CN101633704A - Catalyst component used for ethylene polymerization reaction and catalyst thereof - Google Patents
Catalyst component used for ethylene polymerization reaction and catalyst thereof Download PDFInfo
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Abstract
The invention relates to a catalyst component used for ethylene polymerization reaction and a catalyst thereof. The catalyst component contains magnesium composite, titanium compound, organic alcoholic compound and boron compound. The organic boron compound is selected from at least one of structural formula 1, structural formula 2 and structural formula 3. The catalyst of the invention is quite applicable for a slurry polymerization process of ethylene, and the catalyst has better hydrogen regulation sensitivity and higher catalytic activity.
Description
Technical field
The present invention relates to a kind of catalyst component of ethylene polymerization and preparation method and its catalyzer of catalyst component of being used for.In particular, relate to a kind of catalyst component, catalyst component preparation method and catalyzer that contains organic boron compound.
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 polymer particle, this fine powder easily produces static, causes " airborne dust " phenomenon, also 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.
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.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.
The inventor finds by test, introduces a kind of organoboron compound with special construction in catalyst system, not only make catalyzer have level preferably in hydrogen response and the distribution of polymkeric substance particle diameter, and catalyst activity has also had significant raising.Therefore, catalyzer of the present invention is highly suitable for slurry polymerization process of ethylene, promptly the polymkeric substance that obtains with this catalyzer not only particle diameter evenly, narrow diameter distribution, and this catalyzer has the catalytic activity of better hydrogen regulation sensitivity and Geng Gao.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst component and catalyzer thereof that is used for ethylene polymerization, this catalyzer has advantages such as higher catalytic activity, better hydrogen regulation sensitivity and narrow grain size distribution of polymers.
A kind of catalyst component that is used for vinyl polymerization or copolymerization, this catalyst component comprises the reaction product of following component:
(1) magnesium mixture;
(2) titanium compound;
(3) organic alcohol compound;
(4) organoboron compound;
Magnesium mixture described in the component (1) is that magnesium halide is dissolved in resulting product in the solvent system that contains organic epoxy compounds and organo phosphorous compounds;
Titanium compound general formula described in the component (2) is Ti (OR)
aX
b, R is C in the formula
1～C
14Aliphatic group or aryl, X is a halogen, a is 0,1 or 2, b is 1 to 4 integer, a+b=3 or 4;
Organic alcohol compound described in the component (3) is that carbonatoms is that the straight chain of 1-10, branched alkyl alcohol that carbonatoms is 3-10 or cycloalkanol, carbonatoms are that the fragrant and mellow or aralkyl of 6-20 is pure, and hydrogen atom or carbon atom in described organic alcohol can be replaced by halogen atom;
Organoboron compound described in the component (4) is selected from least a in following structural formula 1, structural formula 2 and the structural formula 3:
In structure is 1 compound, R
1For carbonatoms is the alkyl of 1-10, aryl and the derivative thereof that carbonatoms is 6-10, R
2And R
3For carbonatoms is the 1-10 alkyl; In structure is 2 compound, R
1And R
2For carbonatoms is that 1-10 alkyl, carbonatoms are 6-10 aryl and derivative thereof, R
3For carbonatoms is the 1-10 alkyl; In structure is 3 compound, R
1, R
2And R
3Being respectively carbonatoms is the 1-10 alkyl
Wherein the magnesium halide described in the component (1) 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.Be specially oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, at least a in butadiene double oxide, epoxy chloropropane, methyl glycidyl ether and the 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.Be specially 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: 0.2-10.0mol, preferred 0.3～4.0mol; Organo phosphorous compounds: 0.1～10.0mol, preferred 0.2～4.0mol.
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.
Organic alcohol compound described in the component (3) comprises that carbonatoms is that alcohol, the carbonatoms of straight chain, side chain or the cycloalkyl of 1-10 is alcohol or phenolic compound and the derivative thereof that 6-20 contains aryl, and the hydrogen atom of wherein said pure molecule 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.
Titanium compound general formula described in the component (2) 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.
Organoboron compound in the component (4) comprises: trimethyl borate, triethyl borate, tripropoxy-boron, tributyl borate, triamyl borate, boric acid three own esters, boric acid three monooctyl esters, tricyclohexyl borate, triphenyl borate, boric acid three benzyl esters, the methyl-boron-dihydroxide dimethyl ester, the methyl-boron-dihydroxide diethyl ester, the methyl-boron-dihydroxide dipropyl, the methyl-boron-dihydroxide dibutylester, the methyl-boron-dihydroxide diamyl ester, the methyl-boron-dihydroxide dihexyl, the methyl-boron-dihydroxide dioctyl ester, methyl-boron-dihydroxide two cyclohexyls, the methyl-boron-dihydroxide diphenyl ester, the methyl-boron-dihydroxide dibenzyl ester, the ethyl-boron dihydroxide dimethyl ester, the ethyl-boron dihydroxide diethyl ester, the ethyl-boron dihydroxide dipropyl, the ethyl-boron dihydroxide dibutylester, the ethyl-boron dihydroxide diamyl ester, the ethyl-boron dihydroxide dihexyl, the ethyl-boron dihydroxide dioctyl ester, ethyl-boron dihydroxide two cyclohexyls, the ethyl-boron dihydroxide diphenyl ester, the ethyl-boron dihydroxide dibenzyl ester, tertiary butyl trimethyl borate, tertiary butyl boric acid diethyl ester, tertiary butyl boric acid dipropyl, tertiary butyl boric acid dibutylester, tertiary butyl boric acid diamyl ester, tertiary butyl boric acid dihexyl, tertiary butyl boric acid dioctyl ester, tertiary butyl boric acid two cyclohexyls, tertiary butyl boric acid diphenyl ester, tertiary butyl boric acid dibenzyl ester, the phenyl-boron dihydroxide dimethyl ester, the phenyl-boron dihydroxide diethyl ester, the phenyl-boron dihydroxide dipropyl, the phenyl-boron dihydroxide dibutylester, the phenyl-boron dihydroxide diamyl ester, the phenyl-boron dihydroxide dihexyl, the phenyl-boron dihydroxide dioctyl ester, phenyl-boron dihydroxide benzene cyclohexyl, the phenyl-boron dihydroxide diphenyl ester, the phenyl-boron dihydroxide dibenzyl ester, the p-methylphenyl trimethyl borate, p-methylphenyl boric acid diethyl ester, p-methylphenyl boric acid dipropyl, p-methylphenyl boric acid dibutylester, p-methylphenyl boric acid diamyl ester, p-methylphenyl boric acid dihexyl, p-methylphenyl boric acid dioctyl ester, p-methylphenyl boric acid benzene cyclohexyl, p-methylphenyl boric acid diphenyl ester, p-methylphenyl boric acid dibenzyl ester, the phenylbenzene methyl-borate, the di-t-butyl methyl-borate, the dicyclohexyl methyl-borate, the phenylbenzene ethyl-borate, the di-t-butyl ethyl-borate, the dicyclohexyl ethyl-borate, the phenylbenzene butyl borate, the di-t-butyl butyl borate, one or more mixing wherein such as dicyclohexyl butyl borate are used.
Wherein be preferably trimethyl borate, triethyl borate, tributyl borate, phenyl-boron dihydroxide diethyl ester, cyclohexyl boric acid diethyl ester etc., best is triethyl borate and tributyl borate.
Among the present invention, should contain the organoboron compound of q.s in the solid titanium catalyst component that finally obtains, to improve the over-all properties of catalyzer, organoboron compound also plays the effect of the precipitation additive that promotes the moulding of granules of catalyst precipitating simultaneously.
This is used for the catalyst component of vinyl polymerization or copolymerization, can also comprise a kind of organo-aluminium compound of component (5), and its general formula is AlR
nX
3-n, R is that hydrogen or carbonatoms are 1～20 alkyl in the formula, and X is a halogen, and n is the number of 0＜n≤3.
The general formula of described organo-aluminium compound is AlR
nX
3-n, R is 1～20 alkyl independently for hydrogen or carbonatoms in the formula,, particularly alkyl, aralkyl or aryl; X is 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 the halogenide of preferred alkyl aluminium 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.
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: 0.1-10.0 mole, preferred 1.0-4.0 mole; Organic boride is 0.05～1.0 mole; Aluminum compound is 0～5.0 mole.Titanium compound is 1.0～15.0 moles, preferred 2.0～10.0 moles.
The content range of the composition of gained catalyzer: Ti, Mg, Cl, Si, OR, P, Al is: Ti:4.5～8.5wt%, Mg:13.0～19.0wt%, Cl:57.0～69.0wt%, B:0.2～1.2%wt%, OR:4.0～8.5wt%, P:0.1～1.0wt%, Al:0～0.6wt%.
The catalyst component that is used for vinyl polymerization or copolymerization 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, solvent temperature is 50～90 ℃; In the process that forms component (1) magnesium mixture or at component (1) magnesium mixture, form back adding component (3) organic alcohol compound, add or do not add component (5) organo-aluminium compound then, the reaction regular hour, to reaction soln, wherein in every mole of magnesium halide, the add-on of organic epoxy compounds and organo phosphorous compounds is 0.3～10.0mol and 0.1～10.0mol, and the add-on of component (3) organic alcohol compound is 0.1～10.0mol;
(2) in the presence of component (4) organoboron compound, at-40 ℃～20 ℃, above-mentioned reaction soln and component (2) titanium compound are carried out contact reacts, and mixture slowly is warming up to 50～120 ℃, particle is separated out and formed to solids gradually, after the reaction regular hour, remove unreacted reactant and solvent, and adopt inert diluent to wash, obtain catalyst component of the present invention, wherein in every mole of magnesium halide, the add-on of component (2) titanium compound and component (4) organoboron compound is respectively 1.0～15.0mol and 0.05～1.0mol.
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.
A kind of catalyzer that is used for ethylene polymerization, it comprises the reaction product of following component:
(1) the described catalyst component of claim 1;
(2) general formula is AlR
nX
3-nOrgano-aluminium compound, R is that hydrogen or carbonatoms are 1～20 alkyl in the formula, X is a halogen, 1＜n≤3.
Component (2) formula of is AlR
nX
3-nOrgano-aluminium compound, R can be 1～20 alkyl, particularly alkyl, aralkyl, aryl for hydrogen or carbonatoms in the formula; X is halogen, particularly chlorine and bromine; N is the number of 1＜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 in the component (2), preferred 20-200.
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 organoboron compound of the no reactive hydrogen of employing is a 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 organoboron 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, show better hydrogen regulation sensitivity.
Embodiment
With embodiment the present invention is described below, but and unrestricted invention scope.
Testing method:
Melt index: measure according to ASTM D1238-99.
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 6.0ml, tributyl phosphate 4.0ml, ethanol 5.6ml, 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 3.6ml triethyl borate 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 2.
Embodiment 2
(1) catalyzer is synthetic with embodiment 1.The ethanol consumption changes 6.9ml into by 5.6ml.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1 and table 2.
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 and table 2.
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 6.0ml, tributyl phosphate 4ml, ethanol 5.6ml, 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 4.5ml tributyl borate 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 2.
Embodiment 5
(1) catalyzer is synthetic with embodiment 1.Just the triethyl borate consumption changes 6.0ml into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1 and table 2.
Embodiment 6
(1) catalyzer is synthetic with embodiment 1.Just the triethyl borate consumption changes 2.5ml into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1 and table 2.
Embodiment 7
(1) catalyzer is synthetic with embodiment 1.Just the tributyl borate consumption changes 5.0ml into.
(2) vinyl polymerization is with embodiment 1, and catalyzer is formed and polymerization result sees Table 1 and table 2.
Embodiment 8
(1) catalyzer is synthetic with embodiment 1.Just triethyl borate changes the phenyl-boron dihydroxide diethyl ester into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1 and table 2.
Embodiment 9
(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 2.0ml, tributyl phosphate 6.0ml, ethanol 3.4ml, 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 60ml titanium tetrachloride, add the 3.0ml triethyl borate 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 2.
Embodiment 10
(1) catalyzer is synthetic with embodiment 1.Just triethyl borate changes cyclohexyl ylboronic acid diethyl ester into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1 and table 2.
Embodiment 11
(1) catalyzer is synthetic with embodiment 1.Just triethyl borate changes trimethyl borate into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1 and table 2.
Comparative Examples 1
(1) catalyzer is synthetic with embodiment 1.Just triethyl borate changes Tetra hydro Phthalic anhydride into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1 and table 2.
Comparative Examples 2
(1) catalyzer is synthetic with embodiment 1.Just do not add triethyl borate.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 organoboron 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
| Numbering | ??Ti ??(wt％) | ??Mg ??(wt％) | ??Cl ??(wt％) | ??B ??(wt％) | ??OR ??(wt％) |
| Example 1 | ??8.1 | ??16.0 | ??58.0 | ??0.2 | ??6.7 |
| Example 2 | ??7.9 | ??16.0 | ??59.0 | ??0.2 | ??6.4 |
| Example 3 | ??8.2 | ??15.0 | ??59.0 | ??0.3 | ??6.5 |
| Example 4 | ??8.6 | ??16.0 | ??59.2 | ??0.3 | ??6.3 |
| Example 5 | ??6.8 | ??17.0 | ??59.0 | ??0.2 | ??6.1 |
| Example 6 | ??7.7 | ??17.0 | ??60.0 | ??0.1 | ??5.9 |
| Example 7 | ??8.0 | ??16.0 | ??60.0 | ??0.4 | ??6.4 |
| Example 8 | ??7.9 | ??17.0 | ??58.0 | ??0.2 | ??6.3 |
| Example 9 | ??7.6 | ??16.0 | ??59.1 | ??0.4 | ??6.3 |
| Example 10 | ??7.7 | ??16.0 | ??59.0 | ??0.3 | ??6.3 |
| Example 11 | ??7.8 | ??16.2 | ??58.8 | ??0.3 | ??6.2 |
| Contrast 1 | ??5.5 | ??16.0 | ??60.0 | ??/ | ??/ |
Table 2 polymer performance
Claims (9)
1, a kind of catalyst component that is used for ethylene polymerization, this catalyst component comprises the reaction product of following component:
(1) magnesium mixture;
(2) titanium compound;
(3) organic alcohol compound;
(4) organoboron compound;
Magnesium mixture described in the component (1) is that magnesium halide is dissolved in resulting product in the solvent system that contains organic epoxy compounds and organo phosphorous compounds;
Titanium compound general formula described in the component (2) is Ti (OR)
aX
b, R is C in the formula
1～C
14Aliphatic group or aryl, X is a halogen, a is 0,1 or 2, b is 1 to 4 integer, a+b=3 or 4;
Organic alcohol compound described in the component (3) is that carbonatoms is that the straight chain of 1-10, branched alkyl alcohol that carbonatoms is 3-10 or cycloalkanol, carbonatoms are that the fragrant and mellow or aralkyl of 6-20 is pure, and hydrogen atom or carbon atom in described organic alcohol are randomly replaced by halogen atom;
Organoboron compound described in the component (4) is selected from least a in following structural formula 1, structural formula 2 and the structural formula 3:
In structure is 1 compound, R
1For carbonatoms is the alkyl of 1-10, aryl and the derivative thereof that carbonatoms is 6-10, R
2And R
3For carbonatoms is the 1-10 alkyl; In structure is 2 compound, R
1And R
2For carbonatoms is that 1-10 alkyl, carbonatoms are 6-10 aryl and derivative thereof, R
3For carbonatoms is the 1-10 alkyl; In structure is 3 compound, R
1, R
2And R
3Being respectively carbonatoms is the 1-10 alkyl.
2, the catalyst component that is used for ethylene polymerization according to claim 1 is characterized in that, described component (4) organoboron compound is selected from structural formula 3 compounds at least a.
3, the catalyst component that is used for ethylene polymerization according to claim 1, it is characterized in that described component (4) organoboron compound is selected from least a in trimethyl borate, triethyl borate, tripropoxy-boron, tributyl borate and boric acid three monooctyl esters.
4, the catalyst component of stating according to claim 1 that is used for ethylene polymerization is characterized in that in every mole of magnesium halide in the component (1), component (2) is 1.0～15.0 moles; Component (3) is 0.1～10.0 mole, and component (4) is 0.05～1.0 mole.
5, the catalyst component that is used for ethylene polymerization according to claim 1 is characterized in that also comprising a kind of organo-aluminium compound of component (5), and its general formula is AlR
nX
3-n, R is that hydrogen or carbonatoms are 1～20 alkyl in the formula, and X is a halogen, and n is the number of 1＜n≤3.
6, the catalyst component that is used for ethylene polymerization according to claim 1 is characterized in that in component (1) in every mole of magnesium halide, organic epoxy compounds is 0.2-10.0mol, and organo phosphorous compounds is 0.1～10.0mol.
7, the catalyst component that is used for ethylene polymerization according to claim 1, it is characterized in that described component (1) magnesium mixture also comprises a kind of inert diluent, described inert diluent is at least a in straight-chain paraffin, branched paraffin or the naphthenic hydrocarbon of arene compounds and 3～20 carbon.
8, the preparation method of the described catalyst component of a kind of claim 1, it may further comprise the steps:
(1) magnesium halide is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, solvent temperature is 50～90 ℃; Form back adding component (3) organic alcohol compound in the process that forms component (1) magnesium mixture or at component (1) magnesium mixture, the reaction regular hour is to reaction soln;
(2) in the presence of component (4) organoboron compound, at-40 ℃～20 ℃, above-mentioned reaction soln and component (2) titanium compound are carried out contact reacts, and mixture slowly is warming up to 50～120 ℃, particle is separated out and formed to solids gradually, after the reaction regular hour, removes unreacted reactant and solvent, and adopt the inert diluent washing, obtain catalyst component of the present invention.
9, a kind of catalyzer that is used for ethylene polymerization, it comprises the reaction product of following component:
(1) the described catalyst component of one of claim 1-7;
(2) general formula is AlR
nX
3-nOrgano-aluminium compound, R is that hydrogen or carbonatoms are 1～20 alkyl in the formula, X is a halogen, 0＜n≤3.
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