CN100513433C - Catalyst components in use for polymerizing ethylene, and catalyst - Google Patents
Catalyst components in use for polymerizing ethylene, and catalyst Download PDFInfo
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- CN100513433C CN100513433C CNB2005101174285A CN200510117428A CN100513433C CN 100513433 C CN100513433 C CN 100513433C CN B2005101174285 A CNB2005101174285 A CN B2005101174285A CN 200510117428 A CN200510117428 A CN 200510117428A CN 100513433 C CN100513433 C CN 100513433C
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Abstract
This invention relates to a method for preparing catalyst for ethylene homopolymerization or copolymerization with other alpha-olefins. The catalyst comprises at least one Mg composite, at least one Ti compound, at least one organic alcohol compound, and at least one Si compound. The general formula of the Si compound is R1xR2ySi (OR3) z, where R1 and R2 are alkyl or halogen; R3 is alkyl; x is 0-2; y is 0-2; z is 0-4; x + y + z = 4. The catalyst has such advantages as high catalytic activity, high hydrogen sensitivity and narrow particle size distribution of polymer. The catalyst is suitable for slurry polymerization of ethylene, and combined polymerization process where catalyst with high activity is needed.
Description
Technical field
The present invention relates to a kind of catalyst component that is used for vinyl polymerization or copolymerization, the preparation method of this catalyst component and the catalyzer of this catalyst component.
Technical background
As everyone knows, the catalyst body that contains the Ti/Mg mixture ties up in the poly suitability for industrialized production occupies an leading position, and its research core is nothing more than the hydrogen response of the particle form of the polymerization activity that is catalyzer, catalyzer and size distribution, catalyzer and copolymerization performance or the like.And in slurry polymerization process of ethylene, except that requiring catalyzer should have the advantages of high catalytic activity, polyvinyl size and size distribution that control is produced are crucial.At vinyl polymerization, particularly in the slurry polymerization process of ethene, be easy to produce thinner examples of polymers, this fine powder easily produces static, causes " airborne dust " phenomenon, easily lumps sometimes, causes the obstruction of equipment pipe.And the effective means of the size of controlling polymers and size distribution is the particle diameter and the size distribution of control catalyst.
In the prior art, in order to obtain having the catalyzer of single-size diameter and better particle form, people adopt two following class methods to prepare catalyzer usually.
First kind is magnesium compounds such as magnesium chloride to be dissolved in obtain homogeneous solution in some solvent, and then with this solution and titanium compound and randomly electron donor mix, obtain containing the solids of magnesium, titanium and optional electron donor by sedimentary method, and obtain granules of catalyst after this solids handled with excessive liquid titanium compound.For example disclosed among Chinese patent CN1099041A, the CN1229092 etc.The shortcoming of this traditional method is that the particle diameter and the size distribution of granules of catalyst controlled by precipitation process fully, and this is the recrystallization process of magnesium carrier composition, and its stable control ratio is difficulty.
For example, in patent CN1229092, be carrier with the magnesium chloride, titanium tetrachloride is an active ingredient, the Preparation of catalysts method is as follows: earlier with MgCl
2Be dissolved in the solvent system, form homogeneous transparent solution, then the precipitation additive phthalic anhydride exist and low temperature under with TiCl
4Reaction is separated out solid catalyst by slow intensification.When the catalyst component that makes was used for vinyl polymerization, though the particle form of polymkeric substance is better, the hydrogen response of catalyzer and catalytic activity were also unsatisfactory.Simultaneously, when synthetic this catalyzer, need adopt organism such as phthalic anhydride to promote sedimentary separating out, and need to add a large amount of titanium tetrachlorides as precipitation additive.Therefore not only the existence of acid anhydrides produces adverse influence to catalyzer, and the use of simultaneously a large amount of titanium tetrachlorides also can cause a large amount of wastes and pollution.This kind system also is clamminess easily simultaneously, and catalyzer is difficult to preparation.
Second kind is that the catalyst activity component directly is carried on inert support, and as on the silica gel etc., because the particle diameter of silica gel controls easily, and particle form is better, therefore can obtain evengranular catalyst particle.But because the charge capacity of active ingredient is restricted on the carrier, therefore titanium content is lower in the catalyzer that makes of this method, and polymerization activity is not high.For example: in patent CN1268520, be carrier with magnesium chloride, silicon-dioxide, titanium tetrachloride is an active ingredient, and the Preparation of catalysts method is as follows: with MgCl
2In THF with TiCl
4Reaction is again with the SiO that handled through aluminum alkyls
2Mix, make catalyst component after removing THF, when being used for vinyl polymerization, because the titanium content in the catalyzer is lower, so polymerization activity is lower.Therefore, though this catalyst system can be used for the gas-phase fluidized bed polymerization process of ethene, because lower catalytic activity is difficult to be applicable in the slurry polymerization process of ethylene.
As everyone knows, in slurry polymerization process of ethylene, except that requiring catalyzer should have advantages of high catalytic activity and preferably the size distribution, in order to produce Alathon or multipolymer with better performance, also require catalyzer should have better hydrogen regulation sensitivity, i.e. melting index of regulating final polymkeric substance by hydrogen dividing potential drop in the polymerization process at an easy rate is to obtain the polyvinyl resin of the different commercial trades mark.And the hydrogen response of above-mentioned catalyst system is also unsatisfactory.
Therefore, being starved of provides a kind of catalyzer that is applicable to slurry polymerization process of ethylene, and it is catalytic activity height, even, the narrow diameter distribution of particle diameter not only, and has better hydrogen regulation sensitivity.
Summary of the invention
The invention provides a kind of catalyst component that is used for vinyl polymerization or copolymerization, comprise a kind of magnesium mixture, at least a titanium compound, at least a organic alcohol compound, at least a silicon compound, randomly with a kind of reaction product of organoaluminum.Catalyzer of the present invention be used to have advantages of high catalytic activity, advantages such as better hydrogen regulation sensitivity and narrow grain size distribution of polymers, be highly suitable for slurry polymerization process of ethylene and need in the polymerization mix technology of high activated catalyst.
Wherein said magnesium mixture is that magnesium halide is dissolved in resulting product in the solvent system that contains organic epoxy compounds and organo phosphorous compounds.
Described organic alcohol compound is that carbonatoms is the alcohol of 1-10 straight chain, side chain or cycloalkyl.
Described titanium compound general formula is Ti (OR
2)
aX
2 b, R in the formula
2Be C
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X
2Be halogen, a is 0,1 or 2, and b is 1 to 4 integer, a+b=3 or 4.
Described silicon compound is the silicoorganic compound of non-activity hydrogen atom, and its general formula is R
1 xR
2 ySi (OR
3)
z, R wherein
1And R
2Be respectively alkyl or halogen, R
3Be alkyl, 0≤x≤2,0≤y≤2 and 0≤z≤4.
The general formula of described organo-aluminium compound is AlR
4 nX
1 3-n, R in the formula
4For carbonatoms is 1～20 alkyl, X
1Be halogen, n is the number of 1＜n≤3.
Magnesium mixture of the present invention is that magnesium dihalide is dissolved in the mixture that forms in the solvent system that contains organic epoxy compounds and organo phosphorous compounds.Common this mixture should be the solution of a homogeneous transparent.
Wherein said magnesium halide is selected from the complex compound, magnesium dihalide molecular formula of the water of magnesium dihalide, magnesium dihalide or alcohol one of them or two halogen atoms by alkyl or halogen-oxyl institute metathetical derivative.Concrete compound is as magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium etc., wherein preferred magnesium dichloride.Described halogenated magnesium compound can be used alone or as a mixture.
Organic epoxy compounds described in the solvent system is selected from least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halo fat group alkene or diolefine of carbonatoms.Such as, but be not limited to: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether.
Organo phosphorous compounds described in the solvent system is the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.Concrete as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or phosphorous acid benzene methyl.Wherein in every mole of magnesium halide: organic epoxy compounds: 0.2-10mol, preferred 0.3～4mol; Organo phosphorous compounds: 0.1～10mol, preferred 0.2～4mol mol.
In order to make dissolving more abundant, in this solvent system, can randomly add inert diluent, common this inert diluent comprises arene compounds or alkane derivative, and arene compounds comprises benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, monochlorotoluene and derivative thereof; Alkane comprises a kind of in straight-chain paraffin, branched paraffin or the naphthenic hydrocarbon of 3～20 carbon or their mixture, as butane, and pentane, hexane, hexanaphthene, heptane etc. are as long as help the magnesium halide dissolved to use.Above-mentioned inert diluent can use separately, use also capable of being combined.
Described organic alcohol compound comprises that carbonatoms is that the alcohol of 1-10 straight chain, side chain or cycloalkyl or carbonatoms are that 6-20 fragrant and mellow or aralkyl is pure, and the hydrogen atom of wherein said alcohol or carbon atom can be replaced by halogen atom.The example of alcohol comprises: Fatty Alcohol(C12-C14 and C12-C18), as: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, glycerol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, n-Heptyl alcohol, 2-Ethylhexyl Alcohol, n-Octanol, decyl alcohol etc.; Cycloalkanol is as hexalin, methyl-cyclohexanol; Aromatic alcohol, as phenylcarbinol, methylbenzyl alcohol, α-Jia Jibenjiachun, α, alpha-alpha-dimethyl phenylcarbinol, isopropyl benzene methyl alcohol, phenylethyl alcohol, phenol etc.; Halogen-containing alcohol is as trichlorine methyl alcohol, ethapon and three Mecorals etc.Wherein preferred alcohol, butanols, 2-Ethylhexyl Alcohol, glycerol.
The general formula of described organo-aluminium compound is AlR
4 nX
1 3-n, R in the formula
4Be 1～20 alkyl independently for hydrogen or carbonatoms,, particularly alkyl, aralkyl or aryl; X
1Be halogen, particularly chlorine and bromine; N is the number of 0＜n≤3.Particular compound is as aluminum alkyl halides such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, ethyl aluminum dichlorides, the halogenide of preferred alkyl aluminium wherein, excellent is best with aluminium diethyl monochloride.In the catalyst component of the present invention, organo-aluminium compound is an optional component.Help improving activity of such catalysts and hydrogen response after adding a certain amount of this component, excessively then can suppress activity of such catalysts but add, and system is clamminess, be unfavorable for separating out of catalyzer.
Described titanium compound general formula is Ti (OR)
aX
b, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen, a is 0,1 or 2, b is 1 to 4 integer, a+b=3 or 4.A kind of or its mixture in preferred titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, titanous chloride, dichloro diethoxy titanium, trichlorine one ethanolato-titanium.
Described silicon compound is the silicoorganic compound of non-activity hydrogen atom, and its general formula is R
1 xR
2 ySi (OR
3)
z, R preferably
1And R
2Be respectively carbonatoms and be 1-10 alkyl or halogen, R
3For carbonatoms is 1-10 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4.
The represented silicon compound of above-mentioned general formula comprises: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four (2-ethyl hexyl oxy) silane, ethyl trimethoxy silane, ethyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, the n-propyl triethoxyl silane, the n-propyl Trimethoxy silane, the decyl Trimethoxy silane, the decyl triethoxyl silane, the cyclopentyl Trimethoxy silane, the cyclopentyl triethoxyl silane, 2-methylcyclopentyl Trimethoxy silane, 2,3-dimethylcyclopentyl Trimethoxy silane, cyclohexyl trimethoxy silane, the cyclohexyl triethoxyl silane, methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, tertiary butyl triethoxyl silane, the normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, the isobutyl-Trimethoxy silane, the isobutyl-triethoxyl silane, the cyclohexyl triethoxyl silane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, one chlorine Trimethoxy silane, one chlorine triethoxyl silane, ethyl three isopropoxy silane, vinyl three butoxy silanes, trimethyl phenoxysilane, methyl three allyloxy silane, vinyl nitrilotriacetic base silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diisopropyl dimethoxy silane, the di-isopropyl diethoxy silane, tertiary butyl methyl dimethoxysilane, tertiary butyl methyldiethoxysilane, the tert-pentyl methyldiethoxysilane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, the methylcyclopentyl diethoxy silane, methylcyclopentyl dimethoxy silane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, the aminomethyl phenyl diethoxy silane, aminomethyl phenyl dimethoxy silane, two o-tolyl dimethoxy silane, two o-tolyl diethoxy silanes, tolyl dimethoxy silane between two, tolyl diethoxy silane between two, biconjugate tolyl dimethoxy silane, biconjugate tolyl diethoxy silane, the trimethylammonium methoxy silane, trimethylethoxysilane, three cyclopentyl methoxy silane, three cyclopentyl Ethoxysilanes, one or more mixing wherein such as two cyclopentyl-methyl methoxy silane and cyclopentyl dimethyl methyl TMOS are used.
Wherein be preferably tetraalkoxysilane, for example tetraethoxysilane and four butoxy silanes, best is tetraethoxysilane.
Among the present invention, the silicon compound that should contain q.s in the solid titanium catalyst component that finally obtains is to improve the over-all properties of catalyzer, and silicon compound also plays the effect of the precipitation additive that promotes the moulding of granules of catalyst precipitating simultaneously.Therefore, preparation also can adopt during solid catalyst other compound in preparation process to generate silicon compound.
At the catalyst component that is used for vinyl polymerization or copolymerization of the present invention, the ratio between each reactant is in every mole of magnesium halide in the magnesium mixture, and organic alcohol compound is: 0.1-10 moles, and preferred 1-4 moles; Silicoorganic compound are 0.05～1 mole; Organo-aluminium compound is 0～5 mole.Titanium compound is 1～15 mole, preferred 2～10 moles.
Other content range of the branch of the composition of gained catalyzer: Ti, Mg, Cl, Si, OEt, P, Al: Ti=4.5～7.5% (wt); Mg=14～19% (wt); Cl=58～68% (wt); Si=0.2～1.2% (wt); OEt=4.0～8.5% (wt); P=0.1～1.0% (wt); Al=0～0.6% (wt).
The above-mentioned catalyst component of the present invention can adopt following method preparation:
(1) magnesium halide is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, preferably in solvent system, adds inert diluent, form homogeneous solution, the preferred 50-90 of solvent temperature ℃; In forming the process of solution or solution form the back and add organic alcohol compound, add or do not add organo-aluminium compound, reaction regular hour then.
(2) in the presence of the silicoorganic compound of non-activity hydrogen atom, under the lower temperature, preferably-40 in ℃-20 ℃, above-mentioned solution and titanium compound are carried out contact reacts, the silicoorganic compound of non-activity hydrogen atom also can carry out adding after the contact reacts at solution in (1) step and titanium compound, and mixture slowly is warming up to 60 ℃-110 ℃, particle is separated out and formed to solids gradually, after the reaction regular hour, remove unreacted reactant and solvent, and adopt the inert diluent washing, obtain catalyst component of the present invention.
The present invention also provides the catalyzer of the copolymerization of a kind of equal polymerization reaction that is used for ethene or ethene and other alpha-olefin, and alpha-olefin wherein comprises propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, vinylbenzene, vinyl toluene etc.; It is AlR with (2) general formula that this catalyzer comprises (1) above-mentioned catalyst component of the present invention
5 nX
2 3-nThe reaction product of organo-aluminium compound, R in the formula
5Can be 1～20 alkyl, particularly alkyl, aralkyl, aryl for hydrogen, carbonatoms; X
2Be halogen, particularly chlorine and bromine; N is the number of 0＜n≤3.Particular compound is as aluminum alkyl halides such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, ethyl aluminum dichlorides, wherein preferred trialkyl aluminium compound, excellent with triethyl aluminum, triisobutyl aluminium for well.Wherein the mol ratio of the middle titanium of aluminium and component (1) is 5～500, preferred 20-200 in the component (2).
Liquid polymerization can be adopted during polymerization, also vapour phase polymerization can be adopted.
Liquid polymerization medium comprises: Trimethylmethane, hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, inert solvent such as aliphatic saturated hydrocarbon such as hydrogenated gasoline, kerosene, benzene,toluene,xylene or aromatic hydrocarbon.
In order to regulate the molecular weight of final polymkeric substance, adopt hydrogen to make molecular weight regulator.
Catalyzer of the present invention is because the silicoorganic compound of the no reactive hydrogen of employing are precipitation additive, therefore when Preparation of Catalyst, separate out granules of catalyst at an easy rate, do not need to use a large amount of titanium tetrachlorides to impel sedimentary separating out, also do not need repeatedly to use titanium tetrachloride to handle precipitation, so the add-on of titanium tetrachloride significantly reduces.The adding of silicoorganic compound simultaneously also helps to improve the improvement of the particle form of activity of such catalysts and catalyzer, thereby further improves the particle form of polymkeric substance.When catalyzer is used for vinyl polymerization, shown better hydrogen regulation sensitivity.
Embodiment
With embodiment the present invention is described below, but and unrestricted invention scope.
Embodiment 1
(1) preparation of catalyst component: in the reactor of fully replacing through high pure nitrogen, add the 4.0g magnesium dichloride successively, toluene 50ml, epoxy chloropropane 4.0ml, tributyl phosphate 4.0ml, ethanol 6.4ml, stir down and be warming up to 70 ℃, dissolve fully when solid behind the solution that forms homogeneous and reacted 1 hour under 70 ℃ of conditions.Be cooled to 30 ℃, dripping 4.8ml concentration is the aluminium diethyl monochloride of 2.2M, and keeps reaction 1 hour at 30 ℃.This system is cooled to-5 ℃, slowly drips the 40ml titanium tetrachloride, add the 3ml tetraethoxysilane then, reacted 1 hour.Slowly be warming up to 80 ℃, reacted 2 hours.Stop to stir, leave standstill, the very fast layering of suspension extracts the upper strata stillness of night, twice of toluene wash, hexane wash four times, and high pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution.The catalyzer composition sees Table 1.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M adds catalyzer (containing 0.3 milligram of titanium) the solid hexane solution of above-mentioned preparation, is warming up to 70 ℃, feeding hydrogen makes the still internal pressure reach 0.28Mpa, feed ethene again and make the interior stagnation pressure of still reach 0.73Mpa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 2
(1) catalyzer is synthetic with embodiment 1.Just the ethanol consumption changes 5.9ml into by 6.4ml.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1.
Embodiment 3
(1) catalyzer is synthetic with embodiment 2.Just the aluminium diethyl monochloride consumption changes 3.8ml into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1.
Embodiment 4
(1) preparation of catalyst component: in the reactor of fully replacing through high pure nitrogen, add the 4.03g magnesium dichloride successively, toluene 50ml, epoxy chloropropane 4.0ml, tributyl phosphate 4ml, ethanol 6.4ml, stir down and be warming up to 70 ℃, dissolve fully when solid behind the solution that forms homogeneous and reacted 1 hour under 70 ℃ of conditions.This system is cooled to-5 ℃, slowly drips the 40ml titanium tetrachloride, add the 3ml tetraethoxysilane then, reacted 1 hour.Slowly be warming up to 80 ℃, reacted 2 hours.Stop to stir, leave standstill, the very fast layering of suspension extracts the upper strata stillness of night, twice of toluene wash, hexane wash four times, and high pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution.The catalyzer composition sees Table 1.
(2) vinyl polymerization is with embodiment 1.Polymerization result sees Table 1.
Embodiment 5
(1) catalyzer is synthetic with embodiment 1.Just the tetraethoxysilane consumption changes 2ml into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1.
Embodiment 6
(1) catalyzer is synthetic with embodiment 1.Just the tetraethoxysilane consumption changes 1ml into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1.
Embodiment 7
(1) catalyzer is synthetic with embodiment 1.Just the tetraethoxysilane consumption changes 5ml into.
(2) vinyl polymerization is with embodiment 1, and catalyzer is formed and polymerization result sees Table 1.
Embodiment 8
(1) catalyzer is synthetic with embodiment 4.Just tetraethoxysilane changes silicon tetrachloride into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1.
Comparative Examples 1
(1) catalyzer is synthetic with embodiment 4.Just tetraethoxysilane changes Tetra hydro Phthalic anhydride into.
(2) vinyl polymerization is with embodiment 4.Catalyzer is formed and polymerization result sees Table 1.
Comparative Examples 2
(1) catalyzer is synthetic with embodiment 4.Just do not add tetraethoxysilane.Catalyzer is separated out difficult forming, and precipitation particles is superfine, is difficult to sedimentation, is taken away entirely during suction filtration, fails to form catalyzer.
From the aggregated data of table 2 as can be seen, under same polymerizing condition, catalyst activity of the present invention is higher, and owing in catalyzer of the present invention, introduced silicon compound, make catalyzer separate out the moulding easily control that becomes, gained polymeric size distribution will be narrower than Comparative Examples 1 (with phthalic anhydride as precipitation agent), and it is all less to cross thick or meticulous particle in the polymkeric substance of gained.
Table 1 catalyzer is formed
Table 2 polymer performance
Claims (9)
1, be used for the ethylene polymerization catalysts component, comprise a kind of magnesium mixture, at least a titanium compound, at least a organic alcohol compound, at least a silicon compound, randomly with a kind of reaction product of organoaluminum;
Wherein said magnesium mixture is that magnesium halide is dissolved in resulting product in the solvent system that contains organic epoxy compounds and organo phosphorous compounds;
Described organic alcohol compound is that carbonatoms is that the alcohol of alkyl or cycloalkyl of 1-10 straight chain, side chain or carbonatoms are that 6-20 fragrant and mellow or aralkyl is pure, and hydrogen atom or carbon atom in described organic alcohol can be replaced by halogen atom;
Described titanium compound general formula is Ti (OR)
aX
b, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen, a is 0,1 or 2, b is 1 to 4 integer, a+b=3 or 4;
Described silicon compound is for being R as general formula
1 xR
2 ySi (OR
3)
zShown silicoorganic compound, wherein R
1And R
2Be respectively alkyl or halogen, R
3Be alkyl, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4;
The general formula of described organo-aluminium compound is AlR
4 nX
1 3-n, R in the formula
4For hydrogen or carbonatoms are 1～20 alkyl, X
1Be halogen, n is the number of 1＜n≤3.
2, the ethylene polymerization catalysts component that is used for according to claim 1 is characterized in that, general formula is R
1 xR
2 ySi (OR
3)
zIn, R
1And R
2Be respectively carbonatoms and be 1-10 alkyl or halogen, R
3For carbonatoms is 1-10 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4.
3, the ethylene polymerization catalysts component that is used for according to claim 1 is characterized in that described silicon compound is selected from least a in tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes and four (2-ethyl hexyl oxy) silane.
4, according to the described ethylene polymerization catalysts component that is used for of one of claim 1-3, ratio between each reactant is in every mole of magnesium halide in the magnesium mixture, organic alcohol compound is: 0.1-10 moles, silicoorganic compound are 0.05～1 mole, organo-aluminium compound is 0～5 mole, and titanium compound is 1～15 mole.
According to the described ethylene polymerization catalysts component that is used for of one of claim 1-3, it is characterized in that 5, described solvent system is in every mole of magnesium halide: organic epoxy compounds: 0.3～4mol; Organo phosphorous compounds: 0.2～4mol.
6, according to the described ethylene polymerization catalysts component that is used for of one of claim 1-3, it contains Ti:4.5～7.5wt%, Mg:14～19wt%, Cl:58～68wt%, Si:0.2～1.2%wt%, OR:4.0～8.5wt%, P:0.1～1.0wt%, Al:0～0.6wt%.
7, a kind of ethylene polymerization catalysts that is used for, it comprises the reaction product of following component:
(1) the described catalyst component of one of claim 1-6;
(2) general formula is AlR
5 nX
2 3-nOrgano-aluminium compound, R in the formula
5For hydrogen or carbonatoms are 1～20 alkyl, X
2Be halogen, 0＜n≤3.
8, the ethylene polymerization catalysts that is used for according to claim 7, wherein the mol ratio of the middle titanium of aluminium and component (1) is 20-200 in the component (2).
9, the application of the described catalyzer of claim 7 in vinyl polymerization.
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101174285A CN100513433C (en) | 2005-10-31 | 2005-10-31 | Catalyst components in use for polymerizing ethylene, and catalyst |
| SI200632060A SI1947123T1 (en) | 2005-10-31 | 2006-10-31 | Catalyst component for ethylene polymerization, preparation thereof and catalyst containing the same |
| EP06805124.2A EP1947123B1 (en) | 2005-10-31 | 2006-10-31 | Catalyst component for ethylene polymerization, preparation thereof and catalyst containing the same |
| BRPI0619719-1A BRPI0619719B1 (en) | 2005-10-31 | 2006-10-31 | METHOD FOR PREPARING A CATALYST COMPONENT FOR ETHYLENE POLYMERIZATION |
| ES06805124.2T ES2575358T3 (en) | 2005-10-31 | 2006-10-31 | Catalytic component for the polymerization of ethylene, preparation thereof and catalyst containing it |
| KR1020087011581A KR101433174B1 (en) | 2005-10-31 | 2006-10-31 | Catalyst component for ethylene polymerization, preparation thereof and catalyst containing the same |
| PL06805124.2T PL1947123T3 (en) | 2005-10-31 | 2006-10-31 | Catalyst component for ethylene polymerization, preparation thereof and catalyst containing the same |
| PCT/CN2006/002923 WO2007051410A1 (en) | 2005-10-31 | 2006-10-31 | Catalyst component for ethylene polymerization, preparation thereof and catalyst containing the same |
| MYPI20064416A MY163364A (en) | 2005-10-31 | 2006-10-31 | Catalyst component for ethylene polymerization, preparation thereof and catalyst comprising the same |
| US12/084,258 US20090318643A1 (en) | 2005-10-31 | 2006-10-31 | Catalyst Component for Ethylene Polymerization, Preparation Thereof and Catalyst Comprising the Same |
| RU2008121923/04A RU2375378C1 (en) | 2005-10-31 | 2006-10-31 | Catalyst component for ethylene polymerisation, production thereof and catalyst containing this component |
| US14/611,626 US20150239998A1 (en) | 2005-10-31 | 2015-02-02 | Catalyst component for ethylene polymerization, preparation thereof and catalyst comprising the same |
Applications Claiming Priority (1)
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|---|---|---|---|
| CNB2005101174285A CN100513433C (en) | 2005-10-31 | 2005-10-31 | Catalyst components in use for polymerizing ethylene, and catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1958620A CN1958620A (en) | 2007-05-09 |
| CN100513433C true CN100513433C (en) | 2009-07-15 |
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| CNB2005101174285A Active CN100513433C (en) | 2005-10-31 | 2005-10-31 | Catalyst components in use for polymerizing ethylene, and catalyst |
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| CN101096389B (en) * | 2007-06-22 | 2010-05-19 | 上海化工研究院 | Super-high molecular weight polyethylene catalyzer and preparation method thereof |
| CN101633705B (en) * | 2008-07-24 | 2011-06-15 | 中国石油化工股份有限公司 | Catalyst component used for ethylene polymerization reaction and catalyst thereof |
| CN101993508B (en) * | 2009-08-21 | 2013-03-27 | 中国石油化工股份有限公司 | Catalyst component used for vinyl polymerization and catalyst |
| ES2472668T3 (en) | 2009-08-21 | 2014-07-02 | China Petroleum & Chemical Corporation | Catalyst component for the polymerization of ethylene, preparation thereof and catalyst comprising the catalyst component |
| CN102286119A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Catalyst component and catalyst for polymerization of ethylene |
| CN102295715B (en) * | 2010-06-25 | 2013-09-25 | 中国石油化工股份有限公司 | Catalyst component used for vinyl polymerization reaction and catalyst thereof |
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| CN102432713B (en) * | 2010-09-29 | 2013-07-03 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, preparation method and application thereof |
| CN102453172A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Method for homopolymerizing or copolymerizing ethylene |
| CN102875708A (en) * | 2011-07-14 | 2013-01-16 | 中国石油化工股份有限公司 | Preparation method of catalyst component for ethylene polymerization reaction and catalyst thereof |
| CN102977232B (en) * | 2011-09-02 | 2015-08-19 | 中国石油化工股份有限公司 | A kind of catalyst system for vinyl polymerization |
| CN102977235B (en) * | 2011-09-02 | 2014-12-03 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization and catalyst |
| CN103130931B (en) * | 2011-11-30 | 2016-06-08 | 中国石油天然气股份有限公司 | Spherical ethylene polymerization solid titanium catalyst, preparation and application thereof |
| CN103772550B (en) * | 2012-10-23 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of catalyst component for polymerization of ethylene and catalyst thereof |
| JP2017534725A (en) * | 2014-10-16 | 2017-11-24 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | Catalyst composition for olefin polymerization |
| CN106632755B (en) * | 2015-10-29 | 2019-12-24 | 中国石油化工股份有限公司 | Catalyst system for ethylene polymerization and application thereof |
| CN106699932B (en) * | 2015-11-12 | 2019-03-22 | 营口市向阳催化剂有限责任公司 | Polypropylene polymerization catalyst system and its application containing phosphoric acid ester external electron donor |
| FI3656754T3 (en) | 2017-07-19 | 2024-06-20 | China Petroleum & Chem Corp | Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof |
| CN116606391A (en) * | 2022-02-09 | 2023-08-18 | 中国石油化工股份有限公司 | Olefin polymerization catalyst solid component, preparation method thereof, olefin polymerization catalyst and application |
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