CN100532406C - Catalyst components in use for polymerizing ethylene, and catalyst - Google Patents
Catalyst components in use for polymerizing ethylene, and catalyst Download PDFInfo
- Publication number
- CN100532406C CN100532406C CNB2005101174270A CN200510117427A CN100532406C CN 100532406 C CN100532406 C CN 100532406C CN B2005101174270 A CNB2005101174270 A CN B2005101174270A CN 200510117427 A CN200510117427 A CN 200510117427A CN 100532406 C CN100532406 C CN 100532406C
- Authority
- CN
- China
- Prior art keywords
- compound
- copolymerization
- alkyl
- vinyl polymerization
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
This invention relates to components and preparation method for a composite carrier 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, at least one Si compound, and at least one inorganic inert carrier. The Mg composite is prepared by dissolving Mg compound in organic epoxy compound and organic phosphorus compound system. 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, combined polymerization process where catalyst with high activity and good particle morphology is needed, and gas phase fluidized bed process.
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 the polymerization technique of ethene, except that requiring catalyzer should have the advantages of high catalytic activity, polyvinyl size and size distribution that control catalyst particle and then control are produced are crucial.Along with the exploitation and the widespread use of the application, particularly combination process of frozen state in ethene vapor phase process polymerization technique, activity of such catalysts and particle form are had higher requirement.High performance catalyzer promptly will have higher catalytic activity, good copolymerization performance, good hydrogen response also good particle form will be arranged.High catalytic activity can improve the production load of device, enhance productivity, good particle form can effectively reduce the generation of fine polymer powder, and this fine powder easily produces static, causes " airborne dust " phenomenon, sometimes the caking that easily is clamminess easily causes the obstruction of equipment pipe.In order to prepare catalyzer with good particle form, the general method of loading with that adopts, promptly catalyst component is loaded on the inorganic carriers such as silica gel with good particle form, and the catalyst activity of this method preparation is generally lower at present, can't adapt to the requirement of novel process.
For example: in patent CN1268520, with magnesium chloride, silicon-dioxide is carrier, titanium tetrachloride is an active ingredient, the Preparation of catalysts method is as follows: magnesium chloride is reacted with halogenated titanium in tetrahydrofuran (THF) (THF) equal solvent, mix with the silica-gel carrier of handling through aluminum alkyls again, make catalyst component except that after desolvating, when being used for vinyl polymerization, because the titanium content in the catalyzer is lower, therefore polymerization activity is lower, though adopt halogenated alkane as accelerative activator improving catalyst activity, but still can not satisfy the requirement of gas-phase fluidized-bed frozen state and super frozen state technology, the requirement of the highly active combination process of can not satisfying the demand.
Patent CN1085915A discloses a kind of polyvinyl production method, and the catalyzer that uses has adopted the silica gel that particle diameter is littler, specific surface area is bigger to be carrier, and the particle diameter of silica gel is between 0.1～1.0 μ m.The active ingredient titanous chloride makes by the magnesium metal reduction titanium tetrachloride simultaneously, therefore obtained the catalyzer of greater activity, and hexane extractable content significantly reduces in the ethylene copolymer of gained.But because carrier particle is too little, be easy to assemble, cause the heterogeneity of granules of catalyst easily, increase, improve mobile in order to make the granules of catalyst after the load.This patent has adopted spray-dired method in Preparation of Catalyst, mother liquor is mixed with silica gel filler, be prepared by spray-dired method then, the charge capacity of catalyzer has reached 2.0%～3.0%, catalyst activity is higher, go for the gas-phase fluidized-bed frozen state and the super frozen state polymerization technique of ethene, but for needs high activated catalyst combination process, its grain diameter is easy-regulating not.This method for preparing catalyst apparatus expensive, production efficiency are lower simultaneously.
Therefore, be starved of a kind of active high catalyzer that has good particle form simultaneously, is particularly useful for ethene vapor phase process polymerization technique or combined polymerization technique is provided.
Summary of the invention
The invention provides a kind of catalyst component and catalyzer thereof that is used for vinyl polymerization or copolymerization, it has advantages such as advantages of high catalytic activity, better hydrogen regulation sensitivity and narrow grain size distribution of polymers when being used for vinyl polymerization, be highly suitable for slurry polymerization process of ethylene and need in the polymerization mix technology of high reactivity, good particle form catalyzer, this catalyzer also is suitable for gas fluidized-bed process.
A kind of catalyst component that is used for vinyl polymerization or copolymerization, it is included in, and load has a kind of magnesium mixture on the inorganic oxide carrier, 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 the alcohol of the alkyl or cycloalkyl of 1-10 straight chain, side chain;
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;
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.
Described silicon compound, its general formula are 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.
Wherein said magnesium mixture is that magnesium halide is dissolved 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)
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 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
4Be hydrogen, 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 0.2～4molmol.
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 the alcohol of 1-10 straight chain, side chain or cycloalkyl.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 Al
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.Wherein preferred n is not equal to 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.
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 wherein
1And R
2Be respectively alkyl or halogen, R
3Be alkyl, 0≤x＜2,0≤y＜2 and 0＜z≤4.Concrete silicon compound has: silicon tetrachloride, Silicon bromide, 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 tetramethoxy-silicane, tetraethoxysilane and four butoxy silanes, best is tetraethoxysilane.In the catalyst component of the present invention owing to contain the silicon compound of the non-activity hydrogen atom of q.s, thereby improved the over-all properties of catalyzer, silicon compound also plays the effect of the precipitation additive that promotes the moulding of granules of catalyst precipitating simultaneously.Therefore, when the preparation solid catalyst, also can adopt other compound silicon compound with the above-mentioned non-activity hydrogen atom of generation the present invention in preparation process.
Described inorganic oxide carrier comprises SiO
2, Al
2O
3Or its mixture, the form of carrier is spherical in shape, and its particle diameter is 0.1 μ m～150 μ m, preferred 1 μ m～50 μ m, most preferably 5 μ m～40 μ m.The preferred silica gel that adopts bigger serface is as carrier, and preferred specific surface area is 80m
2/ g～300m
2/ g, this helps improving the charge capacity of magnesium in the catalyzer, and then improves the charge capacity of catalyst activity component, the irregular aggregate of magnesium dichloride occurs in the catalyzer when preventing high Mg content, causes the bad phenomenon of granules of catalyst to occur.Inert support preferably carried out roasting processed or alkylation activation treatment before using.
At the catalyst component that is used for vinyl polymerization or copolymerization of the present invention, in every mole of magnesium halide in the magnesium mixture, organic alcohol compound is: 0.1-10 moles, and preferred 1-4 moles; Organo-aluminium compound is 0～5 mole; Titanium compound is 1～15 mole, preferred 2～10 moles; Silicoorganic compound are 0.05～1 mole; Inorganic oxide carrier is 40～400 grams, preferred 80～150 grams.
Other content range of the branch of the composition of gained catalyzer: Ti, Mg, Cl, Si, OEt, P, Al: Ti=1.5～4.5% (wt); Mg=4～14% (wt); Cl=20～40% (wt); OEt=1.5～4.5% (wt); P=0.05～0.5% (wt); Al=0～0.4% (wt); Inert support=20～80% (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, solvent temperature: 50-90 ℃; In forming the process of solution or solution form the back and add organic alcohol compound; After forming, solution randomly adds organo-aluminium compound.
(2) under lower temperature, in preferred-40 ℃-20 ℃, above-mentioned solution and titanium compound are carried out contact reacts, before this reaction, the reaction back or react in the silicon compound of introducing non-activity hydrogen atom.
(3) in the mixture of step (2) gained, add the good inorganic oxide carrier of activation, silica gel for example, 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.Inorganic oxide carrier also can add reaction system before (2) step, promptly added before adding titanium compound.
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 to adopt the silicoorganic compound of no reactive hydrogen be that precipitation additive and inorganic oxide are as carrier, 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, do not need repeatedly to use titanium tetrachloride to handle precipitation yet, the add-on of titanium tetrachloride therefore significantly reduces, and catalyzer has advantages such as the good and narrow diameter distribution of particle form simultaneously.The adding of silicoorganic compound also helps to improve activity of such catalysts, and when catalyzer is used for vinyl polymerization, has shown better hydrogen regulation sensitivity.This system catalytic activity is higher, and less charge capacity can have greater activity, so catalyzer can load on well and make the particle of catalyzer regular on the inorganic oxide carrier, and can obtain the polymkeric substance of narrow diameter distribution.
Embodiment
With embodiment the present invention is described below, but and unrestricted invention scope.
Example 1
(1) preparation of catalyst component: in the reactor of fully replacing through high pure nitrogen, add the 4.0g magnesium dichloride successively, toluene 80ml, 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-25 ℃, slowly drips the 40ml titanium tetrachloride, stirring reaction 0.5 hour.Add the inert support of handling, stirring reaction 0.5 hour.Add the 3ml tetraethoxysilane then, reacted 1 hour.Slowly be warming up to 85 ℃, 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 the 10mg solid catalyst 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
(2) catalyzer is synthetic with embodiment 1.Just the ethanol consumption changes 3.2ml into by 6.4ml.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1.
Embodiment 4
(1) catalyzer is synthetic with embodiment 2.Just do not add aluminium diethyl monochloride.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1.
Embodiment 5
(1) catalyzer is synthetic with embodiment 3.Just do not add aluminium diethyl monochloride.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1.
Embodiment 6
(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 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.This system is cooled to-25 ℃, adds inert support 5g, stirring reaction 0.5 hour.Slowly drip the 40ml titanium tetrachloride, add the 3ml tetraethoxysilane then, reacted 1 hour.Slowly be warming up to 85 ℃, 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 7
(1) catalyzer is synthetic with embodiment 4.Just the tetraethoxysilane consumption changes 4ml into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1.
Embodiment 8
(1) catalyzer is synthetic with embodiment 4.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 9
(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.
Embodiment 10
(1) catalyzer is synthetic with embodiment 4.Just the ethanol of consumption 5.9ml changes the isooctyl alcohol of 16.4ml 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 do not add tetraethoxysilane.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1.
Claims (9)
1, the catalyst component that is used for vinyl polymerization or copolymerization, it is included in, and load has a kind of magnesium mixture on the inorganic oxide carrier, 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;
Described magnesium mixture is that magnesium dihalide is dissolved in the mixture that forms 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 are randomly 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 catalyst component that is used for vinyl polymerization or copolymerization 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 catalyst component that is used for vinyl polymerization or copolymerization 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, the catalyst component that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that, described inorganic oxide carrier is a silica gel.
5, according to the described catalyst component that is used for vinyl polymerization or copolymerization of one of claim 1-4, it is characterized in that, 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, and inorganic oxide carrier is 40～400 grams.
6, according to the described catalyst component that is used for vinyl polymerization or copolymerization of one of claim 1-4, it is characterized in that, in the solvent system described in the magnesium mixture, in every mole of magnesium halide, organic epoxy compounds: 0.3～4mol; Organo phosphorous compounds: 0.2～4mol.
7, a kind of catalyzer that is used for vinyl polymerization or copolymerization, 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 catalyzer that is used for vinyl polymerization or copolymerization 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 or copolymerization.
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101174270A CN100532406C (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 |
| PCT/CN2006/002923 WO2007051410A1 (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 |
| KR1020087011581A KR101433174B1 (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 |
| EP06805124.2A EP1947123B1 (en) | 2005-10-31 | 2006-10-31 | Catalyst component for ethylene polymerization, preparation thereof and catalyst containing the same |
| ES06805124.2T ES2575358T3 (en) | 2005-10-31 | 2006-10-31 | Catalytic component for the polymerization of ethylene, preparation thereof and catalyst containing it |
| 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 |
| MYPI20064416A MY163364A (en) | 2005-10-31 | 2006-10-31 | Catalyst component for ethylene polymerization, preparation thereof and catalyst comprising the same |
| 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)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101174270A CN100532406C (en) | 2005-10-31 | 2005-10-31 | Catalyst components in use for polymerizing ethylene, and catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1958622A CN1958622A (en) | 2007-05-09 |
| CN100532406C true CN100532406C (en) | 2009-08-26 |
Family
ID=38070487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101174270A Active CN100532406C (en) | 2005-10-31 | 2005-10-31 | Catalyst components in use for polymerizing ethylene, and catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100532406C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040686B (en) * | 2009-10-16 | 2013-05-01 | 中国石油化工股份有限公司 | Catalyst component and catalyst for vinyl polymerization |
| CN102432726A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Polyvinyl resin used for preparing chlorinated polyethylene and preparation method thereof |
| CN104231124B (en) * | 2013-06-08 | 2016-08-10 | 中国石油化工股份有限公司 | Load type non-metallocene catalyst, its preparation method and application thereof |
| CN105017456B (en) * | 2014-04-15 | 2017-06-06 | 中国石化扬子石油化工有限公司 | A kind of ethylene-alpha-olefin copolymer, its manufacture method and its application |
| CN105017459B (en) * | 2014-04-15 | 2017-06-06 | 中国石化扬子石油化工有限公司 | A kind of ethylene-alpha-olefin copolymer, its manufacture method and its application |
| CN114149523B (en) * | 2020-09-05 | 2022-11-18 | 中国石油化工股份有限公司 | Catalyst spherical carrier for olefin polymerization, preparation method and application thereof, and catalyst and application thereof |
-
2005
- 2005-10-31 CN CNB2005101174270A patent/CN100532406C/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN1958622A (en) | 2007-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100513433C (en) | Catalyst components in use for polymerizing ethylene, and catalyst | |
| CN101274967B (en) | Catalyst for ethylene polymerization and components thereof | |
| CN101633704B (en) | Catalyst component used for ethylene polymerization reaction and catalyst thereof | |
| CN1189487C (en) | A method for producing ethylene homo-and co-polymer | |
| CN100532406C (en) | Catalyst components in use for polymerizing ethylene, and catalyst | |
| CN101838353A (en) | Catalyst component for vinyl polymerization and catalyst thereof | |
| CN101353385A (en) | Catalyzer for ethylene polymerization and copolymerization and preparing method thereof | |
| CN103772554A (en) | Ingredients of catalyst for vinyl polymerization and catalyst | |
| CN102295717A (en) | Catalyst compound used for vinyl polymerization reaction and catalyst thereof | |
| CN102875707A (en) | Preparation method of catalyst component for ethylene polymerization or copolymerization and catalyst thereof | |
| CN1213075C (en) | Prepolymerization method of olefin | |
| CN101260166A (en) | Ethene homopolymerization and copolymerization catalyst and preparation method thereof | |
| CN102295715B (en) | Catalyst component used for vinyl polymerization reaction and catalyst thereof | |
| CN102993343B (en) | Catalyst component for ethylene polymerization, and catalyst thereof | |
| CN102040685B (en) | Catalyst component for ethylene polymerization and catalyst | |
| CN102040686B (en) | Catalyst component and catalyst for vinyl polymerization | |
| CN103130931B (en) | A kind of Ball shape ethylene polymerization solid titanium catalytic and Synthesis and applications thereof | |
| CN101633705B (en) | Catalyst component used for ethylene polymerization reaction and catalyst thereof | |
| CN101838352B (en) | Catalyst component for vinyl polymerization or copolymerization and catalyst thereof | |
| CN103087224B (en) | Catalyst ingredient used for ethylene polymerization, and preparation method thereof | |
| CN102060945B (en) | Preparation and application of solid titanium catalyst component for vinyl polymerization | |
| CN1297575C (en) | Catalyst component for ethylene polymerization or copolymerization and its catalyst | |
| CN102286119A (en) | Catalyst component and catalyst for polymerization of ethylene | |
| CN102344515B (en) | Catalyst component for ethylene polymerization and catalyst thereof | |
| CN101519463A (en) | Preparation method of catalyst for ethylene polymerization and copolymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |