GB2525541A

GB2525541A - Widely distributed polyolefin catalyst, and preparation and application thereof

Info

Publication number: GB2525541A
Application number: GB1514409.0A
Authority: GB
Inventors: Kejing Gao; Jianjun Yi; Qigu Huang; Baichun Zhu; Haibing Huang; Zhi Liu; Yonggang Wang; Rongbo Li
Original assignee: Petrochina Co Ltd
Current assignee: Petrochina Co Ltd
Priority date: 2013-01-30
Filing date: 2013-07-11
Publication date: 2015-10-28
Anticipated expiration: 2033-07-11
Also published as: GB2525541B; CN103113499B; JP2016505085A; JP6067886B2; WO2014117308A1; DE112013006537B4; DE112013006537T5; CN103113499A; GB201514409D0

Abstract

The present invention relates to a widely distributed polyolefin catalyst, and preparation and an application thereof. A main catalyst comprises a carrier, a transition metal halide, an organic alcoholic compound, and a siloxane electron donor in a mol ratio of 1:(1-30):(0.5-30):(0.01-5); the transition metal halide is generated by titanate and silicon halide through in-situ reaction in a mol ratio of 1:(1-30):(1-40), and a mol ratio of the titanate and the silicon halide is 1:(0.5-2); a co-catalyst is an organic aluminum compound; and a mol ratio of the transition metal halide in the main catalyst and the co-catalyst is 1:(30-500). The particles in the catalyst of the present invention are excellent in shape and are spherical; the catalyst has high activity and widely distributed polymer molecular weight; the catalyst is applicable to a slurry process, a gas phase polymerization process, or a combined polymerization process; and the preparation method is simple, has low requirements on equipment, and produces little pollution to the environment.

Description

Widely distributed polyolefin catalyst, and preparation and application thereof

Technical Field

The present invention belongs to the field ofolefin polymerization catalyst and olefin polymerization, and particularly relates to a catalyst for polymerization of ethylene or copolymerization of ethylene, a production method for the catalyst and use of the catalyst.

Background

The olefn polymerization catalyst is the core of polymcrization technology of polyolefin. As seen from the progress of olcfin polymerization catalyst, there are mainly two aspects: (1) development of a catalyst capable of producing polyolefin resin with a special performance or bcttcr performance. such as metallocene catalyst and non-metallocene late transition metal catalyst (2) simplification of the catalyst production process, reduction of catalyst cost, and development of environment-friendly technology to improve benefit and enhance competitiveness, based on a further improvement of the performance of the catalyst, for the production of general polyolefin resin. Before the I 980s, the research of polyethylene catalyst was fbcused on the pursuit of catalyst efficiency. After nearly 30 years ofcfforts, the catalytic efficiency of the polyethylene catalyst has been improved, the polyolefin production process is simplified, and the energy consumption and material consumption are reduced.

Patents CN20101O186264.2 and CN200910092169.3 disclose a supported catalyst consisting essentially of a carrier, a titanium halide and an electron donor, wherein the titanium halide is added directly into the catalyst components. Patent CN20101023 1403.9 discloses that widely distributed polyolefin maybe produced by adding organic siloxane in the preparation of the catalyst.

The present application has found that the polymerization or copolymerization of ethylene can he efficiently catalyzed by a catalyst system composed of a main catalyst, produced by loading titanium halide generated by in-situ reaction between titanate and silicon halide onto a carrier, and a co-catalyst, and the molecular weight distribution ofpolyolefin may he broadened by adding siloxane electron donor in the main catalyst components, during the preparation of the catalyst. The main catalyst prepared by the present invention has particles with good morphology, a high loading capacity, and a high activity, and the catalyst will not peel off from the carrier, and is applicable to a sluriy polymerization process. a vapor phase polymerization process, or a combined polymerization process.

Summary of inventi on

An object of the present invention is to provide a catalyst having a high catalytic activity for use in the polymerization of ethylene or copolymerization of ethylene with a comonomer, and the production method thereof The present invention provides an ethylene copolymerization catalyst composed of a main catalyst and a co-catalyst. The main catalyst is composed of a carrier, a transition metal halide, an organic alcohol compound and a siloxane electron donor, and the molar ratio of the carrier, the transition metal halide, the organic alcohol compound and the siloxane electron donor is I: 1-30: 0.5-30 0.0 1-5. The transition metal halide is generated by titanate and silicon halide through in-situ reaction, and the molar ratio of the carrier, the titanate and the silicon halide is 1: 1-30: 1-40, and the molar ratio of the titanate and the silicon halide is I: 0.5-2. The co-catalyst is an organo-alurninum compound. The relation of the amounts of the main catalyst and the co-catalyst is that the molar ratio of the transition metal halide in the main catalyst to the co-catalyst is 1: 3 0-500.

The carrier is a halide carrier, an inorganic oxide carrier or a polymeric carrier.

Among them, the halide carrier is magnesium dihalide, complexes of magnesium dihalide with water or alcohol, derivatives of magnesium dihalides having one or both of halogen atoms substituted with hydroxy or halohydroxy group in the formulae.

Specific compounds thereof maybe at least one ofmagncsiuni diehloride, magnesium dibromide, magnesi urn diiodide, methoxy magnesium chloride, ethoxy magnesium chloride, propoxy magnesium chloride, hutoxy magnesium chloride, phenoxy magnesium chloride, magnesium ethoxide. magnesium isopropoxkle, magnesium butoxide, isopropoxy magnesium chloride, dihutyl magnesium, butylmagnesium chloride and the like. The inorganic oxide carrier is selected from at least one of silica, alumina and the like. The polymeric carrier is selected from polystyrene. Among them, magnesium diehloride, dibutyl magnesium or hutylmagncsium chloride is lDrefened.

One characteristic of the present invention is addition of titanate in the preparation of the main catalyst, wherein the titanate is selected from at least one of a compound having a general formula (1) Ti(OR)4. where R is selected from Ci-C20 aliphatie hydrocarbon group, Co-C20 eyclopentadienyl group and derivatives thereoi Co-C20 aromatic hydrocarbon group, COR' or COOR', where R' is Ci-Cio aliphatic group or CCio aromatic group. R may he specifically selected from: at least one of methyl, ethyl, propyl, hutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isobuty1, tert-butyl.

iso-pentyl, tert-pentyl, 2-ethylhexyl, phenyl, naphthyl, o-methylphenyl, m-methylphenyl. p-methylphenyl, o-sulfophenyl, formyl, aeetyl or benzoyl and the like. Among them, titanium tetrabutoxide is preferred.

The molar ratio of the titanate to the can-icr is preferably 1-30: I. One characteristic of the present invention is addition of silicon halide in the preparation of the main catalyst, wherein the silicon halide is selected from at least p one of a compound having a general formula (2) SiXR.' m, where X is a halogen, preferably Cl, Br, F or the like; R" is H, CrC2O aliphatic hydrocarbon group, Ct-C2o aliphatic alkoxy group, C6-C20 cyclopentadienyl and derivatives thereof; or C6-C20 aromatic hydrocarbon group. R" may be specifically selected from: at least one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, iso-butyl, tert-butyl, iso-pentyl, tert-pentyl, 2-ethyihexyl, phenyl, naphthyl, o-methylphenyl, m-metbylphenyl, p-methylphenyl, o-sulfophenyl, formyl, acetyl or benzoyl and the like. nis 1,2,3, or4; mis 0, 1,2 or 3; n+m =4. Among them, silicon tetrachioride is preferred.

The molar ratio of the silicon halide to the carrier is preferably 1-40: 1.

One characteristic of the present invention is addition of organic alcohol in the preparation of the main catalyst, wherein the organic alcohol is selected from at least one of a compound having a general formula (3) R3OH, where it3 is Ci-C2o aliphatic hydrocarbon group, C6-C2o cyclopentadienyl group and derivatives thereof, or C6-Czo aromatic hydrocarbon group. K3 may be specifically selected from: at least one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, iso-butyl, tert-butyl, iso-pentyl, tert-pentyl, 2-ethylbexyl, benzyl, and the like. Specifically, ethanol, octanol, isooctanol, isopropanol, hexanol, and amyl alcohol are preferred.

The molar ratio of the organic alcohol to the carrier is preferably 3-15: 1.

One characteristic of the present invention is addition of the siloxane electron donor in the preparation of the main catalyst, wherein the siloxane electron donor is represented by a general formula (4): R50_t_OR2 OR3 general formula (4) in the fbnnula (4), it2, R3, it4 and it5 are Ci-Cts alkyl group, C3-C20 cycloalkyl group, or C6-C30 aryl group; two or three of Ri, it3. it, and Ks may be the same, or four of them are different. The siloxane electron donor may be specifically selected from: one or a mixture of triethoxyisopropoxysilane, diethoxyisopropoxy-t-butoxysilane, triisopropoxy-t-butoxysilane, diisopropoxydi-t-butoxysilane, dicthoxycyclohexyloxy-t-butoxysilane, diethoxyphenoxy-t-butoxysilane, ethoxydiisopropoxy-t-butoxysilane or ethoxyisopropoxy-t-butoxycyclohexyloxysilane.

Triethoxyisopropoxysilane, diethoxyisopropoxy-t-butoxysilane, triisopropoxy-t-butoxysilane, diisopropoxydi-t-butoxysilane, diethoxycyclohexyloxy-t-butoxysilane, or ethoxydiisopropoxy-t-butoxysilane is preferred.

The molar ratio of the organic siloxane compound to the carrier is preferably 0.01-5 I. The co-catalyst, organo-aluminum compound is selected from one or a mixture of two of a compound having a general formula A1R5X311, where R5 is hydrogen or a hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms, X is halogen, and n is an integer of 0<n3 Specifically, it may he selected from: one or a mixture of two of trimethyl aluminum, triethyl aluminum, tripropyl aluminum. triisobutyl aluminum. tri-n-hexyl aluminum, tri-tert-butyl aluminum, trioctyl aluminum, diethyl aluminum chloride, ethyl aluminum diebloride, ethylaluminurn sesquichioride and the like; and methyl aluminoxane, ethyl aluminoxane and the like. Among them, one or a mixture of two of triethyl aluminum or triisobutyl aluminum or methyl alurninoxane is preferred.

As a preferred cmhodimcnt of the present invention, the relation of the amounts of the main catalyst and the co-catalyst is that the molar ratio of the transition metal halide to the co-catalyst is 1: 30-500, The present invention provides a production method ftr the olefin polymerization catalyst, comprising thc steps of 1) dispersing the carrier in an organic solvent at 10-150°C, adding the organic alcohol compound, and dissolving; 2) adding the titanate and the siloxane to the solution obtained in step 1) and stirring for 1-5 hours at 10-150°C; 3) adding the silicon halide to the solution obtaincd in step 2) at 10-150°C and stirring for 1-5 hours after dropwise adding, stopping the reaction, standing for precipitation, filtering, and washing and drying the precipitate obtained; 4) dispersing the product obtained in. step 3) in an organic solvent, adding excess TiC14 dropwise at a temperature of -10°C to 30°C, maintaining at the temperature of -10°C to 30°C fbr I hour, slowly warming up to 60°C to 100°C and reacting for 2-5 hours, after the reaction, washing with toluene or n-hexane 4-6 times, filtering, removing unreaeted materials and the solvent, and drying by vacuum suction to give the main catalyst; and 5) mixing the main catalyst and the co-catalyst in a molar ratio of the co-catalyst to the transition metal halide in the main catalyst at 3 0-500: 1, to obtain the olefin polymerization catalyst.

The organic solvent is selected from toluenc, xylene, hexane, heptane, octane or decane, or a mixed solvent thereoL and toluene, hexane, heptane or deeane is preferred.

Ethylene polymerization catalyst provided by the present invention may be used as the catalyst for polymerization of ethylene or copolymerization of ethylene with a-olefin,wherein the u-olefin is preferably propylene, 1-butene. 1-hexene. 1-octene, 1 -decene. 3-methyl-1 -butene, cyclopentene, 4-methyl-l-penl.ene, I.3-butadiene, isoprene, styrene. methyl styrene or the like.

The oleuin polymerization catalyst provided by the present invention has the following advantageous effects: The object of the present invention is to provide ethylene copolymerization catalyst having a good particle morphology in a spherical shapc, and a high activity. The polyethylene obtained by using the catalyst has a wide molecular weight distribution, The catalyst is applicable to a slurry process, a vapor phase polymerization process, or a combined polymerization process. The preparation method thereof is simple, has low requirements on equipment, and produces little pollution on the enviromnent.

DETAILED DESCRIPTiON

Examp]e I 1) Preparation of the main catalyst: Into a fully nitrogen-purged reactor, magnesium dichloride 1 g, ethanol 9 ml, and toluene 70 ml were sequentially added, heated with stirring to 100°C, and maintained for 3 h; after cooling to 60°C, 18.0 ml Ti(OBu)4 was added dropwise with 3.5 g diethoxyisopropoxy-t-hutoxysilane; after reaction for 1 h, 11.0 ml SiC!4 was slowly added dropwise at 10°C; after reaction for 2 h, stirring was stopped, the resultant was left for precipitation and filtered, and the precipitate obtained was washed and dried to give solid particles. The resultant solid particles were dispersed in 30 nil of toluene, 20 ml TiCI4 was added dropwise at 0°C.

then maintained at 0-I 0°C fbr I Ii, and reacted at 60°C for 3 h. Stirring was stopped, and the suspension was allowed to stand, layered, had the supematant removed by suction, washed with toluene twice, and hexane twice, dried with nitrogen flow, to give the main catalyst having a good flowahility, and a narrow particle size distribution.

2) Ethylene copolymerization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg, dehydrated hexane 200 ml, and AlEt3 Solution 1.2 ml (2 mmoi/ml) were sequentially added, I-oetene 35 mL was added, after heated to 80°C, the autoclave was charged with hydrogen gas to 0.28MPa, then with ethylene to 0.73 MPa, and the reaction was carried out at constant pressure and temperature for 2 h. MWD = 42.

3) Ethylene polymerization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg, dehydrated hexane 200 ml.

and A1E13 Solution 1.2 ml (2 mniol/ml) were sequentially added, after heated to 80°C, the autoclave was charged with ethylene to 0.3 MPa, and the reaction was carried out at constant pressure and temperature for 2 h. MWD = 45.

Example 2

1) Preparation of the main catalyst: Into a fully nitrogen-purged reactor, magnesium dichloride 1 g, isooctanol 10 ml, and toluene 60 ml were sequentially added, heated with stirring to 90°C, and maintained for 4 h; after cooling to 70°C, 22.0 ml Ti(OBu)4 was added dropwise with 2.5 g triethoxyisopropoxysilane; after reaction for I h. 14.0 ml S1C14 was slow]y added dropwise at 50°C; after reaction for 3 h, stirring was stopped, the resultant was left for precipitation and filtered, and the precipitate obtained was washed and dried to give solid particles. The resultant solid particles were dispersed in 40 ml of toluene, 25 ml TiCI4 was added dropwise at -5°C, then maintained at 0-10°c: for 2 h, and reacted at 70°C for 4 h. Stirring was stopped, and the suspension was allowed to stand, layered, had the supematant removed by suction, washed with toluene twice, and hexane twice, dried with nitrogen flow, to give the main catalyst having a good flowability, and a narrow particle size distribution.

2) Ethylene eopolymerization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg, dehydrated hexane 200 ml, and AlEti Solution 1.5 ml (2 mmol/ml) were sequentially added, 1 -hexene 40 mL was added, after heated to 80°C, the autoclave was charged with hydrogen gas to 0.28MPa.

then with ethylene to 0.73 MN, and the reaction was carried out at constant pressure and temperature for 2 h. MWD 46.

mid AIEt3 Solution 1.5 ml (2 mmol/ml) were sequentially added, alter heated to 80°C, the autoclave was charged with ethylene to 0.3 MPa, and the reaction was carried out at constant pressure and temperature for 2 h, MWD = 49.

Example 3

1) Preparation of the main catalyst: Into a filly nitrogen-purged reactor, magnesium dichioride 2 g, ethanol 15 ml, and toluenc 90 ml were sequentially added, heated with stirring to 120°C, and maintained for 3 h; after cooling to 100°C, 35.0 ml Ti(OBu)4 was added dropwise with 5g triethoxy-t-butoxysilane; alter reaction for I ii, 22.0 nil SiCI4 was slowly added dropwise at 70°C; after reaction for 2 h. stirring was stopped, the resultant was left thr precipitation and filtered, and the precipitate obtained was washed and dried to give solid particles. The resultant solid particles were dispersed in 50 ml of tolucne, 30 ml TiCl4 was added dropwise at 0°C, then maintained at 0-10°C for I h, and reacted at 65°C for 3 It Stirring was stopped, and the suspension was allowed to stand, layered. had the supematant removed by suction, washed with toluene twice, and hexane twice, dried with nitrogen flow, to give the main catalyst having a good flowability, and a narrow particle size distribution.

2) Ethylene copolymerization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg, dehydrated hexane 200 ml, and AIEt3 Solution 1.2 ml (2 mmol/ml) were sequentially added, 4-methyl-i -pentene ml, was added, after heated to 80°C, the autoclave was charged with hydrogen gas to 0.28MPa, then with ethylene to 0.73 MPa, and the reaction was carried out at constant pressure and temperature for 2 h. MWD = 53.

3) Ethylene polymerization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg, dehydrated hexane 200 ml, and AlEt3 Solution 1.2 ml (2 mmol/nil) were sequentially added, after heated to 20°C, the autoclave was charged with ethylene to 0.3 MPa, and the reaction was carried out at constant pressure and temperature for 2 h. MWD = 58.

Example 4

1) Preparation of the main catalyst: Into a fully nitrogen-purged reactor, magnesium dichioride I g, ethanol 9 ml, and toluene 70 nil were sequentially added, heated with stirring to 100°C, and maintained for 4 h; alter cooling to 90°C, 15.0 ml Ti(OBu)3C1 was added dropwise with 2 g triethoxy-t-butoxysilane and 2 g diethoxyisopropoxy-t-butoxysilane; after reaction for 1 h, 9.0 ml SiCl4 was slowly added dropwise at 20°C; after reaction for 2 h, stirring was stopped, the resultant was left for precipitation and filtered, and the precipitate obtained was washed and dried to give solid particles. The resultant solid particles were dispersed in 30 nil of toluene, ml TiCl4 was added dropwise at 0°C, then maintained at 0-10°C for I h. and reacted at 60°C for 3 h. Stirring was stopped, and the suspension was allowed to stand, layered, had the supcrnatant removed by suction, washed with toluene twice, and hexane twice, dried with nitrogen flow, to give the main catalyst having a good flowability, and a narrow particle size distribution.

2) Ethylene copolyinerization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg. dehydrated hexane 200 ml, and AIR3 Solution 1.2 ml (2 nimol/ml) were sequentially added, 1-hexene 30 mL was added, after heated to 80°C, the autoclave was charged with hydrogen gas to 0.28MPa, then with ethylene to 0.73 MPa, and the reaction was carried out at constant pressure and temperature for 2 Ii. MWD = 50.

3) Ethylene polymerization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg, dehydrated hexane 200 ml, and AIEt3 Solution 1.2 ml (2 mmol/ml) were sequentially added, after heated to 80°C, the autoclave was charged with ethylen.e to 0.3 MN. and the reaction was carried out at constant pressure and temperature for 2 h. MWD = 55.

Example 5

I) Preparation of the main catalyst: Into a fully nitrogen-purged reactor, magnesium dichloride I g, isopropanol 13 ml, and toluene 70 ml were sequentially added, heated with stin-ing to 90°C, and maintained for 3 h; after cooling to 80°C, 15.0 nil Ti(OEt)4 was added dropwise with 5 g diethoxycyclohexyloxy-t-butoxysilane; after reaction for I h, 11.0 ml SiCl4 was slowly added dropwise at 30°C; after reaction for 2 h, stirring was stopped, the resultant wa.s left for precipitation and filtered, and the precipitate obtained was washed and dried to give solid particles. The resultant solid particles were dispersed in 30 ml of toluene, 20 ml T1CI4 was added dropwise at 0°C, then maintained at 0-10°C for I h, and reacted at 60°C for 3 h. Stirring was stopped, and the suspension was allowed to stand, layered. had the supernatant removed by suction, washed with toluene twice, and hexane twice, dried with nitrogen flow, to give the main catalyst having a good flowability. and a narrow particle size distribution, 2) Ethylene copolymerization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg, dehydrated hexanc 200 ml, and AIEt3 Solution 1.3 ml (2 mmol/rnl) were sequentially added, 1-hexene 30 rnL was added, after heated to 80°C, the autoclave was charged with hydrogen gas to 0.28MPa, then with ethylene to 0.73 MPa, and the reaction was carried out at constant pressure and temperature for 2 h. MWD 42.

3) Ethylene polymerization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg, dehydrated hexane 200 ml, and AIEt3 Solution 1.2 ml (2 mmol/ml) were sequentially added, after heated to 80°C, the autoclave was charged with ethylene to 0.3 MPa, and the reaction was earned out at constant pressure and temperature for 2 h. MWD = 38.

Example 6

I) Preparation of the main catalyst: into a fully nitrogen-purged reactor, magnesium dichloride 1 g, isooetanol 9 ml, and tolucne 70 ml were sequentially added, heated with stirring to 100°C, and maintained for 3 h; after cooling to 80°C, 30.0 ml Ti( Pr)4 was added dropwise, and 8 g diethoxyisopropoxyphcnoxysilanc was added; after reaction for 1 h, 11.0 ml SiCl4 was slowly added dropwise at 10°C; after reaction for 2 h. stirring was stopped, the resultant was left for precipitation and filtered, and the precipitate obtained was washed and dried to give solid particles. The resultant solid particles were dispersed in 30 ml oftoluenc, 20 ml TiCI4 was added dropwise at 0°C, then maintained at 0-10°C for I h. and reacted at 60°C for 3 h. Stirring was stopped, and the suspension was allowed to stand, layered, had the supernatant removed by suction, washed with toluene twice, and hexane twice, dried with nitrogen flow, to give the main catalyst having a good flowability. and a narrow particle size distribution.

2) Ethylene copolymerization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg, dehydrated hexane 200 ml, and AlEt3 Solution 1.5 ml (2 mmol/ml) were sequentially added, I -hexene 30 rnL was added, after heated to 80°C. the autoclave was charged with hydrogen gas to 0.28MPa, then with ethylene to 0.73 MPa, and the reaction was carried out at constant pressure and temperature for 2 h. MWD = 46.

3) Ethylene polymerization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg, dehydrated hexane 200 ml, and AJEt3 Solution 1.2 in! (2 mmol/ml) were sequentially added, after heated to 80°C, the autoclave was charged with ethylene to 0.3 MPa, and the reaction was carried out at constant pressure and temperature for 2 Ii. MWD =41.

Example 7

I) Preparation of the main catalyst: Into a fully nitrogen-purged reactor, dibutyl magnesium 1 & n-octanol I ml, and decane 50 ml were sequentially added, heated with stirring to 100°C, and maintained for 3 h; after cooling to 80°C, 40.0 ml Ti(OPr)4 was added dropwise, and 8 g diethoxyisopropoxyphenoxysilane was added; after reaction for I h, 20.0 ml SiCIs was slowly added dropwise at 60°C; after reaction for 2 h, stirring was stopped, the resultant was left for precipitation and filtered, and the precipitate obtained was washed and dried to give solid particles. The resultant solid particles were dispersed in 30 ml of toluene, 20 ml TiCL1 was added dropwise at 0°C, then maintained at 0-10°C for I h, and reacted at 60°C for 3 h. Stirring was stopped, and the suspension was allowed to stand, layered, had the supematant removed by suction, washed with toluene twice, and hexane twice, dried with nitrogen flow, to give the main catalyst having a good flowability, and a narrow particle size distribution.

2) Ethylene copolymerization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg, dehydrated hexane 200 ml, and AlEt3 Solution 1.5 ml (2 mmol/ml) were sequentially added, 1-hexene 30 mL was added, after heated to 80°C, the autoclave was charged with hydrogen gas to 0.28MPa, then with ethylene to 0.73 MPa, and the reaction was carried out at constant pressure and temperature for 2 h. MWD = 46.

3) Ethylene polymerization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg, dehydrated hexane 200 ml, and AIEt3 Solution 1.2 ml (2 mmol/mI) were sequentially added, after heated to 80°C, the autoclave was charged with ethylene to 0.3 MPa, and the reaction was carried out at constant pressure and temperature for 2 h. MWD =41.

Comparative Example 1 I) Preparation of the main catalyst: Into a folly nitrogen-purged reactor, magnesium dichloride & ethanol 3.2 ml, epichlorohydrin 3 ml, tributyl phosphate 6.5 ml, and toluene 75 ml were sequentially added, heated with stirring to 60°C; after the solid was completely dissolved to form a homogeneous solution, the temperature was maintained for I h; after cooling to -25°C, 50.0 ml TiCI4 was added dropwise, hexane ml was added dropwise, and after dropwise adding, tetraethoxy silane 4 ml was added; after reaction for I h, the temperature was sequentially maintained at -10°C for I h, at 0°C for I Ii, at 20°C for I h, and raised to 60°C; hexane 10 ml was added, and the reaction was carried out at constant temperature for 2 it Stirring was stopped, and the suspension was allowed to stand, layered, had the supematant removed by suction, washed with toluene twice, and hexane twice, dried with nitrogen flow, to give the main catalyst having a good flowahility, and a narrow particle size distribution.

2) Ethylene copo]ynierization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg, dehydrated hexane 200 ml, and A1Et3 Solution 1.2 ml (2 mmol/ml) were sequentially addcd, 1 -hexene 30 mL was added, after heated to 80°C, the autoclave was charged with hydrogen gas to 0.28MPa, then with ethylene to 0.73 MPa, and the reaction was carried out at constant pressure and temperature for 2 h. MWD 7,5.

3) Ethylene polymerization: A 0.5 liter stainless steel autoclave was sufficiently purged with nitrogen gas, and then the main catalyst 20mg, dehydrated hexane 200 ml, and A1Et3 Solution 1.2 ml (2 mmol/ml) were sequentially added, after heated to 80°C, the autoclave was charged with ethylene to 0.3 MPa, and the reaction was calTied out at constant pressure and temperature for 2 h. MWD = 6.3.

Industrial Applicability

Particles of the ethylene copolymerization catalyst provided by the present invention are good in morphology and are in a spherical shape. The catalyst has high activity, and the polyethylene obtained by using the catalyst has a wide molecular weight distribution. It is applicable to a slurry' method, a vapor phase polymerization process, or a combined polymerization process. The preparation method thereof is simple, has low requirements on devices, and produces little pollution on the environment.

The results of the Examples are shown in Table 1.

Table I

Example Content of Catalytic Bulk Comonorner Molar transition efficiency density content of metal iii (KgPE/g (g/cm3) comonomcr the main eat) in the F catalyst polymer _____________ (wt%) ___________ ________ ___________________ (mol%) Ti, 5.5 47.4 0.30 l-oetene 0.4 _______ 51.4 0.30 Ethylenehomopolymerization 2 Ti, 5.6 45.3 1-hexene -1.8 _____ 46.3 0.31 Ethylene homopolymerization 3 Ti. 5.4 46.9 0.31 4-methyl-l-pentene 1.2 _____ __________ 48.9 0.31 Ethylene homopolymerization 4 _______ Ti. 5.9 48.6 0.30 1-hexene 2.6 _____________ ___________ 50.5 0.31 Ethylene homopolyrnerization Ti, 5.5 48.8 030 1-hexene 1.8 ____________ __________ 49.1 0.3 I Ethylene hornopolymcrization 6 Ti, 5.8 46.7 0.30 1-hexene 1.7 ____________ ___________ 48.4 0.31 Ethylene homopoiyrnerization 7 Ti,6.1 51.3 0.32 1-hexene 1.8 ______________ ____________ 49.5 0,32 Ethylene hornopolyrnerization Comparative Ti, 4.9 46.2 0.32 1-hexene 1.4 Example 1 47.1 0.32 Ethylene hornopolyrnerization

Claims

CLAIMS1. A widely distributed polyolefin catalyst consisting of a main catalyst and a co-catalyst, characterized in that, the main catalyst is consisting of a carrier, a transition metal halide, an organic alcohol compound, and a siloxane electron donor.
2. The polyolefm catalyst according to claim 1, characterized in that, the molar ratio of the carrier, the transition metal halide, the organic alcohol compound and the siloxane electron donor is I: 1-30:0.5-30:0.001-1.
3. The polyolefin catalyst according to claim 1, characterized in that, the transition metal halide is generated by reaction between titanate and silicon halide during the preparation of the catalyst.
4. The polyolefin catalyst according to claim 1, characterized in that, the molar ratio of the carrier, the titanate, and the silicon halide is 1: 1-30: 1-40.
5. The polyolefin catalyst according to claim I, characterized in that, the molar ratio of the titanate and the silicon halide is I: 0.5-2.
6. The polyolefin catalyst according to claim I, characterized in that, the co-catalyst is an organo-aluminum compound; and the molar ratio of the transition metal halide in the main catalyst to the co-catalyst is I 30-500.
7. The polyolefin catalyst according to claim I, characterized in that, the co-catalyst, organo-aluminum compound is selected from one or a mixture of two of a compound having a general formula AlR5,X3..,,, where K5 is hydrogen or a hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms, X is halogen, and n is an integer of 0<nS3.
8. The polyolefin catalyst according to claim I, characterized in that, the carrier is a halide carrier, an inorganic oxide carrier, or a polymeric carrier.
9. The polyolefin catalyst according to claim 1, characterized in that, the titanate is selected from at least one of a compound having a general formula (1) Ti(OR)4, where K is selected from C1-C20 aliphatic hydrocarbon group, C6-C20 cyclopentadienyl group and derivatives thereof, C6-C20 aromatic hydrocarbon group, COlt' or COOK,, where It' is CrCJ0 aliphatic group or C6-C10 aromatic group.
10. The polyolefin catalyst according to claim 1, characterized in that, the silicon halide is selected from at least one of a compound having a general formula (2) SiXK' where X is a halogen, preferably Cl, Br, F or the like; K" is H, C1-C20 aliphatic hydrocarbon group, C1-C20 aliphatic alkoxy group, C4-C20 cyclopentadienyl and derivatives thereof, or C6-C20 aromatic hydrocarbon group; n is 1,2, 3, or4;mis 0, 1,2or3; n+m4.
11. The polyolefin catalyst according to claim 1, characterized in that, the organic alcohol is selected from at least one of a compound having a general formula (3) R3OH, where It3 is C,-C20 aliphatic hydrocarbon group, C6-C20 cyclopentadienyl group and derivatives thereof, or C6-C20 aromatic hydrocarbon group.
12. The polyolefin catalyst according to claim 1, characterized in that, the siloxane electron donor is represented by a general formula (4): 0R4 R50_t_OR2 OR3 general formula (4) in the formula (4), R2* it3, 14 and It, are C3-C,, alkyl group, C3-C20 cycloalkyl group, or C6-C30 aryl group; two or three of K2, it3, It4 and it, may be the same, or four of them are different.
13. A production method for the polyolefin catalyst according to claim I, characterized in comprising the steps of: I) dispersing the carrier in an organic solvent at 10-150°C, adding the organic alcohol compound, and dissolving; 2) adding the titanate and the siloxane to the solution obtained in step I) and stirring for 1-5 hours at 10-150°C; 3) adding the silicon halide to the solution obtained in step 2) at 10-150°C and stirring for 1-5 hours after dropwise adding, stopping the reaction, standing for precipitation, filtering, and washing and drying the precipitate obtained; 4) dispersing the product obtained in step 3) in an organic solvent, adding excess TiCl4dropwise at a temperature of -10°C to 30°C, maintaining at the temperature of -10°C to 30°C for 1 hour, slowly warming up to 60°C to 100°C and reacting for 2-5 hours, after the reaction, washing with toluene or n-hexane 4-6 times, filtering, removing unreacted materials and the solvent, and drying by vacuum suction to give the main catalyst; and 5) mixing the main catalyst and the co-catalyst in a molar ratio of the transition metal halide to the co-catalyst at 1: 30-500, to obtain the olefin polymerization catalyst.
14. The production method according to claim 13, characterized in that, the organic solvent is selected from toluene, xylene, hexane, heptane, octane, or decane, or a mixed solvent thereof.
15. Use of the polyolefin catalyst according to claim 1 as the catalyst for polymerization of ethylene or copolymerization of ethylene with a comonomer.