CN88103215A - Catalyst for olefin polymerization and process for olefin polymerization - Google Patents

Catalyst for olefin polymerization and process for olefin polymerization Download PDF

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CN88103215A
CN88103215A CN88103215.8A CN88103215A CN88103215A CN 88103215 A CN88103215 A CN 88103215A CN 88103215 A CN88103215 A CN 88103215A CN 88103215 A CN88103215 A CN 88103215A
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compound
aikyiaiurnirsoxan beta
metal compound
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polymerization
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CN1020735C (en
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木冈护
筒井俊之
丰田昭德
柏典夫
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Mitsui Chemical Industry Co Ltd
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Mitsui Petrochemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof

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Abstract

The invention is composed of (A)]A transition metal compound of group IVB of the periodic Table of the elements or [ A1]A solid catalyst component comprising a particulate carrier and [ B ] a transition metal compound of group IVB of the periodic Table supported thereon]Aluminoxanes and [ C]By the general formula [ I]Or of the general formula [ II]Organoaluminum compound of
Rm 1Al(OR2)3-m [I]
Rn 3Al[OSiR3 4]3-n [II](in the formula, R1、R2And R3Represents a hydrocarbon group, R4A hydrocarbon group, an alkoxy group or an aryloxy group, and m and n are positive numbers of 0 < m < 3 and 0 < n < 3, respectively) in the presence of an olefin polymerization catalyst, and an olefin polymer or copolymer having a narrow composition distribution, a large bulk specific gravity, a uniform particle size and a small amount of fine powder can be obtained by utilizing the large polymerization activity of the catalyst.

Description

The invention relates to the polymerizing catalyst of alkene and use the olefine polymerizing process of this catalyzer.In detail, even be about reducing the usage quantity of expensive aikyiaiurnirsoxan beta, also can make alkene carry out polymerization, and can produce the catalyzer of the olefin polymer of macromolecule with its excellent polymerization activity, and the polymerization process that uses this catalyzer.In more detail, be about narrow in range of molecular weight distributions and be applicable under the situation of two or more olefinic polymerizations, can obtain molecular weight distribution and form the catalyzer of the narrow olefin copolymer of distribution range and use the polymerization process of this catalyzer with its excellent polymerization activity polymerization, and can make that molecular weight distribution is narrow, packing ratio is great, the catalyzer of powdered high quality liner olefin polymkeric substance and use the polymerization process of this catalyzer.
In the past, as alpha-olefinic polymer, particularly ethene polymers or ethene.The manufacture method of alpha-olefin copolymer, be under the situation that the Titanium series catalyst of being made up of titanium compound and organo-aluminium compound or the vanadium series catalyst be made up of vanadium compound and organo-aluminium compound exist, make ethene or ethene and alpha-olefin carry out the polymeric method.
On the one hand, the Ziegler-type olefin polymerization catalysis about new has proposed the catalyzer of being made up of zirconium compounds and aikyiaiurnirsoxan beta recently.
Open on the clear 58-19309 communique the spy, put down in writing by the compound of representing with following formula that contains transition metal.
(cyclopentadiene) 2MeRHal
(in the formula, R is cyclopentadiene, C 1-C 6Alkyl, halogen, M eBe transition metal, H aL is a halogen).
With the wire aikyiaiurnirsoxan beta of representing with following formula
Al 2OR 4〔Al（R）-O〕 n
(in the formula, R is methyl or ethyl, and n is the number of 4-20) or the ring-type aikyiaiurnirsoxan beta of representing with following formula
Figure 88103215_IMG1
(in the formula, the definition of R and n is same as described above)
Under the situation that the catalyzer of forming exists, under-50 ℃-200 ℃ temperature, make ethene and C 3-C 12One or more alpha-olefins carry out the polymeric method.On the same disclosed communique, also put down in writing the poly density that is obtained for regulating, under the situation of the alpha-olefin of the long key of a part of 10 weight % or mixture existence, carry out the polymerization of ethene at least.
Open on the clear 59-95292 communique the spy, put down in writing about with following formula
Figure 88103215_IMG2
(in the formula, n is 2-40 to the wire aikyiaiurnirsoxan beta of expression, and R is C 1-C 6Alkyl), and the discovery of the manufacture method of the ring-type aikyiaiurnirsoxan beta of representing with following formula
Figure 88103215_IMG3
(in the formula, the definition of n and R is same as described above).On same communique, also put down in writing and made with identical manufacture method, for example, after two (cyclopentadienyl) compound with methylaluminoxane and titanium or zirconium, carry out the polymerization of alkene, the transition metal of then per 1 gram, each hour can obtain the above polyethylene of 2,500 myriagrams.
Open the spy and to disclose a kind of method of making the catalyzer of for olefines polymerization on the clear 60-35005 communique, the aluminum oxide that following formula is represented
Figure 88103215_IMG4
(in the formula, R 1Be C 1-C 10Alkyl, R 0Be R 1Or the expression bonded-O-) at first react with magnesium compound, then resultant of reaction is carried out chlorination, further use T again i, V, Z rOr C rCompound is handled.On same communique, also put down in writing above-mentioned catalyzer and be specially adapted to ethene and C 3-C 12The copolymerization of the mixture of alpha-olefin.
Open the spy and to disclose a kind of catalyst system that the reactor blending polymkeric substance is used of making on the clear 60-35006 communique, it is by the 1-of different two or more transition metal, 2-or 3-cyclopentadiene or derivatives thereof (a) and aikyiaiurnirsoxan beta (b) combination.In the embodiment (1) of this communique, proposed with two (pentamethyl-cyclopentadienyl) methylcyclopentadienyl zirconiums and aikyiaiurnirsoxan beta as catalyzer, make ethene and propylene carry out polymerization, can obtain number-average molecular weight and be 15,300, weight-average molecular weight is 36,400 and to contain the propylene composition be 3.4% polyethylene.In addition, in the embodiment 2 of this communique, with two (pentamethyl-cyclopentadiene) zirconium dichloride, two (methyl cyclopentadiene) zirconium dichloride and aikyiaiurnirsoxan beta as catalyzer, make ethene and propylene carry out polymerization, obtain by containing number-average molecular weight 2,200, weight-average molecular weight 11,900 and contain the toluene soluble part of 30 moles of % propylene and contain number-average molecular weight 3,000, weight-average molecular weight 7, the toluene insoluble of 400 and 4.8 moles of % propylene is partly formed contains number-average molecular weight 2,000, the polyethylene and the ethene of weight-average molecular weight 8,300 and 7.1 moles of % propylene.The blend of propylene copolymer.Equally, in embodiment 3, put down in writing by molecular weight distribution (M w/ M n) 4.57 and the soluble part of 20.6 moles of % of propylene composition and molecular weight distribution be 3.04 and the propylene composition be the new LDPE (film grade) formed of the insoluble part of 2.9 moles of % and the blend of ethylene-propylene copolymer.
Open on the clear 60-35007 communique the spy, having put down in writing ethene is alpha-olefin more than 3 separately or with carbonatoms, under the situation that the catalyst system of aromatic ring alkene metal derivative and the ring-type aikyiaiurnirsoxan beta represented with following formula exists, carries out the polymeric method
Figure 88103215_IMG5
(in the formula, R is that carbonatoms is the alkyl of 1-5, and the definition of n is same as described above).With the resulting polymkeric substance of this method, according to the record of this communique, not only have the weight-average molecular weight of about 500-about 1,400,000, but also have the molecular weight distribution of 1.5-4.0.
In addition, open on the clear 60-35008 communique, put down in writing owing to used the catalyst system that contains 2 kinds of aromatic ring alkene metal derivatives and aikyiaiurnirsoxan beta at least, thereby prepare and have the wide polyethylene of range of molecular weight distributions or ethene and C the spy 3-C 10The multipolymer of alpha-olefin.On this communique, the molecular weight distribution (M that above-mentioned co-polymer had of record w/ M n) be 2-50.
Also have, open clear 60-260602 communique and the spy opens on the clear 60-130604 communique the spy, proposed to use by transistion metal compound and be mixed with the method that catalyzer that machine aluminium compound forms makes olefinic polymerization, this is mixed with machine aluminium compound and is made up of aikyiaiurnirsoxan beta and organo-aluminium compound, put down in writing owing to added organo-aluminium compound, thereby improved the polymerization activity of per unit transition metal.But, use these methods, all still there is the problem that expensive aikyiaiurnirsoxan beta consumption is many, per unit aikyiaiurnirsoxan beta activity is low.
In addition, in these look-ahead techniques, the catalyzer that forms by transistion metal compound that is proposed and aikyiaiurnirsoxan beta, more superior significantly than its polymerization activity of catalyst system that forms by transistion metal compound and organo-aluminium compound known to the former people, and in the catalyst system that is proposed, major part is soluble in reaction system.And be to adopt solution polymerization system mostly, except existing the polymerization system soltion viscosity significantly uprises, also have by the aftertreatment of these solution systems the bulk specific gravity of polymkeric substance little, thereby be difficult to obtain the problem of powdered high-quality polymkeric substance.
On the one hand, one or both compositions in above-mentioned transistion metal compound and the aikyiaiurnirsoxan beta are loaded in the porous inorganic oxygen compound supported catalyst of silicon oxide, silica alumina, aluminum oxide etc., in suspension polymerization system or gas phase polymerization system, carry out the polymerization of alkene with this catalyzer.
For example, open clear 60-35006 communique the above-mentioned spy who quotes, the spy opens clear 60-35007 communique and the spy opens on the clear 60-35008 communique, put down in writing to use transistion metal compound and aluminum oxide are loaded in supported catalysts such as silicon oxide, silica alumina, aluminum oxide.
In addition, open clear 60-106808 communique and the spy opens on the clear 61-106809 communique the spy, proposed to give and carried out resultant and the organo-aluminium compound that obtains after the reason of contact position earlier and polyolefine is had in the presence of the packing material of affinity at the high activated catalyst composition of titaniferous that dissolves in hydrocarbon solvent and/or zirconium and weighting agent, make ethene or ethene and alpha-olefin carry out polymerization, and make the method for compositions of forming by polyethylene-based polymkeric substance and packing material.
Open on the clear 61-31404 communique the spy, proposed in the presence of silicon-dioxide or aluminum oxide, by trialkylaluminium and water react and resultant, in the presence of the mixed catalyst of forming by this resultant and transistion metal compound, make the method for ethene or ethene and alpha-olefine polymerizing or copolymerization again.
In addition, open on the clear 61-276805 communique the spy, the reaction mixture that has proposed in zirconium compounds and aikyiaiurnirsoxan beta, trialkylaluminium to be reacted and obtain, again in this mixture, the catalyzer that the reaction mixture that the inorganic oxide of the surface hydroxyl that contains silicon oxide etc. is reacted obtain is formed exists down, makes alkene carry out the polymeric method.
Also have, open on clear 61-108610 communique and the clear 61-296008 communique of Te Kai the spy, there is down the method for carrying out olefinic polymerization in the supported catalyst that the transistion metal compound of aromatic ring alkene metal derivative etc. and aikyiaiurnirsoxan beta is loaded in inorganic oxide etc.
But, in these look-ahead techniques, use the solid catalyst on the carrier of being loaded in proposed, even alkene is carried out polymerization or copolymerization in suspension polymerization system or gas phase polymerization system, compare with above-mentioned solution polymerization system, polymerization activity also significantly reduces, and does not bring into play the inherent feature that is become the catalyzer that branch forms by transition metal compound catalyst composition and alumoxane catalyst fully, and the polymer that is generated does not have the relevant performance of powder of enough bulk specific gravitys etc. yet.
The purpose of this invention is to provide so a kind of olefin polymerization catalysis and make the method for olefin polymer with this catalyzer.This catalyzer is with the high polymerization activity of its per unit aikyiaiurnirsoxan beta, it is narrow and in molecular weight distribution and form and distribute all narrow olefin copolymer, particularly molecular weight distribution and form the ethylene that distribution range is narrow and molecular weight is big during olefinic polymerization more than two kinds to produce molecular weight distribution.
Also have, purpose of the present invention provides a kind of olefin polymer that can make and has big olefin polymerization catalysis of big bulk specific gravity and excellent powder characteristic and polymerization activity and the method for carrying out olefinic polymerization with this catalyzer.
The invention provides the catalyzer of forming by following one-tenth branch:
The transistion metal compound of (A) periodic table of elements IV B family,
(B) aikyiaiurnirsoxan beta, and
(C) general expression (I) or general expression (II)
R 1mAl（OR 2） 3-m〔Ⅰ〕
R 3nAl〔OSiR 4 3〕 3-n〔Ⅱ〕
The organo-aluminium compound of expression, (in the formula, R 1, R 2, R 3The expression alkyl, R 4Expression alkyl, alkoxyl group or aryloxy, m and n are respectively 0＜m＜3 and 0＜n＜3), and in the presence of this catalyzer, make the olefine polymerizing process of olefinic polymerization or copolymerization.
In addition, according to the present invention, also provide the catalyzer of forming by following one-tenth branch:
(A ') is loaded in the solid catalyst component of the periodic table of elements IV B group transition metal compound on the particulate carrier,
(B) aikyiaiurnirsoxan beta, and
(C) general expression (I) or general expression (II)
R 1mAl（OR 2） 3-m〔Ⅰ〕
R 3nAl〔OSiR 4 3〕 3-n〔Ⅱ〕
The organo-aluminium compound of expression, (in the formula, R 1, R 2, R 3The expression alkyl, R 4Expression alkyl, alkoxyl group or aryloxy, m and n are respectively the integer of 0＜m＜3 and 0＜n＜3), and in the presence of this catalyzer, make the olefine polymerizing process of olefinic polymerization or copolymerization.
In the present invention, so-called " polymerization " this speech is not only applicable to homopolymerization and closes, and comprises copolymerization yet.Simultaneously, so-called " polymkeric substance " speech not only has the implication of homopolymer, and comprises the implication of co-polymer.
Employed catalyzer in first embodiment of the present invention is formed by 3 catalyst components (A), (B), (C).
The transition metal of the periodic table of elements IV B family in the catalyst component (A) is to select from the group of being made up of titanium, zirconium and hafnium.As the transition element in the catalyst component (A), for well, and zirconium is best with titanium and zirconium.
About the example of the transistion metal compound of the periodic table of elements IV B family in the catalyzer (A), can enumerate to have the zirconium compounds of conjugated pi electron base as dentate.
Above-mentioned is that the zirconium compounds of dentate for example descends formula III to have the conjugated pi electron base
R 1 kR 2 lR 3 mR 4 nZ r（Ⅲ）
The compound of expression.(in the formula, R 1Representative ring alkadiene alkyl or its substituent, R 2, R 3And R 4Be loop chain diene alkyl, aryl, alkyl, cycloalkyl, aralkyl, halogen atom, hydrogen, OR a, SR b, NR c 2Or PR d 2, R a, R b, R cAnd R dBe alkyl, the silylation of alkyl, cycloalkyl, aryl, aralkyl etc., 2 R cAnd R dCan form ring after the connection.k≥1，k+1+m+n＝4。In addition, R 2During for loop chain diene alkyl, R 1And R 2Also can combine) with the low alkyl group form.Can enumerate for example cyclopentadienyl, methyl cyclopentadienyl, ethyl cyclopentadienyl, pentamethyl-cyclopentadienyl, dimethyl cyclopentadienyl, indenyl, tetrahydro indenyl etc. as the loop chain diolefine.Can enumerate for example methyl, ethyl, propyl group, sec.-propyl, butyl, hexyl, octyl group, 2-ethylhexyl, decyl, oleyl etc. as alkyl.Can enumerate for example phenyl, tolyl etc. as aryl.Can enumerate for example phenmethyl, 2-methyl-2-hydrocinnamyl etc. as aralkyl.Can enumerate for example cyclopentyl, cyclohexyl, ring octyl group, two ring (2,2,1) heptane bases, ring nonyl and these basic alkyl substituents as cycloalkyl.Can enumerate for example TMS, triethyl silyl, phenyl dimethylsilyl, tri-phenyl-silane base etc. as silylation.Also can enumerate other unsaturated cycloaliphatic base about unsaturated aliphatic bases such as vinyl, allyl group, propenyl, pseudoallyl, 1-butylene base and cyclohexenyl etc.Can enumerate for example fluorine, chlorine, bromine etc. as halogen atom.Can enumerate the low-grade alkylidene of methylene radical, ethylidene, propylidene, butylidene etc. as low-grade alkylidene.
Can enumerate following compound as this zirconium compounds:
Two (cyclopentadienyl) monochlor(in)ate one zircoium hydride,
Two (cyclopentadienyl) monobromination one zircoium hydride,
Two (cyclopentadienyl) hydrogenated methyl zirconium,
Two (cyclopentadienyl) ethyl zircoium hydride,
Two (cyclopentadienyl) cyclohexyl zircoium hydride,
Two (cyclopentadienyl) phenyl zircoium hydride,
Two (cyclopentadienyl) phenmethyl zircoium hydride,
Two (cyclopentadienyl) neo-pentyl zircoium hydride,
Two (methyl cyclopentadienyl) monochlor(in)ate one zircoium hydride,
Two (indenyl) monochlor(in)ate one zircoium hydride,
Two (cyclopentadienyl) zirconium dichloride,
Two (cyclopentadienyl) dibrominated zirconium,
Two (cyclopentadienyl) methyl monochlor(in)ate zirconium,
Two (cyclopentadienyl) ethyl monochlor(in)ate zirconium,
Two (cyclopentadienyl) cyclohexyl monochlor(in)ate zirconium,
Two (cyclopentadienyl) phenyl monochlor(in)ate zirconium,
Two (cyclopentadienyl) phenmethyl monochlor(in)ate zirconium,
Two (cyclopentadienyl) zirconium dichloride,
Two (tetramethyl-ring pentadienyl) zirconium dichloride,
Two (indenes) zirconium dichloride,
Two (indenes) dibrominated zirconium,
Two (cyclopentadienyl) phenyl zirconium,
Two (cyclopentadienyl) diphenyl-methyl zirconium,
Two (cyclopentadienyl) methoxyl group chlorination zirconium,
Two (cyclopentadienyl) oxyethyl group zirconium chloride,
Two (cyclopentadienyl) butoxy zirconium chloride,
Two (cyclopentadienyl) 2-ethyl hexyl oxy zirconium chloride,
Two (cyclopentadienyl) methyl ethoxy zirconium,
Two (cyclopentadienyl) methyl butoxy zirconium,
Two (cyclopentadienyl) ethyl oxyethyl group zirconium,
Two (cyclopentadienyl) phenyl ethoxy zirconium,
Two (cyclopentadienyl) phenmethyl oxyethyl group zirconium,
Two (methyl cyclopentadienyl) oxyethyl group zirconium chloride,
Two indenes oxyethyl group zirconium chlorides,
Two (cyclopentadienyl) oxyethyl group zirconium chloride,
Two (cyclopentadienyl) butoxy zirconium chloride,
Two (cyclopentadienyl) 2-ethyl hexyl oxy zirconium chloride,
Two (cyclopentadienyl) phenoxy group zirconium chloride,
Two (cyclopentadienyl) cyclohexyloxy zirconium chloride,
Two (cyclopentadienyl) phenyl methoxyl group chlorination zirconium,
Two (cyclopentadienyl) methylbenzene methoxyl group zirconium,
Two (cyclopentadienyl) trimethylsiloxy group alkane zirconium chloride,
Two (cyclopentadienyl) triphenyl siloxy zirconium chloride,
Two (cyclopentadienyl) thio-phenyl zirconium chloride,
Two (cyclopentadienyl) thio-ethyl zirconium chloride,
Two (cyclopentadienyls) two (diformamide) zirconium,
Two (cyclopentadienyl) diethylamide zirconium,
Two (indenyl) oxyethyl group zirconium chlorides of ethene,
Two (4,5,6,7-tetrahydrochysene-1-indenyl) the oxyethyl group zirconium chlorides of ethene,
Two (indenyl) zirconium dimethyls of ethene,
Two (indenyl) diethyl zirconiums of ethene,
Two (indenyl) diphenyl-methyl zirconiums of ethene,
Two (indenyl) methyl monobromination zirconiums of ethene,
Two (indenyl) ethyl monochlor(in)ate zirconiums of ethene,
Two (indenyl) phenmethyl monochlor(in)ate zirconiums of ethene,
Two (indenyl) methyl monochlor(in)ate zirconiums of ethene,
Two (indenyl) zirconium dichlorides of ethene,
Two (indenyl) dibrominated zirconiums of ethene,
Two (4,5,6, the 7-tetrahydrochysene-1-indenyl) zirconium dimethyls of ethene,
Two (4,5,6,7-tetrahydrochysene-1-indenyl) the monochlor(in)ate zirconiums of ethene,
Two (4,5,6, the 7-tetrahydrochysene-1-indenyl) zirconium dichlorides of ethene,
Two (4,5,6,7-tetrahydrochysene-1-indenyl) the dibrominated zirconiums of ethene,
Two (4-methyl isophthalic acid-indenyl) zirconium dichlorides of ethene,
Two (5-methyl isophthalic acid-indenyl) zirconium dichlorides of ethene,
Two (6-methyl isophthalic acid-indenyl) zirconium dichlorides of ethene,
Two (7-methyl isophthalic acid-indenyl) zirconium dichlorides of ethene,
Two (5-methoxyl group-1-indenyl) zirconium dichlorides of ethene,
Two (2, the 3-dimethyl-1-indenyl) zirconium dichlorides of ethene,
Two (4, the 7-dimethyl-1-indenyl) zirconium dichlorides of ethene,
Two (4, the 7-dimethoxy-1-indenyl) zirconium dichlorides of ethene,
Two (indenyl) dimethoxy zirconiums of ethene,
Two (indenyl) diethoxy zirconiums of ethene,
Two (indenyl) methoxyl group chlorination zirconiums of ethene,
Two (indenyl) oxyethyl group zirconium chlorides of ethene,
Two (indenyl) methyl ethoxy zirconiums of ethene,
Two (4,5,6,7-tetrahydrochysene-1-indenyl) the dimethoxy zirconiums of ethene,
Two (4,5,6,7-tetrahydrochysene-1-indenyl) the diethoxy zirconiums of ethene,
Two (4,5,6,7-tetrahydrochysene-1-indenyl) the methoxyl group chlorination zirconiums of ethene,
Two (4,5,6,7-tetrahydrochysene-1-indenyl) the oxyethyl group zirconium chlorides of ethene,
Two (4,5,6,7-tetrahydrochysene-1-indenyl) the methyl ethoxy zirconiums of ethene,
Can enumerate following compound as this titanium compound:
Two (cyclopentadienyl) monochlor(in)ate one titanium hydride,
Two (cyclopentadienyl) hydrogenated methyl titanium,
Two (cyclopentadienyl) phenyl titanium chloride,
Two (cyclopentadienyl) phenmethyl titanium chloride,
Two (cyclopentadienyl) titanium dichloride,
Two (cyclopentadienyl) diphenyl-methyl titanium,
Two (cyclopentadienyl) oxyethyl group titanium chloride,
Two (cyclopentadienyl) butoxy titanium chloride,
Two (cyclopentadienyl) methyl ethoxy titanium,
Two (cyclopentadienyl) phenoxy group titanium chloride,
Two (cyclopentadienyl) trimethylsiloxy group titanium chloride,
Two (cyclopentadienyl) thio-phenyl titanium chloride,
Two (cyclopentadienyls) two (diformamide) titanium,
Two (cyclopentadienyl) diethoxy titanium,
Two (indenyl) titanium dichloride of ethene,
Two (4,5,6, the 7-tetrahydrochysene-1-indenyl) titanium dichloride of ethene,
Can enumerate following compound as hafnium compound:
Two (cyclopentadienyl) monochlor(in)ate one hydrogenation hafnium,
Two (cyclopentadienyl) ethyl hydrogenation hafnium,
Two (cyclopentadienyl) phenyl hafnium chloride,
Two (cyclopentadienyl) hafnium dichloride,
Two (cyclopentadienyl) diphenyl-methyl hafnium,
Two (cyclopentadienyl) oxyethyl group hafnium chloride,
Two (cyclopentadienyl) butoxy hafnium chloride,
Two (cyclopentadienyl) methyl ethoxy hafnium,
Two (cyclopentadienyl) phenoxy group hafnium chloride,
Two (cyclopentadienyl) thio-phenyl hafnium chloride,
Two (cyclopentadienyls) two (diethylamide) hafnium,
Two (indenyl) hafnium dichloride of ethene,
Two (4,5,6, the 7-tetrahydrochysene-1-indenyl) hafnium dichloride of ethene.
Catalyst component (B) is an aikyiaiurnirsoxan beta.
As the aikyiaiurnirsoxan beta that catalyst component (B) uses, can enumerate the organo-aluminium compound that for example general expression (VII) and general expression (VIII) are represented:
Figure 88103215_IMG6
Figure 88103215_IMG7
In this aikyiaiurnirsoxan beta, R be methyl, ethyl, just-alkyl of propyl group, sec.-propyl, just-butyl, different-butyl etc., for well, be best with methyl, ethyl, sec.-propyl with methyl, m is more than 2, preferably the integer more than 5.
In addition, aikyiaiurnirsoxan beta of the present invention, in above-mentioned general expression (VII) or (VIII), the part of R is the halogen atom of chlorine, bromine etc., and can be that content of halogen is the following halogenation aikyiaiurnirsoxan beta of 40 weight %.In addition, the part of R can be that hydroxyl, alkoxyl group are or/and aryloxy.
As the manufacture method of this aikyiaiurnirsoxan beta, can enumerate following example:
(1) at the salt that contains the compound of planar water, contains crystal water for example in the hydrocarbon dielectric suspensions of magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, cerous chlorate hydrate etc., add trialkylaluminium after, make the method for its reaction.
(2) in the medium of benzene, toluene, ether, tetrahydrofuran (THF) etc., make trialkylaluminium directly act on the method for water.
In these methods, relatively good with employing method (1).Have again, in this aikyiaiurnirsoxan beta, also can contain a spot of organo-metallic composition.For example except that above-mentioned trialkylaluminium, also can there be the organometallic compound composition of halogenous organo-aluminium compound and organo-magnesium compound etc.
In the method for the invention, as the employed organo-aluminium compound of the constituent of catalyzer (C), can enumerate the organo-aluminium compound of general expression (I) and general expression (II) expression
R 1mAl（OR 2） 3-m〔Ⅰ〕
R 3nAl〔OSiR 4 3〕 3-n〔Ⅱ〕
(in the formula, R 1, R 2And R 3The expression alkyl, R 4Expression alkyl, alkoxyl group or aryloxy, m and n are 0＜m＜3 and 0＜n＜3).In the organo-aluminium compound of this general expression (I) and general expression (II) expression, as R 1, R 2And R 3Specifically, can enumerate the following example: the carbonatoms of methyl, ethyl, just-propyl group, sec.-propyl, just-butyl, tert-butyl, the second month in a season-butyl, isobutyl-, n-hexyl, just-octyl group, 2-ethylhexyl etc. is at the saturated or unsaturated aliphatic hydrocarbon of the straight or branched of 1-10, or the carbonatoms of cyclohexyl, methylcyclopentyl, methylcyclohexyl etc. is the aliphatic hydrocarbon of 4-10, and the carbonatoms of phenyl, tolyl, xylyl, naphthyl etc. is at aryl radical of 6 to 16 etc.In addition, at the organo-aluminium compound of general expression (I) or general expression (II) expression, as R 1And R 3, serve as better with a chain alkyl, and good especially be branched-chain alkyl.In addition, in organo-aluminium compound, as R with general expression (II) expression 1Specifically, can enumerate methyl, ethyl, propyl group, sec.-propyl, just-carbonatoms of butyl, different-butyl etc. is 1 to 10 aliphatic group, the carbonatoms of cyclohexyl, methylcyclopentyl, ethyl cyclohexyl etc. is 4 to 10 aliphatic group, the carbonatoms of phenyl, tolyl, xylyl, naphthyl etc. is the aromatic hydrocarbon of 6-16, and the carbonatoms of methoxyl group, oxyethyl group, propoxy-, butoxy, isobutoxy, cyclohexyl, methyl cyclopentyloxy, methyl cyclohexane oxygen base etc. is 4 to 10 alkoxyl group, phenoxy group, tolyloxy, naphthyloxy etc.Also have, in general expression (I), m is 0＜m＜3, is preferably the positive number of 1≤m≤2.5, and that good especially is m=2.In addition, in general expression (II), n is 0＜n＜3, is preferably the positive number of 1≤n≤2.5, and that good especially is n=2.
As organo-aluminium compound (C) with general expression (I) expression, specifically, can enumerate the following example: the diethyl aluminum methoxide, the di-isopropyl aluminum methoxide, the diisobutyl aluminum methoxide, the diisobutyl aluminum ethoxide, two-2-methyl-butyl-aluminum methoxide, two-3-methyl butyl aluminum methoxide, two 2-methyl amyl aluminum methoxides, two 3-methyl amyl aluminum ethoxides, two 4-methyl amyl propoxy-aluminium, two 2-methyl hexyl butoxy aluminium, the dialkyl group aluminum alkoxide of two 3-methyl hexyl cyclohexyloxy aluminium etc., two 2-ethylhexyl phenoxy group aluminium, the bicyclic alkyl aluminum alkoxide of dicyclohexyl aluminum methoxide etc., phenylbenzene methoxy base aluminium, two alkoxy aryl aluminium of two tolyl aluminum methoxides etc., ethyl dimethoxy aluminium, the sec.-propyl aluminum methoxide, the isobutyl-aluminum methoxide, 2-methyl butyl dimethoxy aluminium, 3-methyl butyl dimethoxy aluminium, 2-methyl amyl dimethoxy aluminium, 3-methyl amyl dimethoxy aluminium, 4-methyl amyl dimethoxy aluminium, 2-methyl hexyl dipropoxy aluminium, 3-methyl hexyl two cyclohexyloxy aluminium, the alkyl dialkoxy aluminium of 2-ethylhexyl two phenoxy group aluminium etc., cyclohexyl dimethoxy aluminium, the cycloalkyl alkoxy aluminium of ring octyl group diethoxy aluminium etc., the phenyl aluminum methoxide, the alkoxy aryl aluminium of tolyl aluminum ethoxide etc. reaches alkyl alkoxy half aluminium of m=1.5 in these organo-aluminium compounds etc.In these organo-aluminium compounds, serve as better with the dialkyl group aluminum alkoxide, and two iso-alkyl aluminum alkoxides are good especially.
In addition, as organo-aluminium compound (C), specifically, can enumerate in general expression (II) expression:
Et 2AlO-Si
Figure 88103215_IMG8
OMe
Figure 88103215_IMG9
、
iso Pr 2Al-O-Si OEt
Figure 88103215_IMG11
、
iso Bu 2Al-O-Si
Figure 88103215_IMG12
OMe
Figure 88103215_IMG13
、
iso Bu 2Al-O-Si OEt
Figure 88103215_IMG15
、
iso Bu 2Al-O-Si
Figure 88103215_IMG16
O n-Bu
Figure 88103215_IMG17
、
iso Bu 2Al-O-Si
Figure 88103215_IMG18
O n-HexyI 、
iso OctyI 2Al-O-Si
Figure 88103215_IMG20
OEt
Figure 88103215_IMG21
、
iso Bu 2Al-O-SiMe 3、
iso Bu 2Al-O-SiEt 3、
Iso Bu 2Al-O-SiPh 3Deng.
This organo-aluminium compound (C) also can add the compound that generates this organo-aluminium compound (C) in reaction system.
In the method for the invention, catalyzer is to be formed by above-mentioned transistion metal compound (A), above-mentioned aikyiaiurnirsoxan beta (B) and above-mentioned organo-aluminium compound (C).In addition, also can contain the conduct electron donor of composition arbitrarily.This electron donor composition also can with above-mentioned transistion metal compound (A), this aikyiaiurnirsoxan beta (B) and this organo-aluminium compound (C) together, supply with polymerization reaction system, as wherein the ligand or the resultant of reaction of arbitrary composition also can be supplied with polymerization reaction system.As electron donor, can enumerate following example: the oxygenatedchemicals of the compounds of the atoms metal combination-O-C key of carboxylic-acid, ester class, ethers, ketone, aldehydes, alcohols, phenol, amides, aluminium, silicon etc. etc.; Nitrile, amine, phosphine class etc.; For example, the ratio of electron donor is for this transition metal electronics (M), normally scope of 0-1 mole of 1 grammeatom.
In the method for the invention, also can be with catalyst component (A), (B), (C) difference supply response system.In addition, 2 catalyst components are contacted and remaining catalyst component difference supply response system in advance.In addition, also can make catalyst component all in advance the contact after, resupply reaction system.
When the contacting in advance of catalyst component (A) and (B), the concentration as this transition metal atoms is generally 2.5 * 10 -4-1.5 * 10 -1Grammeatom/liter, be 5.0 * 10 preferably -4-1.0 * 10 -1Grammeatom/liter scope, after the concentration conversion of aikyiaiurnirsoxan beta becomes the aluminium atom, be generally the 0.05-5 grammeatom/liter, with the 0.1-3 grammeatom/liter scope serve as better.Temperature in contact in advance is generally-50-100 ℃, and mixing time was generally 0.1 minute-50 hours.
Employed catalyzer in the 2nd scheme of the present invention, by solid catalyst component (A '), catalyst component (B), and (C) form.
In the method for the invention, employed solid catalyst component (A ') is the solid catalyst component that is loaded with the transistion metal compound of periodic table of elements IV B family on particulate carrier at least, or use and on particulate carrier, to be loaded with the transistion metal compound of periodic table of elements IV B family and the solids component of aikyiaiurnirsoxan beta composition (B), can obtain that packing ratio is great with good polymerization activity polymerization, powdery, fine olefin polymer.
The carrier that constitutes this solid catalyst component (A ') is a particulate carrier, can use any in inorganics particulate carrier or the organism particulate carrier.
As the inorganics particulate, specifically, can enumerate following material: SiO 2, Al 2O 3, MgO, ZrO 2, TiO 2, B 2O 3, CaO, ZnO, ThO 2Deng, or the mixture of these compounds, for example:
SiO 2-MgO、SiO 2-Al 2O 3、
SiO 2-TiO 2、SiO 2-V 2O 5、
SiO 2-Cr 2O 3SiO 2-TiO 2-MgO etc.
These inorganics particulate carriers normally 150-1000 ℃, preferably behind 200-800 ℃ roasting temperature, use.In the middle of these carriers, preferably from SiO 2And Al 2O 3In select a kind of carrier at least as main component.In addition, this inorganic particles carrier also can contain minor N a 2CO 3, K 2CO 3, CaCO 3, MgCO 3, Na 2CO 4, Al 2(SO 4) 3, BaSO 4, KNO 3, Mg(NO 3) 2, Al(NO 3) 3, Na 2O, K 2O, Li 2Compositions such as the carbonate of O etc., vitriol, nitrate, oxide compound.This carrier is because its kind and method for making difference, and its character is also different, and employed in the present invention carrier, particle diameter are 5-200 μ m for well, and 10-150 μ m is better, and that best is 20-100 μ m.
As this organism particulate carrier, specifically, can enumerate following material: the Polyolefin and of polyethylene, polypropylene, poly-1-butylene, poly(4-methyl-1-pentene) etc. carries out the polyolefine that obtains after the copolymerization or various polyester, polymeric amide, polyvinyl chloride, polymethylmethacrylate, polymethyl acrylate, polystyrene, other various natural polymers and various monomeric compound with the starting monomer of these polymkeric substance.This carrier is owing to its kind and method for making difference, and its character is also different.Employed in the present invention carrier, particle diameter be 5-200 μ m for well, be preferably 10-150 μ m, that best is 20-100 μ m.
The molecular weight of these carriers is that these compounds can be as any molecular weight of solid existence.For example: with the polyethylene is example, can use have about 1,000-10, the polyethylene of the weight-average molecular weight of 000,000 scope.
This particulate carrier also can contact processing in advance with compound, and these compounds are for being loaded in organo-aluminium compound, the aluminium alkoxide compound on the periodic table of elements IV B group transition metal compound in advance or containing the compound etc. of halogen.
As this organo-aluminium compound, specifically, can enumerate the following material: trimethyl aluminium, triethyl aluminum, three just-trialkylaluminium of butyl aluminium, triisobutyl aluminium etc.; Alkenyl aluminium as the aluminium of prenyl; The alkyl alkoxy aluminium of dimethyl methoxy base aluminium, diethyl aluminum methoxide, dibutyl butoxy aluminium, diisobutyl aluminum methoxide etc.; Except that the alkyl sesquialter aluminum alkoxide of methyl sesquialter aluminum methoxide, ethyl sesquialter aluminum methoxide etc., also have with R ' 2.5Al(OR ") 0.5Aluminum alkyls Deng alkoxyization in the average integral part of expression; Part is by halogenated aluminum alkyls etc. in the alkyl al dichlorides that dimethylaluminum chloride, diethyl aluminum chloride, dimethyl aluminum bromide, alkyl-al hydride, alkyl sesquialter aluminum chloride, methylaluminum dichloride, ethylaluminum dichloride as methylaluminum sesquichloride, ethyl sesquialter aluminum chloride are such etc.As these organo-aluminium compounds, be preferably trialkylaluminium, dialkylaluminum chloride, dialkyl group aluminum alkoxide, good especially is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, dimethylaluminum chloride, diethyl aluminum chloride, diisobutyl aluminum methoxide.In addition, contact the employed aikyiaiurnirsoxan beta of processing in advance, can enumerate the compound of the organoaluminum of general expression (IV) and general expression (V) expression as particulate carrier:
Figure 88103215_IMG22
In the formula, R 5Be the alkyl of methyl, ethyl, propyl group, butyl etc., methyl, ethyl are better, and best is methyl; In addition, X is the halogen atom of chlorine, bromine etc., R 6Be R 5The alkyl that is exemplified or for above-mentioned halogen, in addition, a is generally 1-80, is better with 1-30; B is generally 0-80, is that better a+b is generally 4-100, is better with 8-50 with 0-30.In addition, general expression (IV) and (V)
Figure 88103215_IMG24
The unit promptly can be the block combination, also can be the combination of systematicness or the random combination of irregularity.
In addition, the employed silane compound that contains halogen is with general expression (VI) when the processing of contact in advance of this particulate carrier
SiXcR 7doR 8 （4-c-d）〔Ⅵ〕
The silane compound that contains halogen of expression is for well.X is Cl or Br in the formula, R 7And R 8For hydrogen atom or carbonatoms are that alkyl, aryl or the carbonatoms of 1-12 is the cycloalkyl of 3-12, C is the number of 1-4, and d is the number of 0-4, and c+d is the number of 1-4.
Specifically, can enumerate following material: silicon tetrahydride, Silicon bromide, tri-chlorination silane, the tri-chlorination methyl-monosilane, the tri-chlorination ethylsilane, the tri-chlorination propyl silane, the tri-chlorination phenyl silane, tri-chlorination hexamethylene silane, tribromide silane, the tribromide ethylsilane, the dichloride dimethylsilane, the dichloride methyl-monosilane, the benzene dichloride base silane, the tri-chlorination methoxy silane, the tri-chlorination Ethoxysilane, tri-chlorination propoxy-silane, tri-chlorination phenoxy group silane, the tribromide Ethoxysilane, the dichloride methoxy silane, dichloride dimethoxy silane, trichlorosilicane alkanol etc., the silane compound of being made up of the mixture of these compounds and the compound that chooses from these compounds that contains halogen is wherein particularly with silicon tetrachloride, tri-chlorination silane, the tri-chlorination methyl-monosilane is for well.
Employed other compound when the contact in advance of this particulate carrier is handled, adducible organic boron, organic-magnesium, organic zinc, organolithium etc.
Contact this organometallic compound when handling or the usage ratio of this silane compound in advance with the organometallic compound of this particulate carrier or silane compound, constituting the organometallic compound of per 1 gram particulate carrier or the atoms metal of silane compound is the 0.01-50 milligram-atom, be the 0.05-30 milligram-atom preferably, good especially is the scope of 0.1-20 milligram-atom.Add this particulate carrier be scattered in the inert media and at least a material in above-mentioned organic compound or the above-mentioned silane compound, can it be 0-120 ℃ in temperature, be preferably 10-100 ℃, good especially is under 20-90 ℃, time is 10 minutes 10-10 hour, be preferably 20 fens-5 hours, good especially is 30 minutes-3 hours, and pressure is normal pressure, reduces pressure or add to depress and handle.
The transition metal of the periodic table of elements IV B family in solid catalyst component (A ') is selected from titanium, zirconium and hafnium.As the transition metal in the solid catalyst component (A '), serve as better with titanium and zirconium, and best with zirconium.
Example as the transistion metal compound of the periodic table of elements IV B family in the solid catalyst component (A '), can enumerate with zirconium, titanium and the hafnium compound of conjugated pi electron base, with identical in the catalyzer of in the 2nd scheme of the present invention, having been narrated (A) as dentate.
About periodic table of elements IV B group transition metal compound being loaded in the method on this particulate carrier, can enumerate following several example: by the method for carrying is reacted by the functional group on transistion metal compound and particulate carrier surface; After maybe this particulate carrier being contacted processing in advance with above-mentioned organo-aluminium compound, aikyiaiurnirsoxan beta or the silane compound etc. that contains halogen, or do not contact processing in advance, just contact, and it is loaded in method on the particulate carrier with transistion metal compound; Or after in the unreactive hydrocarbons medium, contacting like this, make the evaporation of this hydrocarbon medium again and method on carrying; In the unreactive hydrocarbons medium with this particulate carrier with after aikyiaiurnirsoxan beta contacts, make the medium evaporation again, or add aikyiaiurnirsoxan beta and do not dissolve or difficult solvability solvent, and after preparation is loaded with the particulate carrier of aikyiaiurnirsoxan beta, transistion metal compound be in contact with it and make method on its year; Or after in the unreactive hydrocarbons medium, carrying out this contact, make the evaporation of this hydrocarbon medium and make method on its year; Or after this contact, add the insoluble or the difficult solvability solvent of this transition metal, this transistion metal compound is separated out and be loaded in method on this particulate carrier.
Catalyzer (B) is identical with the catalyst component of having narrated in the present invention's first scheme (B).
In the present invention, the mode to polymerization reaction system supply aikyiaiurnirsoxan beta (B), can adopt following method:
(1) use do not carry aikyiaiurnirsoxan beta solid catalyst component as solid catalyst component (A '), this solid catalyst component (A ') and aikyiaiurnirsoxan beta (B) are supplied with the method for polymerization system respectively.
(2) use the transistion metal compound of periodic table of elements IV B family and aikyiaiurnirsoxan beta (B) are loaded in solid catalyst component on the particulate carrier as solid catalyst component (A '), this solid catalyst component is supplied with the method for polymerization reaction system.
(3) solid catalyst component that uses above-mentioned (2) is as solid catalyst component (A '), with aikyiaiurnirsoxan beta (B) and this solid catalyst component (A ') together, and the method for supply polymerization reaction system.
This solid catalyst component (A ') its preparation method is that transistion metal compound and the aikyiaiurnirsoxan beta (B) with periodic table of elements IV B family is loaded on the particulate carrier.This method can adopt the method for following (a) to (d) that proposed in the clear 61-311287 of Japanese patent application number and clear 61-311286 number.(a) suspension that is scattered in the particulate carrier in the aluminoxanes solution and the insoluble or indissoluble solvent phase of aikyiaiurnirsoxan beta are contacted, after formation is loaded with the particulate carrier of aikyiaiurnirsoxan beta, the solution of this carrier and periodic table of elements IV B group transition metal compound is contacted and form solids component, prepare the method for solid catalyst for olefin polymerization as feature.
Again in detail, exactly the insoluble of aikyiaiurnirsoxan beta or indissoluble solvent are joined in the suspension of being made up of aluminoxanes solution and particulate carrier, or the suspension that the solution of aikyiaiurnirsoxan beta and this carrier are formed joined in this insoluble or indissoluble solvent, aikyiaiurnirsoxan beta is separated out, again according to circumstances, boil off the solvent of dissolving aikyiaiurnirsoxan beta from above-mentioned mixing suspension, promoting separating out of aikyiaiurnirsoxan beta, thereby obtain being loaded with the particulate carrier of aikyiaiurnirsoxan beta.Then, will by this year aikyiaiurnirsoxan beta carrier and the suspension of the insoluble or indissoluble solvent composition of aikyiaiurnirsoxan beta and the solution of the transistion metal compound of periodic table of elements IV B family contact, the transition metal compound catalyst composition is downloaded on this carrier that aikyiaiurnirsoxan beta is arranged, thereby makes solid catalyst for olefin polymerization.
The solvent of the insoluble or indissoluble of aikyiaiurnirsoxan beta is being contacted by in the solution of this aikyiaiurnirsoxan beta and the suspension that particulate carrier is formed, in this process, with respect to the ratio of the insoluble or indissoluble solvent of this aikyiaiurnirsoxan beta of these aluminoxanes solution 100 weight parts 10-10 normally, 000 weight part, be preferably the scope of 100-1000 weight part, the temperature during contact is generally-100-300 ℃, and good is-50-100 ℃, be preferably-scope of 30-50 ℃, contact is normally under agitation carried out.
Above-mentioned aluminoxanes solution is at least by aikyiaiurnirsoxan beta and be used to dissolve the solvent composition of aforesaid aikyiaiurnirsoxan beta.As the method that obtains aluminoxanes solution, can enumerate the method or the heating that mix two kinds of compounds simply and carry out later examples such as blended method.The amount of solvent is that solvent is the 0.1-50 liter when the aluminium in the aikyiaiurnirsoxan beta is 1 gram in this aluminoxanes solution, is preferably the 0.2-10 liter, is more preferably the scope that 0.3-2 rises.
In addition, being dispersed in this carrier amount in the particulate carrier suspension of above-mentioned aluminoxanes solution, concerning per 1 liter of aluminoxanes solution, is the 1-500 gram, for well, is preferably the scope that 20-100 restrains with the 10-200 gram.
In addition, in this contact, with respect to the aluminium of 1 grammeatom in the aikyiaiurnirsoxan beta suspension of this solid state, the amount of this used transistion metal compound is the 0.0005-1 grammeatom, and for well, reasonable is the scope of 0.002-0.04 grammeatom with the 0.001-0.1 grammeatom.
In addition, the temperature in this when contact is-50-200 ℃, with-20-100 ℃ for well, reasonablely be-scope of 10-50 ℃.This contact can under agitation be carried out usually.
The solution of above-mentioned transistion metal compound dissolves the solvent of transistion metal compound by this transistion metal compound and above-mentioned being used at least and forms.As the method that obtains transistion metal compound solution, can enumerate simply method with two kinds of compound; Or carry out example such as blended method after the heating, the quantity of solvent in this transistion metal compound solution concerning per 1 grammeatom transistion metal compound, is the 1-500 liter, is upgraded to 2-200, is the scope of 3-100 liter preferably.
The solid catalyst for olefin polymerization of the invention described above the 2nd scheme can also prepare by (b) method, this method is that the suspension of the particulate carrier in the transistion metal compound solution that is scattered in aikyiaiurnirsoxan beta and periodic table of elements IV B family and the insoluble or indissoluble solvent of aikyiaiurnirsoxan beta are contacted, make it form solids component, prepare the method for catalyst for olefines polymerizing as feature.
In more detail, can descend method is example: the insoluble of aikyiaiurnirsoxan beta or indissoluble solvent are joined in the suspension of being made up of aikyiaiurnirsoxan beta and periodic table of elements IV B group transition metal compound and particulate carrier, or will join in this insoluble or indissoluble solvent by the transistion metal compound of aikyiaiurnirsoxan beta and periodic table of elements IV B family and suspension that particulate carrier is formed, aikyiaiurnirsoxan beta and transistion metal compound are separated out, again according to circumstances, the solvent of dissolving aikyiaiurnirsoxan beta is evaporated from above-mentioned mixing solutions and removes, to promote separating out of aikyiaiurnirsoxan beta and/or transistion metal compound, method makes the solid catalyst for olefin polymerization that is loaded with transistion metal compound and aikyiaiurnirsoxan beta on particulate carrier thus.
In the suspension that will form by the transistion metal compound solution of this aikyiaiurnirsoxan beta and periodic table of elements IV B family and particulate carrier and technological process that the insoluble of this aikyiaiurnirsoxan beta or indissoluble solvent contact, for the solution of the transistion metal compound of this aikyiaiurnirsoxan beta of 100 weight parts and periodic table of elements IV B family, the ratio insoluble or the indissoluble solvent of this aikyiaiurnirsoxan beta is generally 10-10,000 weight part, good is the scope of 100-1000 weight part, the temperature of contact is 100-300 ℃, good is-50-100 ℃, reasonablely be-scope of 30-50 ℃, contact can be carried out under agitation condition usually.
The solution of above-mentioned aikyiaiurnirsoxan beta and transistion metal compound is formed by aikyiaiurnirsoxan beta and transistion metal compound and the aforesaid solvent that is used for dissolving aikyiaiurnirsoxan beta at least.As the method that obtains this solution, can enumerate simply method, or carry out the blended method after the heating two kinds of compound.Quantity of solvent in this solution for per 1 grammeatom aluminium in the aikyiaiurnirsoxan beta, for the 0.1-50 liter, is upgraded to 0.2-10, preferably the scope that rises for 0.3-2.
The aikyiaiurnirsoxan beta in this solution and the amount ratio of transistion metal compound, for the per 1 grammeatom aluminium in the aikyiaiurnirsoxan beta, can enumerate this transistion metal compound is 0.0005-1, and for well, reasonable is the example of the scope of 0.002-0.04 with 0.001-0.1.
In addition, the amount of this carrier in the above-mentioned particulate carrier suspension that is scattered in aikyiaiurnirsoxan beta and the transistion metal compound solution for per 1 liter of this solution, is the 1-500 gram, and good is 10-200 gram, the scope that restrains for 20-100 preferably.
In addition, the temperature during contact is generally-100-300 ℃, and good is-50-100 ℃, reasonablely is-scope of 30-50 ℃, and contact can be carried out under agitation condition usually.
The solid catalyst for olefin polymerization of the invention described above can also prepare with (C) method, this method is that the suspension that is scattered in the particulate carrier in the insoluble of aikyiaiurnirsoxan beta or the indissoluble solvent is contacted with aluminoxanes solution, after formation is loaded with the particulate carrier suspension of aikyiaiurnirsoxan beta thus, this carrier that has carried is contacted with the solution of the transistion metal compound of periodic table of elements IV B family, and form solids component.With this method is the solid catalyst that feature prepares for olefines polymerization.
In detail, this method is that aluminoxanes solution is joined in the suspension that is scattered in the particulate carrier in the insoluble or indissoluble solvent of aikyiaiurnirsoxan beta, or will join in the solution of aikyiaiurnirsoxan beta by the suspension that the insoluble of aikyiaiurnirsoxan beta or indissoluble solvent and particulate carrier are formed, aikyiaiurnirsoxan beta is separated out, again according to circumstances, the solvent of dissolving aikyiaiurnirsoxan beta evaporate from above-mentioned mixing suspension and removes, promoting separating out of aikyiaiurnirsoxan beta and/or transistion metal compound, thereby obtain the particulate carrier of year aikyiaiurnirsoxan beta.Then, the carrier of this year of aikyiaiurnirsoxan beta is contacted with the solution of the transistion metal compound of periodic table of elements IV B family with the suspension that the insoluble of aikyiaiurnirsoxan beta or indissoluble solvent are formed, the transition metal compound catalyst composition is loaded with on this carrier that has been loaded with aikyiaiurnirsoxan beta, thereby makes the solid catalyst of for olefines polymerization.
In the suspension that is formed by the inertia of this aikyiaiurnirsoxan beta or insoluble solvent and particulate carrier, for per 1 liter of this solvent, the amount of this carrier is generally the 1-500 gram, good is the 10-200 gram, the reasonable scope that restrains for 20-100.In addition, the temperature when the solution of this suspension and aikyiaiurnirsoxan beta contacts is generally-100-300 ℃, and good is-50-100 ℃, reasonablely is-scope of 30-50 ℃.In addition, this contact can under agitation be carried out usually.In addition, the amount of the aluminoxanes solution during this contact for this suspension of 100 weight parts, is generally the 1-1000 weight part, and good is the scope of 10-100 weight part.
The aluminoxanes solution that is used for this contact is formed by the solvent of aikyiaiurnirsoxan beta and aforementioned dissolving aikyiaiurnirsoxan beta at least.As the method that obtains this solution, can enumerate simply two kinds of compounds are carried out the blended method, or carry out blended method etc. after the heating, quantity of solvent in this solution, when the aluminium in the aikyiaiurnirsoxan beta is 1 grammeatom, be the 0.1-50 liter, good is the 0.2-10 liter, reasonable scope for the 0.3-2 liter.
In addition, when the solution of the transistion metal compound of particulate carrier that carries aikyiaiurnirsoxan beta and periodic table of elements IV B family contacts, be loaded in per 1 in the carrier with respect to this and restrain the aluminium atom, this transistion metal compound is the 0.0005-1 grammeatom, good is the 0.001-0.1 grammeatom, and reasonable is the scope of 0.002-0.04 grammeatom.
In addition, the temperature in this when contact is generally-50-200 ℃, and good is-20-100 ℃, reasonablely is-scope of 10-50 ℃, and this contact can be carried out under agitation condition usually.
The solution of above-mentioned transistion metal compound is formed by the solvent of this transistion metal compound and aforesaid dissolving transistion metal compound at least.As the method that obtains transistion metal compound solution, can enumerate and two kinds of compounds be carried out carrying out blended method etc. after blended method or the heating simply.Quantity of solvent in the solution of this transistion metal compound for the transistion metal compound of 1 grammeatom, for the 1-500 liter, is upgraded to 2-200, reasonable scope for the 3-100 liter.
(d) suspension that is scattered in the particulate carrier in the insoluble or indissoluble solvent of aikyiaiurnirsoxan beta is contacted with the solution of the transistion metal compound of aikyiaiurnirsoxan beta and periodic table of elements IV B family, thereby form the solids component of the particulate carrier of the transistion metal compound that is loaded with aikyiaiurnirsoxan beta and periodic table of elements IV B family, make the method for solid catalyst for olefin polymerization as feature.
In detail, adducible example is that the solution with the transistion metal compound of aikyiaiurnirsoxan beta and periodic table of elements IV B family joins in the suspension that is dispersed in particulate carrier in the insoluble or indissoluble solvent of aikyiaiurnirsoxan beta, or will add by the suspension that the insoluble of aikyiaiurnirsoxan beta or indissoluble solvent and particulate carrier are formed in the solution of aikyiaiurnirsoxan beta, aikyiaiurnirsoxan beta and transistion metal compound are separated out, again according to circumstances, the solvent of dissolving aikyiaiurnirsoxan beta and transistion metal compound evaporated from above-mentioned mixing suspension remove, to promote separating out of aikyiaiurnirsoxan beta and/or transistion metal compound, prepare transition metal and aikyiaiurnirsoxan beta therefrom and be loaded in solid catalyst for olefin polymerization on the particulate carrier.
In the suspension that is formed by the insoluble of this aikyiaiurnirsoxan beta or indissoluble solvent and particulate carrier, the amount of this carrier is generally the 1-500 gram for 1 liter of this solvent, and for well, reasonable is the scope that 20-100 restrains with the 10-200 gram.In addition, the temperature when the solution of the transistion metal compound of this suspension and aikyiaiurnirsoxan beta and periodic table of elements IV B family contacts, usually at-100-300 ℃, with-50-100 ℃ for well, reasonablely be-scope of 30-50 ℃.In addition, this contact can under agitation be carried out usually.Aikyiaiurnirsoxan beta during this contact and the amount of this transistion metal compound solution for this suspension of 100 weight parts, are generally the 1-1000 weight part, and good is the scope of 10-100 weight part.
The used aikyiaiurnirsoxan beta and the solution of transistion metal compound in this contact, at least the solvent by aikyiaiurnirsoxan beta, transistion metal compound and aforesaid dissolving aikyiaiurnirsoxan beta is formed, and the method that obtains this solution can be enumerated simply and will carry out blended method etc. after two kinds of compound or the heating.The amount of solvent in this solution for 1 grammeatom aluminium in the aikyiaiurnirsoxan beta, for the 0.1-50 liter, is upgraded to 0.2-10, reasonable scope for the 0.3-2 liter.
In addition, the amount of transistion metal compound in this solution, for 1 grammeatom aluminium, this transistion metal compound is the 0.0005-1 grammeatom, for well, reasonable is the scope of 0.002-0.04 grammeatom with the 0.001-0.1 grammeatom.
In addition, this contact temperature is generally-50-200 ℃, and good is-20-100 ℃, reasonablely is-scope of 10-50 ℃, and this contact can under agitation be carried out usually.
Suitable solvents as periodic table of elements IV B group transition metal compound for example can be enumerated: the hydrocarbon that contains halogen of the aromatic hydrocarbon of benzene, toluene, ethylbenzene, propyl benzene, butylbenzene, dimethylbenzene etc. and chlorobenzene, ethylene dichloride etc.
Insoluble or indissoluble solvent as periodic table of elements IV B group transition metal compound for example can be enumerated: the aliphatics of pentane, hexane, decane, dodecane, lam-oil, hexanaphthene or alicyclic hydrocarbon.
Solvent as aikyiaiurnirsoxan beta for example can be enumerated: the aromatic hydrocarbon of benzene, toluene, ethylbenzene, propyl benzene, butylbenzene, dimethylbenzene etc.
Solvent as the insoluble or indissoluble of aikyiaiurnirsoxan beta for example can be enumerated: the alicyclic hydrocarbon of the aliphatic hydrocarbon of the straight or branched of pentane, hexane, decane, dodecane, lam-oil, hexanaphthene etc. and hexanaphthene, two ring (2,2,1) heptane, ethylcyclohexane etc.
As the insoluble of aikyiaiurnirsoxan beta or indissoluble solvent, preferably use to have than the also high solvent of employed solvent boiling point when obtaining aluminoxanes solution.
In aforesaid method, prepared solid catalyst component (A '), for per 100 gram particulate carriers, the content of transition metal atoms is the 0.5-500 milligram-atom, and good is the 1-200 milligram-atom, and reasonable is the 3-50 milligram-atom.Catalyzer (B) is for per 100 gram particulate organic compound carriers, and the aluminium atom content of aikyiaiurnirsoxan beta is 5-50,000 milligram-atom, and good is the 50-10.000 milligram-atom, reasonable is 100-4,000 milligram-atom.In this solid catalyst component (A '), the ratio (Al/M) of aluminium atom and transition metal atoms is at 1-1000, and that good is 6-600, preferably in the scope of 15-300.In this solid catalyst component (A), the median size of solid catalyst be 5-200 μ m good for 10-150 μ m, reasonable is 20-100 μ m.
With respect to atom, be generally the 0-1 mole, good is the scope of 0.1-0.6 mole.
Method of the present invention, to making olefin polymer, the multipolymer of particularly making ethene and ethene and alpha-olefin is effective.Can carry out the example of polymeric alkene with catalyzer of the present invention, can enumerate as carbonatoms is the alpha-olefin of 2-20, for example ethene, propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-12 (carbon) alkene, 1-14 (carbon) alkene, 1-16 (carbon) alkene, 1-18 (carbon) alkene, 1-20 (carbon) alkene etc.In these alkene, the polymerization of ethene or ethene and carbonatoms are that the copolymerization of alpha-olefin of 3-10 is comparatively suitable.
In the method for the invention, the polymerization of alkene normally adopts the liquid polymerization method of gas phase polymerization process or slurry polymerization process etc. to carry out.In slurry polymerization, can use unreactive hydrocarbons as solvent, also can be with alkene self as solvent.
About hydrocarbon solvent, specifically can enumerate as the aliphatic hydrocarbon of butane, Trimethylmethane, pentane, hexane, octane, decane, dodecane, n-Hexadecane, octadecane etc., the clicyclic hydrocarbon of pentamethylene, methylcyclopentane, hexanaphthene, cyclooctane etc., the petroleum fractions of lam-oil, light oil etc. etc.
When implementing method of the present invention with the liquid polymerization of slurry polymerization process etc. or gaseous polymerization, the usage ratio of this transistion metal compound is the concentration of this transition metal atoms in the polymerization reaction system, is generally 10 -8-10 -2Grammeatom/liter, good is 10 -7-10 -3Grammeatom/liter.
In addition, implementing occasion of the present invention with liquid polymerization or gaseous polymerization, the usage quantity of aikyiaiurnirsoxan beta be converted into aluminium atom in the reaction system be 6 milligram-atoms/liter below, 3 milligram-atoms that good is/liter below, be preferably the 0.01-2 milligram-atom/liter, 0.02-1 milligram-atom that good especially is/liter scope.In addition, the ratio of the aluminium atom total amount that the aluminium atom consumption of aikyiaiurnirsoxan beta composition (B) and this aikyiaiurnirsoxan beta composition (B) and organo-aluminium compound composition (C) add up to is generally 20-95%, and good is the scope of 40-92%; Equally, the ratio of the aluminium atom total amount of the consumption of the aluminium atom of organo-aluminium compound composition (C) and above-mentioned (B) and (C) is generally 5-80%, and is good in the scope of 8-60%.In the method for the invention, the ratio of the transition metal atoms in the aluminium atom of the total amount of aikyiaiurnirsoxan beta composition (B) and organo-aluminium compound composition (C) and the reaction system is generally 20-10, and 000, that good is 40-5,000, that good especially is 60-2,000 scope.
When implementing method of the present invention with the liquid polymerization of slurry polymerization process etc., polymerization temperature is-50-120 ℃ usually, 0-100 ℃ scope that good is.
When implementing method of the present invention with gaseous polymerization, usually polymerization temperature is a 0-120 ℃ of good scope for 20-100 ℃.
Polymerization pressure is generally normal pressure-100 kilograms per centimeter 2, good is the 2-50 kilograms per centimeter 2, polymerization can intermittent type, semi continuous, and any mode in the continous way is carried out.
And also can be divided into two different stages of reaction conditions carries out polymerization.
In the method for the invention, when adopting slurry polymerization process or gaseous polymerization, be preferably in the preceding elder generation of olefinic polymerization and in the presence of aforementioned catalyzer, carry out the polymerization of giving of alkene.Give in the polymerization, the transition metal compound catalyst composition (A) to the periodic table of elements IV B family of per 1 grammeatom can restrain with 1-1000, and good with the 5-500 gram, reasonable alkene with the 10-200 gram carries out polymerization.As being used to give polymeric alkene, for example can enumerating, ethene and carbonatoms are the alpha-olefin of 3-20, for example propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-12 (carbon) alkene, 1-14 (carbon) alkene etc., but be best with ethene.
Give the polymeric temperature and be-20-70 ℃, good is-10-60 ℃, and reasonable is 0-50 ℃ scope.
This treatment process can adopt any method of intermittent type or continous way, and can or add with normal pressure to depress and carry out.In giving polymerization, the such molecular weight regulator of hydrogen is coexisted with it so that control prepared give the limiting viscosity (η) that aggressiveness measures in 135 ℃ of naphthalanes at least can be more than 0.2dl/g, that good is 0.5-20dl/g.
Giving polymerization can carry out down or in the unreactive hydrocarbons solvent solvent-free.On the operation viewpoint, think that to give polymerization in unreactive hydrocarbons solvent better.Give the polymeric unreactive hydrocarbons solvent as being used for this, the aforesaid solvent that can enumerate or indissoluble insoluble to aikyiaiurnirsoxan beta is an example.
In giving polymerization, give the concentration that catalyst concentration in the polymerization reaction system is generally the transition metal atoms in this catalyzer, this concentration is 10 -6-1 grammeatom/liter, good is 10 -4-10 -2Grammeatom/liter scope.
(embodiment)
Below, specifically describe the present invention with embodiment.
(preparation of methylaluminoxane)
Al 2(SO 4) 314H 2O37 gram and 125 milliliters of toluene join with 400 milliliters of the abundant metathetical of nitrogen and have in the glass flask of agitator, after 0 ℃ of cooling, the time of 125 milliliters of toluene solutions that contain 50 milliliters of trimethyl aluminiums with 1 hour are dripped off.Then, be warmed up to 40 ℃ with 2 hours times, under this temperature condition, continue reaction 40 hours.After the reaction, carry out solid-liquid separation, from parting liquid, remove low boilers, again toluene is joined in the residual heavy-gravity liquid, take as toluene solution fully with vaporizer by filtration.
In addition, the molecular weight of being tried to achieve by the decline of the zero pour in the benzene is 888, thereby the polymerization degree of this aikyiaiurnirsoxan beta is 15.
Embodiment 1
With 350 milliliters of toluene and 150 milliliters of 4-methyl-1-pentenes join fully carry out in 1 liter of glass reactor of metathetical with nitrogen after, supply with ethene with the speed of 155Nl/hr on one side, add on one side the toluene solution that is scaled the methylaluminoxane of the diisobutyl aluminum methoxide of 0.38 mmole and 0.75 mmole by the aluminium atom respectively, be scaled the toluene solution of dicyclopentadiene zirconium dichloride of 0.0025 mmole by zirconium atom after, the temperature of reaction solution is adjusted to 20 ℃ with frozen water.Add the dicyclopentadiene zirconium dichloride, after 15 minutes, add about 5 ml methanol again and stop polymerization, carry out thorough drying after, measures polymers obtained must measuring and is 14.8 and restrain.
Embodiment 2-4
Except employed diisobutyl aluminum methoxide 0.38 mmole among the embodiment 1 is converted into the amount or compound of table 1, other all experimentizes with embodiment 1 identical method.The result is as shown in table 1.
Comparative example 1
The diisobutyl aluminum methoxide in not using embodiment 1, other all uses the method identical with embodiment 1 to experimentize, and the result is as shown in table 1.
Figure 88103215_IMG25
Embodiment 5
(preparation of solid catalyst)
After joining the toluene solution that contains 67 milliliters of aforementioned methylaluminoxane that are equivalent to 100 mmole Al atoms in 300 milliliters of reactors that can reduce pressure and have agitator, in room temperature and under stirring, in about 0.5 hour time, add 100 milliliters purified just-decane makes methylaluminoxane separate out thus.Then, on one side with vacuum pump with 4 torrs that reduce pressure of the pressure in the reactor, with about 3 hours time the temperature in the reactor is risen to 35 ℃ on one side, thereby removes the toluene in the reactor, methylaluminoxane is separated out.Filter this reaction solution with strainer, remove liquid phase part after, solid part just is being resuspended in-decane in, and add the toluene solution of 5 milliliters of dicyclopentadiene zirconium dichlorides containing 0.2 mmole.After at room temperature mixing 1 hour, remove liquid phase part, thereby make the solid catalyst of for olefines polymerization with strainer.
In this solid catalyst, zirconium content is 0.6 weight %, and aluminium content is 47 weight %, and by microscopic, the median size of trying to achieve catalyzer is approximately 30 μ m.
(giving polymerization)
In the reactor of 400 milliliters of belt stirrers, under nitrogen atmosphere 100 milliliters purified just-after decane and diisobutyl aluminum methoxide 50 mmoles, the above-mentioned solid catalyst that is equivalent to 0.1 mmole zirconium add, speed with 4Nl/hr is supplied with ethene 1 hour, the temperature of this moment remains on 20 ℃, ethene is used nitrogen replacement after supplying with and finishing in the system, clean once with the purified hexane, be resuspended in the hexane, be kept in the catalyst container.
(polymerization)
Joining with nitrogen abundant metathetical volume as dispersion agent sodium-chlor 250 gram is in 2 liters the autoclave, Yi Bian be heated to 90 ℃, Yi Bian carry out reduced pressure treatment with vacuum pump with 2 hours time, makes below internal drop to 50 mmhg in the autoclave.Then, temperature in the autoclave is dropped to 75 ℃, with in the autoclave with after the ethene displacement, add again aforementioned give that polymerization uses be scaled the solid catalyst component of 0.005 mmole by zirconium atom, add hydrogen 50N milliliter to the autoclave closed system, with the ethene pressurization make in the autoclave in press to 8 kilograms per centimeter 2Stirring velocity is brought up to per minute 300 changes, and carries out polymerization in 1 hour under 80 ℃.
After polymerization ends, polymkeric substance in the reactor and sodium-chlor are all taken out, join in about 1 liter water, by stirring in about 5 minutes, sodium-chlor almost all was dissolved in the water, and only has polymkeric substance to float on the surface, the polymkeric substance that recovery floats on the surface, after fully cleaning with methyl alcohol, at a dry night, the result is as shown in table 2 under 80 ℃ of decompressions.
Comparative example 2
The diisobutyl aluminum methoxide in not using embodiment 5, other all experimentizes with similarly to Example 5 operation, and the result is as shown in table 2.
Figure 88103215_IMG26
Embodiment 6
Except the diisobutyl aluminum methoxide among the embodiment 5 is changed into isoBu 2AlPOSiEt 2Outward, other all experimentizes with similarly to Example 5 operation, and the result is as shown in table 2.
Embodiment 7
(being loaded in the preparation of the solid catalyst on the carrier)
Is 67 milliliters of toluene solutions of the aforementioned methylaluminoxane that contains the Al atom that is equivalent to 100 mmoles and median size that (Mitsui Petrochemical Industries Ltd.'s system, commodity are called ミ ベ ロ ソ for the polyethylene powders of 35 μ m
Figure 88103215_IMG27
) 4 grams, join in 300 milliliters of reactors that have agitator that can reduce pressure, under stirring at room, big in 0.5 hour 100 milliliters of addings just-decane, methylaluminoxane is separated out.Then, by on one side with vacuum pump with 4 torrs that reduce pressure in the reactor, on one side in 3 hours, reactor temperature is brought up to 45 ℃, thereby remove the toluene in the reactor, methylaluminoxane is further separated out.After using strainer that reacting liquid filtering is removed liquid phase part, with solid part just-decane in resuspending, 5 milliliters of toluene solutions of the dicyclopentadiene zirconium dichloride that contains 0.24 mmole were joined in the suspension in 1 hour, after at room temperature mixing, again with 4 torrs that at room temperature in 30 minutes, reduce pressure in the reactor, after removing toluene, the diisobutyl aluminum methoxide of 10 mmoles is joined in this suspension, after at room temperature mixing 60 minutes, be cooled to-20 ℃, filter this suspension, thereby make the solid catalyst of for olefines polymerization.
The content of zirconium in the resulting solid catalyst for the polyethylene that per 100 grams are used as carrier, is 10 mmoles.The content of Al for the polyethylene that per 100 grams are used as carrier, is 2.2 moles.Use microscopic, try to achieve the catalyzer median size and be approximately 40 μ m.
(giving polymerization)
In the reactor of 400 milliliters of belt stirrers, under nitrogen atmosphere, add 100 milliliters of purified just-decane and be equivalent to the above-mentioned solid catalyst of 0.1 mmole zirconium after, in 1 hour, supply with ethene with the speed of 4Nl/hr.Temperature during this period remains on 20 ℃, after ethene is supplied with and to be finished, after replacing with nitrogen in the system, cleans once with the purified hexane, and resuspending is kept in the catalyst container in hexane.
(polymerization)
250 gram sodium-chlor as dispersion agent are joined to carry out abundant metathetical volume with nitrogen be in 2 liters the autoclave, be heated to 90 ℃ on one side, in 2 hours, carry out reduced pressure treatment with vacuum pump on one side, make below internal drop to 50 mmhg in the autoclave.Then, temperature in the autoclave is reduced to 75 ℃, in autoclave with after the ethene displacement, carrying out giving after solid catalyst component that polymeric is scaled 0.005 mmole with zirconium atom adds, autoclave as closed system, add the hydrogen of 50Nml, pressurize with ethene, make in the autoclave in press to 8 kilograms per centimeter 2, stirring velocity is brought up to per minute 300 change, under 80 ℃, carry out polymerization in 1 hour.
After polymerization ends, polymkeric substance in the autoclave and sodium-chlor are all taken out, join in about 1 liter water, by about 5 minutes stirring, sodium-chlor almost all is dissolved in the water, only there is polymkeric substance to float on the surface, reclaims the polymkeric substance that this floats on the surface, after fully cleaning with methyl alcohol, a dry night under 80 ℃ of decompressions, the receipts amount of resulting polymkeric substance is 103 grams, the MFl(melt flow index) be 3.4dg/min, apparent bulk density is 0.45 grams per milliliter.
Comparative example 3
The diisobutyl aluminum methoxide in not using embodiment 7, other all experimentizes with similarly to Example 1 operation, and the result is as shown in table 3.
Embodiment 8
(being loaded in the preparation of the solid catalyst on the carrier)
Is 67 milliliters of toluene solutions that contain the aforementioned methylaluminoxane that is equivalent to 100 mmole Al atoms and median size that (Mitsui Petrochemical Industries, Ltd.'s system, trade name are ミ ベ ロ Application for the polyethylene powders of 35 μ m
Figure 88103215_IMG28
) 4 the gram, join in 300 milliliters of reactors that have agitator that can reduce pressure, under stirring at room in 0.5 hour the adding 100 milliliters just-decane, methylaluminoxane is separated out.Then, by on one side with vacuum pump with 4 torrs that reduce pressure in the reactor, on one side in 3 hours, the temperature in the reactor is brought up to 45 ℃, thereby remove the toluene in the reactor, methylaluminoxane is separated out again.With strainer with reacting liquid filtering, after removing liquid phase part, with solid part just-carry out resuspending in the decane, in 1 hour, join in this suspension 5 milliliters of toluene solutions of the dicyclopentadiene zirconium dichloride that contains 0.24 mmole, after at room temperature mixing, with at room temperature in 30 minutes, being decompressed to 4 torrs in the reactor, remove after the toluene again, this suspension is filtered, thereby make the solid catalyst of for olefines polymerization.
The zirconium content of resulting solid catalyst for the polyethylene that per 100 grams are used as carrier, is 10 mmoles; The content of Al for the polyethylene that per 100 grams are used as carrier, is 1.9 moles.Use microscopic, the catalyzer median size of trying to achieve is approximately 40 μ m.
(giving polymerization)
In the reactor of 400 milliliters of belt stirrers, under nitrogen atmosphere, add 100 milliliters of purified just-the diisobutyl aluminum methoxide of decane and 50 mmoles, be equivalent to the above-mentioned solid catalyst of 0.1 mmole zirconium after, speed with 4Nl/hr supplies ethene 1 hour, temperature during this period remains on 20 ℃, after ethene is supplied with and to be finished, after replacing with nitrogen in the system, clean once with the purified hexane again, resuspending is stored in the catalyst container in hexane.
(polymerization)
Carry out the polymerization of alkene with the method identical with embodiment 1.
Comparative example 4
The diisobutyl aluminum methoxide in not using embodiment 8, other all experimentizes with embodiment 1 identical operations, and the result is as shown in table 3.
Embodiment 9
(being loaded in the preparation of the solid catalyst on the carrier)
67 milliliters of toluene solutions of the aforementioned methylaluminoxane that contains the Al atom that is equivalent to 100 mmoles and in 500 ℃ of silicon that roasting forms in 12 hours (テ " t " ソ Application society system #952) 2 grams join in 300 milliliters of reactors that have agitator that can reduce pressure, under stirring at room in 0.5 hour 100 milliliters of purified of adding just-decane, methylaluminoxane is separated out.Then, Yi Bian will be decompressed to 4 torrs in the reactor with vacuum pump, Yi Bian in 3 hours, the temperature in the reactor is risen to 35 ℃, remove the toluene in the reactor, methylaluminoxane is separated out again.With strainer with reacting liquid filtering, after removing liquid phase part, with solid part just-carry out resuspending in the decane, 5 milliliters of toluene solutions that will contain the dicyclopentadiene zirconium dichloride of 0.2 mmole join in the suspension, in mixed at room temperature after 1 hour, remove liquid phase part with strainer, thereby make the solid catalyst of for olefines polymerization.
The silicon that the content of zirconium is used as carrier with respect to per 100 grams in the resulting solid catalyst is 7 mmoles, and the silicon that the content of Al is used as carrier with respect to per 100 grams is 2.4 moles, uses microscopic, and the median size of the catalyzer of trying to achieve is approximately 40 μ m.
The solvent-free polymeric that gives polymerization and ethene is used with embodiment 2 identical operations and is experimentized, and the result is as shown in table 3.
Comparative example 5
Except without the diisobutyl aluminum methoxide among the embodiment 9, other all identical with embodiment 9 method experimentizes, and the result is as shown in table 3.
(synthesizing of aikyiaiurnirsoxan beta)
37 gram Al 2(SO 4) 314H 2O and 125 milliliters of toluene join in the flask of fully replacing with nitrogen, be cooled to 0 ℃ after, will be with 125 milliliters of dilution with toluene the trimethyl aluminium of 500 mmoles splash in the reaction flask.Then, be warmed up to 40 ℃, under this temperature, continue reaction 10 hours.After the reaction, carry out solid-liquid separation, from filtrate, remove toluene again, obtain aikyiaiurnirsoxan beta 13 grams of white solid by filtration.Trying to achieve molecular weight by the decline of the zero pour in the benzene is 930, and represented m value is 14 in catalyst component (B).
Embodiment 10
(being loaded in the preparation of the solid catalyst on the carrier)
In abundant metathetical 200 ml flasks with nitrogen, (median size is 70 μ m, and specific surface area is 260m at 700 ℃ of silicon that form through roasting in 5 hours to add 52 grams 2/ g, pore volume is 1.65cm 2/ g), toluene solution (Al is 1 mol) and 50 milliliters of toluene of 26 milliliters of dimethyl monochlor(in)ate aluminium, 80 ℃ of heating 2 hours.Then, carry out solid-liquid separation, obtain catalyst component by filtration.This catalyst component is moved in 50 milliliters of toluene, in this catalyst component, add the toluene solution (Z of 43 milliliters dicyclopentadiene zirconium dichloride again rBe 0.04 mol), 80 ℃ of heating 1 hour, carry out solid-liquid separation by filtration then, in resulting solids component, under stirring at room, in 30 minutes, add toluene solution 19.6 milliliters (Al is 1.03 moles) and 80 milliliters of toluene of aikyiaiurnirsoxan beta.Then, after at room temperature stirring 30 minutes, at room temperature remove toluene with vaporizer, obtaining containing the zirconium amount is that 0.08 weight %, aluminum content are the solids component of 10 weight %.
Except giving the polymeric scale replaces with 1/2nd the scale of embodiment 8, this catalyst-free polymerization of giving polymerization and ethene all uses the method identical with embodiment 8 to carry out.
Comparative example 6
The diisobutyl aluminum methoxide in not being added in embodiment 10, all use the method identical with embodiment 4 to experimentize, the result is as shown in table 4.
Embodiment 11
(being loaded in the preparation of the solid catalyst on the carrier)
Being 400 milliliters at volume has agitator and in the abundant metathetical glass flask, at room temperature 50 milliliters of the toluene solutions of the aikyiaiurnirsoxan beta that contains 2 mmoles is added to 5 gram silicon (テ " t " the ソ Application society systems that form through roasting in 12 hours by at 800 ℃ with nitrogen #952) and in the suspension formed of 100 milliliters of toluene, the temperature of this mixed solution is brought up to 50 ℃, 50 ℃ of reactions 2 hours, liquid portion was removed with strainer in the reaction back of ending from reaction solution, and residual solid part is resuspended in 100 milliliters the toluene.Under 25 ℃, add to 9.4 milliliters of toluene solutions that contain the dicyclopentadiene zirconium dichloride of 0.38 mmole in this suspension, reaction is 2 hours under 25 ℃ of stirrings, reaction is removed liquid portion with strainer after ending from this suspension, remaining solid part is washed 2 times with toluene, and obtains solid catalyst component (A ').Year zirconium amount in this solid catalyst component (A ') is 0.6 weight %.The toluene solution of 47 milliliters of aikyiaiurnirsoxan beta (Al is 1.03 mol) and 50 milliliters of toluene are joined in the above-mentioned solid catalyst component (A ') of 2 grams, after at room temperature stirring 30 minutes, at room temperature remove toluene and obtain being loaded with the solids component of aikyiaiurnirsoxan beta with vaporizer.
Method according to embodiment 8 is implemented the following solvent-free polymeric that gives polymerization and ethene, the results are shown in table 4.
Comparative example 7
The diisobutyl aluminum methoxide in not using embodiment 5, all use the method identical to experimentize, the results are shown in table 2 with embodiment 4.
Embodiment 12
(preparation of solid catalyst component (A '))
Have in the vial of agitator 400 milliliters of the abundant metathetical of nitrogen, add by the silicon that forms through roasting in 12 hours at 800 ℃ (テ " t " ソ Application society system #952) mixing suspension of 3 grams and 50 milliliters of compositions of trichlorosilane stirred 2 hours under 50 ℃ of temperature, and reaction is removed liquid phase part with strainer after ending from this reaction solution, residual solid part is resuspended in 50 milliliters of toluene.300 milliliters of toluene solutions that will contain the dicyclopentadiene zirconium dichloride of 15 mmoles join in this suspension, stir 2 hours under 50 ℃ of temperature, and it is reacted.Reaction is removed liquid phase part with strainer after ending from this suspension, residual solid part is cleaned twice with toluene, thereby obtain solid catalyst component (A ').Year zirconium amount in this catalyst component (A ') is 1.2 weight %.47 milliliters of toluene solutions of aikyiaiurnirsoxan beta (Al is 1.03 mol) and toluene are joined in the 1 above-mentioned solid catalyst component of gram (A ') for 50 milliliters, after at room temperature stirring 30 minutes, at room temperature remove toluene again, obtained carrying the solids component of aikyiaiurnirsoxan beta with vaporizer.
Give the solvent-free polymeric of polymerization and ethene below the method enforcement according to embodiment 8.The result is as shown in table 4.
Comparative example 8
The diisobutyl aluminum methoxide in not using embodiment 12, all use the method identical with embodiment 10 to implement, the result is as shown in table 4.
Embodiment 13
The amount of used methylaluminoxane makes 30 mmoles into by 100 mmoles in the solid catalyst except embodiment 8 preparation is loaded on the carrier, the diisobutyl aluminum methoxide that adds giving in the polymerization is in addition made into beyond 15 mmoles by 50 mmoles, all use the method identical with embodiment 8 to give the solvent-free polymeric of polymerization and ethene, experimental result is as shown in table 5.
Comparative example 9
The diisobutyl aluminum methoxide in not using embodiment 13, all use with embodiment 13 identical operations to experimentize, the result is as shown in table 5.
Embodiment 14
Except with (iso Bu) 2Al-O-SiEt 3Replace outside the diisobutyl aluminum methoxide among the embodiment 13, all use the method identical to experimentize with embodiment 13.Experimental result is listed in table 5.
Comparative example 10
Except not using (the iso Bu) among the embodiment 14 2Al-O-SiEt 3All use the method identical to experimentize outward, with embodiment 14.The result is as shown in table 5.
Figure 88103215_IMG29
Figure 88103215_IMG30
The possibility of using on the industry
First scheme of the present invention be by aikyiaiurnirsoxan beta and Organoaluminoxy and with and new catalyst that the effect that multiplies each other of the excellence that has significantly reduces the aikyiaiurnirsoxan beta consumption, and with this catalyst to the olefine polymerizing process that equal polymerization and the combined polymerization of alkene brings very big polymerization activity, can obtain the narrow olefin polymer of molecular weight distribution with this polymerization. In the occasion of alpha-olefinic copolymerization, can make narrow polymer and the copolymer of composition distribution.
Utilize the catalyst of alternative plan of the present invention and with the olefine polymerizing process of this catalyst, add above-mentioned advantage, can make that packing ratio is great, epigranular, polymer and copolymer that fine powder is few.

Claims (10)

1, by the transistion metal compound of [A] periodic table of elements IV B family,
[B] aikyiaiurnirsoxan beta and
[C] is by general expression [I] or general expression [II]
R 1mAl(OR 2) 3-m[Ⅰ]
R 3nAl[OSiR 4 3] 3-n[Ⅱ]
The organo-aluminium compound of expression (in the formula, R 1, R 2And R 3The expression alkyl, R 4Expression alkyl, alkoxyl group or aryloxy, m and n are respectively the positive number of 0＜m＜3 and 0＜n＜3) catalyzer formed exists down, makes the olefine polymerizing process of olefinic polymerization or copolymerization.
2, according to the said olefine polymerizing process of claim 1, above-mentioned (A) periodic table of elements IV B group transition metal compound is at least a compound of selecting from zirconium compounds, titanium compound and the hafnium compound of base as dentate that conjugated pi electron is arranged.
3, by the transistion metal compound of (A) periodic table of elements IV B family,
(B) aikyiaiurnirsoxan beta and
(C) is with general expression (I) or (II)
R 1mAl（OR 2） 3-m〔Ⅰ〕
R 3nAl〔OSiR 4 3〕 3-n〔Ⅱ〕
The organo-aluminium compound of expression (in the formula, R 1, R 2And R 3The expression alkyl, R 4Expression alkyl, alkoxyl group or aryloxy, m and n are respectively the positive number of 0＜m＜3 and 0＜n＜3) formed olefin polymerization catalysis.
4, according to the said olefin polymerization catalysis of claim 3, the transistion metal compound of above-mentioned (A) periodic table of elements IV B family is a selected at least a compound from zirconium compounds, titanium compound and the hafnium compound of base as dentate that conjugated pi electron is arranged.
5, be loaded with on particulate carrier by (A ') transistion metal compound of periodic table of elements IV B family solid catalyst component,
(B) aikyiaiurnirsoxan beta and
(C) is with the organo-aluminium compound of general expression (I) or (II) expression
R 1mAl（OR 2） 3-m〔Ⅰ〕
R 3nAl〔OSiR 4 3〕 3-n〔Ⅱ〕
(in the formula, R 1, R 2And R 3The expression alkyl, R 4Expression alkyl, alkoxyl group or aryloxy, m and n are respectively the positive number of 0＜m＜3 and 0＜n＜3) formed catalyzer exists down, makes the olefine polymerizing process of olefinic polymerization or copolymerization.
6, according to the said olefine polymerizing process of claim 5, above-mentioned particulate carrier will contact processing earlier in advance before carrying above-mentioned periodic table of elements IV B group transition metal compound.
7, according to the said polymerization process of claim 5, above-mentioned (A ') periodic table of elements IV B group transition metal compound is a selected at least a compound from zirconium compounds, titanium compound and the hafnium compound of base as dentate that conjugated pi electron is arranged.
8, be loaded with on particulate carrier by (A ') transistion metal compound of periodic table of elements IV B family solid catalyst component,
(B) aikyiaiurnirsoxan beta and
(C) is with the organo-aluminium compound of general expression (I) or general expression (II) expression
R 1mAl（OR 2） 3-m〔Ⅰ〕
R 3nAl〔OSiR 4 3〕 3-n〔Ⅱ〕
(in the formula, R 1, R 2And R 3The expression alkyl, R 4Expression alkyl, alkoxyl group or aryloxy, m and n are respectively the positive number of 0＜m＜3 and 0＜m＜3) and the olefin polymerization catalysis of formation.
9, according to the said olefin polymerization catalysis of claim 8, above-mentioned particulate carrier will contact processing earlier in advance before carrying above-mentioned periodic table of elements IV B group transition metal compound.
10, according to the olefin polymerization catalysis of claim 8, above-mentioned (A ') periodic table of elements IV B group transition metal compound is a selected at least a compound from zirconium compounds, titanium compound and the hafnium compound of base as dentate that conjugated pi electron is arranged.
CN88103215A 1987-04-20 1988-04-20 Catalyst for polymerizing olefin and process for polymerizing olefin Expired - Fee Related CN1020735C (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP62095446A JPH0794499B2 (en) 1987-04-20 1987-04-20 Olefin Polymerization Method
JP95445/87 1987-04-20
JP62095445A JPH0794498B2 (en) 1987-04-20 1987-04-20 Olefin Polymerization Method
JP95446/87 1987-04-20

Publications (2)

Publication Number Publication Date
CN88103215A true CN88103215A (en) 1988-12-07
CN1020735C CN1020735C (en) 1993-05-19

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CN (1) CN1020735C (en)
AT (1) ATE154943T1 (en)
DE (1) DE3855955T2 (en)

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DE3855955D1 (en) 1997-08-07
CN1020735C (en) 1993-05-19
KR920002769B1 (en) 1992-04-03
ATE154943T1 (en) 1997-07-15
DE3855955T2 (en) 1997-11-20
KR890700616A (en) 1989-04-26

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