CN102344507A - Catalyst component for vinyl polymerization and catalyst thereof - Google Patents
Catalyst component for vinyl polymerization and catalyst thereof Download PDFInfo
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- CN102344507A CN102344507A CN2010102403795A CN201010240379A CN102344507A CN 102344507 A CN102344507 A CN 102344507A CN 2010102403795 A CN2010102403795 A CN 2010102403795A CN 201010240379 A CN201010240379 A CN 201010240379A CN 102344507 A CN102344507 A CN 102344507A
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Abstract
The invention relates to a catalyst component for vinyl polymerization, a catalyst and a preparation method thereof; the catalyst component is obtained through the following reaction steps: (1) allowing an organo-magnesium compound, at least one organo-titanium compound, and at least one boron compound to react so as to obtain a reaction product A; (2) allowing the reaction product A to react with at least one organo-aluminium compound to obtain a reaction product B; (3) allowing the reaction product B to react with at least one inorgano-titanium compound to obtain the final catalyst component. The catalyst of the invention has the advantages of high catalytic activity, good hydrogen response, and narrow polymer particle size distribution, and is quite applicable to ethane slurry polymerization process and combination polymerization process which requires catalysts with high activity.
Description
Technical field
The present invention relates to a kind of catalyst component that is used for ethylene polymerization, the preparation method of this catalyst component and this catalyzer.
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 fine polymer powder, this fine powder is prone to produce static, is prone to caking, 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, two class methods below people adopt usually prepare catalyzer.
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 through 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 through precipitation process fully, and this is the recrystallization process of magnesium carrier composition, and its stable 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 following: earlier with MgCl
2Be dissolved in the solvent system, form homogeneous transparent solution, then the precipitation additive phthalic anhydride exist and low temperature under and TiCl
4Reaction is separated out solid catalyst through slow intensification.When the catalyst component that makes was used for vinyl polymerization, though the particle form of polymkeric substance is better, the fine polymer powder that catalyzer prepares in industrial production was still more, and the hydrogen response and the catalytic activity of catalyzer are also unsatisfactory simultaneously.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.
Second kind is the carrier that preparation earlier has good particle form, carries titanium then, and prepared in reaction obtains highly active polyolefin catalyst.Chinese patent CN85105150 for example, patents such as CN101300278.
Chinese patent CN85105150 at first adopts magnesium halide and titan-alkoxide reaction; Generate solid magnesium-containing carrier with the aluminum alkyls reaction then with better particle form; This carrier and titanium tetrachloride reaction obtain solid catalyst at last, and the polyethylene polymer of this Preparation of Catalyst has characteristics such as tap density height, active height.But magnesium halide and titan-alkoxide reaction product fail to form solution in this Preparation of catalysts process when reacting with aluminum alkyls; The magnesium-containing carrier particle form that obtains is not ideal enough; The polymkeric substance segmentation content of preparation is still more, and the hydrogen regulation performance of this catalyzer is slightly poor simultaneously.
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,, also requiring catalyzer should have better hydrogen regulation sensitivity in order to produce Alathon or multipolymer with better performance; The melting index of promptly regulating final polymkeric substance through 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; Not only catalytic activity is high for it, particle diameter evenly, narrow diameter distribution, and have better hydrogen regulation sensitivity, advantage such as the polymkeric substance tool uniform particles of its preparation, narrow diameter distribution, segmentation content are few.
Summary of the invention
The technical problem that the present invention will solve has provided a kind of catalyzer that is used for ethylene polymerization; This catalyst activity is high, particle diameter is even, narrow diameter distribution; And have better hydrogen regulation sensitivity, the polymer beads of its preparation evenly, narrow diameter distribution, segmentation content be few.
A kind of catalyst component that is used for vinyl polymerization or copolymerization, it obtains through comprising following reactions step:
(1) a kind of organo-magnesium compound, at least a organic titanic compound and the reaction of at least a boron cpd are obtained reaction product A; The general formula of described organo-magnesium compound is MgR
1 x(OR
2)
yCl
z, R wherein
1And R
2Be respectively carbonatoms and be 1～10 alkyl, x, y, z are positive integer, 0≤x≤2,0≤y≤2 and 0≤z≤1, x and y can not be 0 simultaneously, and x+y+z=2; The general formula of described organic titanic compound is Ti (OR
3)
aX
1 b, R in the formula
3For carbonatoms is 1～14 aliphatic alkyl or aromatic hydrocarbyl, X
1Be halogen, a is 1,2,3 or 4, and b is 0,1,2,3, a+b=4; The general formula of described boron cpd is R
4 xR
5 yB (OR
6)
z, R wherein
4And R
5Be respectively carbonatoms and be 1～10 alkyl or halogen, R
6For carbonatoms is 1～10 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤1 and 0≤z≤3, and x+y+z=3; In every mole of organo-magnesium compound, organic titanic compound is 1～10 mole, and boron cpd is 0.1～2 mole;
(2) reaction product A and the reaction of at least a organo-aluminium compound are obtained reaction product B; The general formula of described organo-aluminium compound is AlR
7 nX
2 3-n, R wherein
7For hydrogen or carbonatoms are 1～20 alkyl, X
2Be halogen, n is 1,2 or 3; In every mole of organo-magnesium compound, organo-aluminium compound is 0.5～10 mole;
(3) reaction product B and the reaction of at least a inorganic titanium compound are obtained the final catalyst component;
The general formula of described inorganic titanium compound is TiX
3 n, X
3Be halogen, n=4; In every mole of organo-magnesium compound, inorganic titanium compound is 0.5～10 mole.
Its formula of is MgR
1 x(OR
2)
yCl
zThe preferred R of organo-magnesium compound
1And R
2For carbonatoms is 1～10 alkyl, x, y; Z is a positive integer; 0≤x≤2,0≤y≤2 and 0≤z≤1, x and y can not be 0 simultaneously; And x+y+z=2, particular compound is like diethoxy magnesium, dibutoxy magnesium, two octyloxy magnesium, butyl octyl magnesium, magnesium ethide, dibutylmagnesium, dibutyl magnesium ethide or dioctyl magnesium.
The general formula of described organic titanic compound is Ti (OR
3)
aX
1 b, R in the formula
3For carbonatoms is 1～14 aliphatic alkyl or aromatic hydrocarbyl, X
1Be halogen, a is 1,2,3 or 4, and b is 0,1,2,3, a+b=4; Preferred four titanium alkoxides, like purity titanium tetraethoxide, four titanium butoxide, the tetramethoxy titanium, dimethoxy diethylammonium titanium, four hexyloxy titaniums, four the last of the ten Heavenly stems oxygen base titanium, benzyloxy-4 titanium, four phenoxide titaniums etc.; Four titan-alkoxides most preferably, its general formula is Ti (OR
3)
aX
1 b, R in the formula
3For carbonatoms is 1～14 aliphatic alkyl, X
1Be halogen, a is 2,3 or 4, and b is 4-a, purity titanium tetraethoxide for example, four titanium butoxide; In 1 mole of organo-magnesium compound, the consumption of organic titanic compound is generally 1～10 mole, preferred 1～4 mole.
Its general formula of described boron cpd is R
4 xR
5 yB (OR
6)
z, R wherein
4And R
5Be respectively carbonatoms and be 1～10 alkyl or halogen, R
6For carbonatoms is 1～10 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤1 and 0≤z≤3, and x+y+z=3; Preferred alkoxyl group borine, its general formula is R
4 xR
5 yB (OR
6)
z, R wherein
4And R
5Be respectively carbonatoms and be 1～10 alkyl or halogen, R
6For carbonatoms is 1～10 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤1 and 0≤z≤3, and x+y+z=3.
Particular compound comprises: trimethoxy borine, triethoxy borine, tripropoxy borine, tributoxy-boron alkane, ethyl dimethoxy borine, ethyl diethoxy borine, methyl dimethoxy oxygen base borine, methyl diethoxy borine, n-propyl diethoxy borine, n-propyl dimethoxy borine, decyl dimethoxy borine, decyl diethoxy borine, cyclopentyl dimethoxy borine, cyclopentyl diethoxy borine, 2-methylcyclopentyl dimethoxy borine, 2,3-dimethylcyclopentyl dimethoxy borine, cyclohexyl dimethoxy borine, cyclohexyl diethoxy borine, methyl dimethoxy oxygen base borine, methyl diethoxy borine, ethyl diethoxy borine, vinyl-dimethyl oxygen base borine, vinyl diethoxy borine, tertiary butyl diethoxy borine, normal-butyl dimethoxy borine, normal-butyl diethoxy borine, isobutyl-dimethoxy borine, isobutyl-diethoxy borine, cyclohexyl diethoxy borine, cyclohexyl dimethoxy borine, phenyl dimethoxy borine, diethylamino phenyl oxygen base borine, a chlorine dimethoxy borine, a chlorine diethoxy borine, ethyl diisopropoxy borine, vinyl dibutoxy borine, dimethyl phenoxy borine, methyl two allyloxy borines, vinyl diacetoxyl borine, dimethyl-one methoxyl group borine, dimethyl-one oxyethyl group borine, di-isopropyl one methoxyl group borine, di-isopropyl one oxyethyl group borine, tertiary butyl methyl one methoxyl group borine, tertiary butyl methyl one oxyethyl group borine, tert-pentyl methyl one oxyethyl group borine, two cyclopentyl, one methoxyl group borine, two cyclopentyl, one oxyethyl group borine, methylcyclopentyl one oxyethyl group borine, methylcyclopentyl one methoxyl group borine, phenylbenzene one methoxyl group borine, phenylbenzene one oxyethyl group borine, aminomethyl phenyl one oxyethyl group borine, aminomethyl phenyl one methoxyl group borine, two o-tolyl one methoxyl group borine, two o-tolyl one oxyethyl group borine, two between tolyl one methoxyl group borine, two between wherein one or more such as tolyl one oxyethyl group borine, biconjugate tolyl one methoxyl group borine, biconjugate tolyl one oxyethyl group borine mix and use; Wherein preferred trimethoxy borine, triethoxy borine, tripropoxy borine and tributoxy-boron alkane, most preferably triethoxy borine; In 1 mole of magnesium compound, the consumption of boron cpd is generally 0.1～2 mole, preferred 0.1～1 mole.
Among the present invention, the boron cpd that in the solid titanium catalyst component that finally obtains, should contain q.s is to improve the over-all properties of catalyzer, and boron cpd also plays the effect of the precipitation additive that promotes the moulding of granules of catalyst precipitating simultaneously.In addition, also can adopt other the compound that in preparation process, can generate above-mentioned boron compound.
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 verivate thereof; Alkane comprises a kind of in straight-chain paraffin, branched paraffin or the naphthenic hydrocarbon of 3～20 carbon or their mixture, like 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.
The general formula of described organo-aluminium compound is AlR
7 nX
2 3-n, R in the formula
7For hydrogen or carbonatoms are 1～20 alkyl, these groups can be the same or different, X
2Being halogen, can be that the same halogen atom also can be different halogen atom.These compounds comprise, triethyl aluminum, aluminium diethyl monochloride, dichloro one aluminium triethyl, sesquialter aluminium triethyl, dichloro aluminium isobutyl, triisobutyl aluminium, a chlorine di-isopropyl aluminium, a chloromethyl n-propyl aluminium, a chlorodiphenyl base aluminium etc.; Wherein preferred sesquialter aluminium triethyl, aluminium diethyl monochloride, dichloro one aluminium triethyl; In 1 mole of organo-magnesium compound, the consumption of organo-aluminium compound is generally 0.5～10 mole, preferred 1～5 mole.
A kind of or its mixture in the preferred titanium tetrachloride of described inorganic titanium compound, titanium tetrabromide and the titanium tetra iodide; In 1 mole of organo-magnesium compound, the consumption of described inorganic titanium compound is generally 0.5～10 mole, preferred 1～5 mole.
The above-mentioned catalyst component of the present invention can adopt following method preparation:
(1) organo-magnesium compound and organic titanic compound are formed clear solution in the presence of inert diluent, preferred 60～150 ℃ of solvent temperature with the boron cpd reaction regular hour, obtains reaction product A then;
(2) under suitable temperature, in preferred 0 ℃～70 ℃, reaction product A and organo-aluminium compound are carried out contact reacts under agitation condition, after the reaction regular hour, obtaining reaction product B with the inert diluent washing is the good carrier granule of particle form;
(3) under suitable temperature; In preferred 0 ℃～100 ℃, reaction product B and inorganic titanium compound are carried out contact reacts, and mixture is warming up to 60 ℃～110 ℃; After the reaction regular hour; Remove unreacted reactant and solvent, and adopt the inert diluent washing, obtain catalyst component of the present invention (1).
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 terminal olefin, and terminal olefin wherein comprises propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, vinylbenzene, vinyl toluene etc.; It is that general formula is AlR with catalyst component (2) that this catalyzer comprises above-mentioned catalyst component of the present invention (1)
8 nX
4 3-nThe reaction product of organo-aluminium compound, R in the formula
8For hydrogen, carbonatoms 1～20 alkyl, particularly alkyl, aralkyl, aryl; X
4Be halogen, particularly chlorine and bromine; N is the number of 0＜n≤3.Particular compound is like trimethylaluminium, 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, dichloro one aluminium triethyl etc.; 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 in the component (2), preferred 20～200.
Slurry polymerization can be adopted during polymerization, also vapour phase polymerization can be adopted.
The slurry 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 has advantages such as advantages of high catalytic activity, better hydrogen regulation sensitivity and narrow grain size distribution of polymers, segmentation content are few, is highly suitable for slurry polymerization process of ethylene and needs in the polymerization mix technology of high activated catalyst.
Embodiment
Testing method:
1, the size-grade distribution of catalyzer: MASTERSIZE particles distribution instrument, normal hexane be as dispersion agent, useful range 0.02～2000 μ m
2, the relative weight per-cent of element (Mg, Ti) in the catalyst system: plasma emission spectrum (ICP)
3, the relative weight per-cent of chlorine element in the catalyst system: silver nitrate titration method
4, the relative weight per-cent of element silicon in the catalyst system: X-ray fluorometry
5, the mensuration of melting index: ASTM-D 1238
6, the mensuration of tap density: DIN-53194
With embodiment the present invention is described below, but and unrestricted invention scope.
Embodiment 1
(1) preparation of catalyst component: in the reactor drum of fully replacing through high pure nitrogen; Add 4.0g (0.035mol) diethoxy magnesium successively; Under stirring, 60ml toluene, 8.0g (0.035mol) purity titanium tetraethoxide be warming up to 140 ℃ of reactions 4 hours, after solid dissolves the solution that forms homogeneous fully.Be cooled to 45 ℃, drip 1.31g (0.009mol) triethoxy borine, react 0.5 hour, slowly dripping 114ml concentration is the dichloro one aluminium triethyl toluene solution of 2M, dropwise the back and keep reaction 1 hour at 45 ℃, after be warmed up to 60 ℃ and continue to react 1 hour.This system is cooled to 30 ℃, lets solid precipitation, filter out filtrating, and, in solids, add the 60ml hexane and stir, slowly drip the 40ml titanium tetrachloride, 30 ℃ of reactions 1 hour with 60ml hexane wash solid twice.Stop to stir, leave standstill, the very fast layering of suspension-s extracts the upper strata stillness of night, 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 is seen table 1.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, adds the 1L hexane; The triethyl aluminum 1.0ml of concentration 1M adds the solid catalyst of above-mentioned preparation, is warming up to 70 ℃; Feeding hydrogen makes the still internal pressure reach 0.50Mpa; Feed ethene again and make the interior stagnation pressure of still reach 1.0Mpa (gauge pressure), polymerization is 2 hours under 90 ℃ of conditions, and polymerization result is seen table 1.
Embodiment 2
(1) catalyzer is synthetic with embodiment 1.Just purity titanium tetraethoxide 8.0g (0.035mol) changes four titanium butoxide 11.9g (0.035mol) into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result is seen table 1.
Embodiment 3
(1) catalyzer is synthetic with embodiment 1.Just dichloro one aluminium triethyl changes the dichloro aluminium isobutyl into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result is seen table 1.
Embodiment 4
(1) catalyzer is synthetic with embodiment 2.Just dichloro one aluminium triethyl changes the dichloro aluminium isobutyl into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result is seen table 1.
Embodiment 5
(1) catalyzer is synthetic with embodiment 2.Just the triethoxy borine changes tributoxy-boron alkane into, and consumption is 3.4ml (0.0126mol).
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result is seen table 1.
Comparative Examples 1
(1) the synthetic CN85105150 embodiment 1 said method of pressing of catalyst component prepares.
(2) the vinyl polymerization condition is with embodiment 1, and polymerization result is seen table 1.
Comparative Examples 2
(1) catalyzer is synthetic with embodiment 2.Just do not add the triethoxy borine.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result is seen table 1.
Can find out that from the aggregated data of table 1 under same polymerizing condition, catalyst activity of the present invention is higher, hydrogen regulation performance is better, and gained polymeric size distribution is narrower, and it is all less to cross thick or meticulous particle in the polymkeric substance.
Table 1
Claims (14)
1. catalyst component that is used for ethylene polymerization, it obtains through comprising following reactions step:
(1) a kind of organo-magnesium compound, at least a organic titanic compound and the reaction of at least a boron cpd are obtained reaction product A;
The general formula of described organo-magnesium compound is MgR
1 x(OR
2)
yCl
z, R wherein
1And R
2Be respectively carbonatoms and be 1～10 alkyl, x, y, z are positive integer, 0≤x≤2,0≤y≤2 and 0≤z≤1, x and y can not be 0 simultaneously, and x+y+z=2;
The general formula of described organic titanic compound is Ti (OR
3)
aX
1 b, R in the formula
3For carbonatoms is 1～14 aliphatic alkyl or aromatic hydrocarbyl, X
1Be halogen, a is 1,2,3 or 4, and b is 0,1,2,3, a+b=4;
The general formula of described boron cpd is R
4 xR
5 yB (OR
6)
z, R wherein
4And R
5Be respectively carbonatoms and be 1～10 alkyl or halogen, R
6For carbonatoms is 1～10 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤1 and 0≤z≤3, and x+y+z=3;
In every mole of organo-magnesium compound, organic titanic compound is 1～10 mole, and boron cpd is 0.1～2 mole;
(2) reaction product A and the reaction of at least a organo-aluminium compound are obtained reaction product B; The general formula of described organo-aluminium compound is AlR
7 nX
2 3-n, R wherein
7For hydrogen or carbonatoms are 1～20 alkyl, X
2Be halogen, n is 1,2 or 3; In every mole of organo-magnesium compound, organo-aluminium compound is 0.5～10 mole;
(3) reaction product B and the reaction of at least a inorganic titanium compound are obtained the final catalyst component; The general formula of described inorganic titanium compound is TiX
3 n, X
3Be halogen, n=4; In every mole of organo-magnesium compound, inorganic titanium compound is 0.5～10 mole.
2. the catalyst component that is used for ethylene polymerization according to claim 1; The consumption that it is characterized in that each reactant is in every mole of organo-magnesium compound; Organic titanic compound is 1～4 mole; Boron cpd is 0.1～1 mole, and organo-aluminium compound is 1～5 mole, and inorganic titanium compound is 1～5 mole.
3. the catalyst component that is used for ethylene polymerization according to claim 1 is characterized in that described organic titanic compound general formula is Ti (OR
3)
aX
1 b, R in the formula
3For carbonatoms is 1～14 aliphatic alkyl, X
1Be halogen, a is 2,3 or 4, and b is 4-a.
4. the catalyst component that is used for ethylene polymerization according to claim 1 is characterized in that described organic titanic compound is selected from purity titanium tetraethoxide or four titanium butoxide.
5. the catalyst component that is used for ethylene polymerization according to claim 1 is characterized in that described boron cpd general formula is R
4 xR
5 yB (OR
6)
z, R wherein
4And R
5Be respectively carbonatoms and be 1～10 alkyl or halogen, R
6For carbonatoms is 1～10 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤1 and 0≤z≤3, and x+y+z=3.
6. the catalyst component that is used for ethylene polymerization according to claim 1 is characterized in that described boron cpd is selected from least a in trimethoxy borine, triethoxy borine, tripropoxy borine and the tributoxy-boron alkane.
7. the catalyst component that is used for ethylene polymerization according to claim 1 is characterized in that described organo-aluminium compound is selected from sesquialter aluminium triethyl, aluminium diethyl monochloride or dichloro one aluminium triethyl.
8. the catalyst component that is used for ethylene polymerization according to claim 1 is characterized in that described inorganic titanium compound is selected from least a in titanium tetrachloride, titanium tetrabromide and the titanium tetra iodide.
9. the catalyst component that is used for ethylene polymerization according to claim 1, the general formula that it is characterized in that described organo-magnesium compound is MgR
1 x(OR
2)
yCl
z, R wherein
1And R
2Be respectively carbonatoms and be 1～10 alkyl, x, y, z are positive integer, 0≤x≤2,0≤y≤2 and 0≤z≤1, x and y can not be 0 simultaneously, and x+y+z=2.
10. the catalyst component that is used for ethylene polymerization according to claim 1 is characterized in that described organo-magnesium compound is selected from diethoxy magnesium, dibutoxy magnesium, two octyloxy magnesium, butyl octyl magnesium, magnesium ethide, dibutylmagnesium, dibutyl magnesium ethide or dioctyl magnesium.
11. the described a kind of preparation method who is used for the catalyst component of ethylene polymerization of claim 1, it may further comprise the steps:
(1) with organo-magnesium compound and organic titanic compound, in the presence of inert diluent, form clear solution, solvent temperature is 60 ℃～150 ℃, obtains reaction product A with the boron cpd reaction then;
(2), reaction product A and organo-aluminium compound are reacted under agitation condition, with obtaining reaction product B after the inert diluent washing at 0 ℃～70 ℃;
(3) at 0 ℃～100 ℃, reaction product B and inorganic titanium compound are reacted, and mixture is warming up to 60 ℃～110 ℃, remove unreacted reactant and solvent, and adopt the inert diluent washing, obtain final reacting product.
12. a catalyzer that is used for ethylene polymerization, it comprises the reaction product of following component:
(1) the described catalyst component of one of claim 1-10;
(2) general formula is AlR
8 nX
4 3-nOrgano-aluminium compound, R wherein
8For hydrogen or carbonatoms are 1～20 alkyl, X
4Be halogen, n is 1,2 or 3.
13. the catalyzer that is used for ethylene polymerization according to claim 12, wherein the mol ratio of the middle titanium of aluminium and component (1) is 5～500 in the component (2).
14. the catalyzer that is used for ethylene polymerization according to claim 12, wherein the mol ratio of the middle titanium of aluminium and component (1) is 20～200 in the component (2).
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Application publication date: 20120208 |