The above resultant polyethylenes have a largely decreased Ml and Fl. results clearly indicate that the catalysts according to the By comparing Comparative Example 1 and Comparative present invention have not only very high activity, but also Example 3, it can be seen that the activity of the catalyst is 45 excellent hydrogen response, thus Suitable for ethylene increased from 1200 g PE/g Cat to 394.6 g PE/g Cat, at the (co)polymerization by a gas phase process and a slurry same time, M1 is decreased from 0.51 g/10 min to 0.18 g/10 process, especially for the gas phase fluidized bed proceSS min. Further, by comparing Comparative Example 2 and operated in a condensed State. Since the catalysts according Comparative Example 4, it can be seen that the activity of to the present invention have a high activity, the polyethyl the catalyst is increased from 1160 g PE/g Cat to 2402 g 50 enes made by using them have low ash content. By employ PE/g Cat, at the same time, M1 is decreased from 0.52 g/10 ing the catalysts according to the present invention, various min to 0.20 g/10 min. These results clearly demonstrate that brands of polyethylene resins, especially LLDPE resins can by Simply replacing Silica gel having a Smaller Specific be produced with low cost and high quality. Surface area with Silica gel having a larger specific Surface What is claimed is: area, the activity of the catalyst is Substantially increased and 55 1. A Supported catalyst component comprising: however, its hydrogen response Substantially deteriorates. Therefore, Such an increase in the activity makes no Sense (i) a titanium-containing active component comprising for the preparation of ethylene polymerS having certain melt the reaction product of: a) at least one titanium compound; indexes. b) at least one magnesium compound, wherein the In order to overcome Such a disadvantage, a halide 60 promoter such as ClCCH-OH or ClCCOCl is incorporated magnesium compound is represented by the follow during the preparation of the catalyst according to the ing general formula: present invention and the experimental results indicate that the activity of the catalyst is Substantially enhanced and at the same time, polyethylenes have a constant Ml. For 65 wherein X is Cl, Br, I or combinations thereof example, by comparing Example 1 and Comparative c) at least one halide promoter; Example 3, it can be seen that the activity of the catalyst is d) at least one electron donor; and US 6,642,325 B2 11 12 (ii) a porous inert carrier material, wherein Said porous consisting of alkyl esters of C-C Saturated aliphatic car inert carrier material is Spherical or spheroidal Silica gel boxylic acids, alkyl esters of C7-Cs aromatic carboxylic having an average particle size of 10 to 100 microns acids, C-C aliphatic esters, C-C cyclic ethers, C-C, and a specific surface area of 300 to 1000 m/g, said Saturated aliphatic ketones and mixtures thereof. active component being Supported on the carrier mate 9. The Supported catalyst component according to claim 8 rial. wherein Said electron donor is Selected from the group 2. The Supported catalyst component according to claim 1 consisting of methyl formate, ethyl acetate, butyl acetate, wherein Said titanium compound is represented by any of the diethyl ether, dihexyl ether, tetrahydrofuran, acetone, methyl following general formulae: isobutyl ketone and mixtures thereof. 10. The Supported catalyst component according to claim Ti(OR), X, or TIX 1 wherein the magnesium compound, the electron donor and the halide promoter are used in amounts of 0.5 to 50 moles, wherein R is a C-C aliphatic hydrocarbyl, X is F, Cl, Br 0.5 to 50 moles and 0.5 to 50 moles, per mole of the titanium or combinations thereof and n is an integer of 1 to 4. compound, respectively. 3. The Supported catalyst component according to claim 2 15 11. The Supported catalyst component according to claim wherein Said titanium compound is Selected from titanium 1 wherein Said Silica gel has a pore Volume of 1.0 to 6.0 ml/g tetrachloride, titanium trichloride, titanium tetrabromide, and an average pore diameter of 5 to 45 nanometers. titanium tetraiodide, titanium tetrabutoxide, titanium 12. The Supported catalyst component according to claim tetraethoxide, triethoxy titanium chloride, diethoxy titanium 1 wherein Said Silica gel has a specific Surface area of 400 dichloride, ethoxy titanium and mixtures thereof. to 800 m /g. 4. The Supported catalyst component according to claim 1 13. The Supported catalyst component according to claim wherein Said magnesium compound is Selected from the 12 wherein Said Silica gel has an average particle Size of 20 group consisting of magnesium, dichloride, magnesium to 80 microns, a pore volume of 2.0 to 5.0 ml/g and an dibromide, magnesium diiodide and mixtures thereof. average pore diameter of 10 to 35 nanometers. 5. The Supported catalyst component according to claim 1 25 14. The Supported catalyst component according to claim wherein Said halide promoter is a class of compounds 1 wherein Said Silica gel has a specific Surface area of 600 represented by general formula F-R'R.X.s.l. wherein F to 800 m /g. represents a functional group Selected from the group con 15. A catalyst comprising the reaction product of: A) the sisting of aldhehyde, acyl, hydroxyl, amino, and ester; R. Supported catalyst component according to claim 1, and B) represents a divalent C-C aliphatic or aromatic group an alkyl aluminum compound. which is attached to the functional group F, R represents 16. The catalyst according to claim 15 wherein the alkyl hydrogen, unsubstituted or halogen-Substituted C-C alkyl, aluminum compound is Selected from the group consisting C-C cycloalkyl or Co-Co aromatic groups, b is 0, 1 or 2 of AlEt, Al(iso-Bu), Al(n-CH), Al(n-CH2), AlEta Cl and X is F, Cl or Br. and mixtures thereof. 6. The Supported catalyst component according to claim 5 35 17. A method for ethylene (co)polymerization compris wherein Said halide promoter is Selected from the group ing: consisting of 2,2,2-trichloroethanol, 2,2-dichloroethanol, 2-chloroethanol, 1,1-dimethyl-2,2,2-trichloroethanol, (i) providing the catalyst component of claim 15, and 4-chlorobutanol, para-chlorophenol, iso-chlorophenol, (ii) copolymerizing ethylene and another olefin in a gas ortho-chlorophenol and 2-chlorocyclohexanol. phase or Slurry proceSS in the presence of Said catalyst. 7. The Supported catalyst component according to claim 5 40 18. A method for ethylene polymerization comprising: wherein Said halide promoter is Selected from the group (i) providing the catalyst of claim 15; and consisting of trichloroacetyl chloride, dichloroacetyl (ii) polymerizing ethylene by a gas phase fluidized bed chloride, chloroacetyl chloride, o-chlorobenzoyl chloride process operated in a condensed State in the presence of and 2-chlorocyclohexyl carbonyl chloride. Said catalyst. 8. The Supported catalyst component according to claim 1 45 wherein Said electron donor is Selected from the group