CN101633705A - 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 organic silicon compound. The organic silicon compound is selected from at least one of structural formula A, structural formula B and structural formula C. The catalyst production of the invention has simple reclaiming process; and when the catalyst is used for ethylene slurry polymerization, the catalyst has the advantages of high catalytic activity, even grain diameter, narrow grain diameter distribution and better hydrogen regulation sensitivity.
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 a kind of catalyst component, catalyst component preparation method and catalyzer that contain with silicoorganic compound of special construction.
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.
For example, in patent CN1229092, be carrier with the magnesium chloride, titanium tetrachloride is an active ingredient, the Preparation of catalysts method is as follows: earlier with MgCl
2Be dissolved in the solvent system, form homogeneous transparent solution, then the precipitation additive phthalic anhydride exist and low temperature under with TiCl
4Reaction is separated out solid catalyst by slow intensification.When the catalyst component that makes was used for vinyl polymerization, though the particle form of polymkeric substance is better, the hydrogen response and the catalytic activity of catalyzer were unsatisfactory.Simultaneously, when synthetic this catalyzer, need adopt organism such as phthalic anhydride as precipitation additive promoting sedimentary separating out, and need to add a large amount of titanium tetrachlorides.Therefore not only the existence of acid anhydrides produces adverse influence to catalyzer, and the use of simultaneously a large amount of titanium tetrachlorides also can cause a large amount of wastes and pollution.This kind system also is clamminess easily simultaneously, and catalyzer is difficult to preparation.
Second kind is that the catalyst activity component directly is carried on inert support, and as on the silica gel etc., because the particle diameter of silica gel controls easily, and particle form is better, therefore can obtain evengranular catalyst particle.But because the charge capacity of active ingredient is restricted on the carrier, therefore titanium content is lower in the catalyzer that makes of this method, and polymerization activity is not high.For example: in patent CN1268520, be carrier with magnesium chloride, silicon-dioxide, titanium tetrachloride is an active ingredient, and the Preparation of catalysts method is as follows: with MgCl
2In THF with TiCl
4Reaction is again with the SiO that handled through aluminum alkyls
2Mix, make catalyst component after removing THF, when being used for vinyl polymerization, because the titanium content in the catalyzer is lower, so polymerization activity is lower.Therefore, though this catalyst system can be used for the gas-phase fluidized bed polymerization process of ethene, because lower catalytic activity is difficult to be applicable in the slurry polymerization process of ethylene.
As everyone knows, in slurry polymerization process of ethylene, except that requiring catalyzer should have advantages of high catalytic activity and preferably the size distribution, in order to produce Alathon or multipolymer with better performance, also require catalyzer should have better hydrogen regulation sensitivity, i.e. melting index of regulating final polymkeric substance by hydrogen dividing potential drop in the polymerization process at an easy rate is to obtain the polyvinyl resin of the different commercial trades mark.And the hydrogen response of above-mentioned catalyst system is also unsatisfactory.
Application number is that 200510117428.5 Chinese patent discloses a kind of catalyzer that is used for ethylene polymerization, its have high reactivity, particle diameter evenly, advantage point such as narrow diameter distribution.But we find, in the Industrial processes of catalyzer, because this catalyzer has added the more lower boiling silicoorganic compound of tetraethoxy one class, recovery process in Catalyst Production, easily and titanium tetrachloride together azeotropic steam, the titanium tetrachloride purity that reclaims use is decreased, therefore, be starved of the defective that provides a kind of new catalyzer to avoid described catalyzer to exist.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst component and catalyzer thereof that is used for vinyl polymerization or copolymerization, this catalyzer has advantages such as advantages of high catalytic activity, better hydrogen regulation sensitivity and narrow grain size distribution of polymers.
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) silicoorganic 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;
Silicoorganic compound described in the component (4) are selected from least a among following structural formula A, structural formula B and the structural formula C:
In structural formula A, R
1, R
2, R
3And R
4Be respectively carbonatoms and be 1～10 aliphatic group, carbonatoms and be 3～10 alicyclic hydrocarbon radical, carbonatoms and be 6～10 aryl and derivative thereof, R
5And R
6It for carbonatoms 1～10 aliphatic group;
In structural formula B, R
1, R
2, R
3And R
4For carbonatoms is 1～10 aliphatic group, R
5And R
6Be respectively carbonatoms and be 1～10 aliphatic group, carbonatoms and be 3～10 alicyclic hydrocarbon radical, carbonatoms and be 6～10 aryl and derivative thereof;
In structural formula C, R
1, R
2, R
3, R
4, R
5And R
6It for carbonatoms 1～10 aliphatic group.
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 halogenated aliphatic 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.
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.
Organic alcohol compound described in the component (3) comprises that carbonatoms is that the straight chain of 1-10, branched alkyl alcohol that carbonatoms is 3-10 or cycloalkanol, carbonatoms are 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.
The represented silicoorganic compound of general formula in the component (4) comprise: the hexa methoxy sily oxide, six oxyethyl group sily oxide, six propoxy-sily oxide, six butoxy sily oxide, six (2-ethyl hexyl oxy) sily oxide, 1,1,3,3-tetramethyl--dimethoxy sily oxide, 1,1,3,3-tetramethyl--diethoxy sily oxide, 1,1,3,3-tetramethyl--dibutoxy sily oxide, 1,1,3,3-tetramethyl--two octyloxy sily oxide, 1,1,3,3-tetraethyl--dimethoxy sily oxide, 1,1,3,3-tetraethyl--diethoxy sily oxide, 1,1,3,3-tetraethyl--dibutoxy sily oxide, 1,1,3,3-tetraethyl--two octyloxy sily oxide, 1,1,3,3-tetrem thiazolinyl-dimethoxy sily oxide, 1,1,3,3-tetrem thiazolinyl-diethoxy sily oxide, 1,1,3,3-tetrem thiazolinyl-dibutoxy sily oxide, 1,1,3,3-tetrem thiazolinyl-two octyloxy sily oxide, 1,1,3,3-tetrapropyl-dimethoxy sily oxide, 1,1,3,3-tetrapropyl-diethoxy sily oxide, 1,1,3,3-tetrapropyl-dibutoxy sily oxide, 1,1,3, the 3-tetrabutyl-dimethoxy sily oxide, 1,1,3, the 3-tetrabutyl-diethoxy sily oxide, 1,1,3, the 3-tetrabutyl-dibutoxy sily oxide, 1,1,3,3-tetra-tert-dimethoxy sily oxide, 1,1,3,3-tetra-tert-diethoxy sily oxide, 1,1,3,3-tetra-tert-dibutoxy sily oxide, 1,1,3,3-Fourth Ring amyl group-dimethoxy sily oxide, 1,1,3,3-Fourth Ring amyl group-diethoxy sily oxide, 1,1,3,3-Fourth Ring amyl group-dibutoxy sily oxide, 1,1,3,3-Fourth Ring hexyl-dimethoxy sily oxide, 1,1,3,3-Fourth Ring hexyl-diethoxy sily oxide, 1,1,3,3-Fourth Ring hexyl-dibutoxy sily oxide, 1,1,3,3-four decyls-dimethoxy sily oxide, 1,1,3,3-four decyls-diethoxy sily oxide, 1,1,3,3-tetraphenyl-diethoxy sily oxide, 1,1,3,3-tetraphenyl-diethoxy sily oxide, 1,1,3,3-tetramethoxy-dimethyl sily oxide, 1,1,3,3-tetraethoxy-dimethyl sily oxide, 1,1,3,3-four butoxy-dimethyl sily oxide, 1,1,3,3-four octyloxies-dimethyl sily oxide, 1,1,3,3-tetramethoxy-diethyl sily oxide, 1,1,3,3-tetraethoxy-diethyl sily oxide, 1,1,3,3-four butoxy-diethyl sily oxide, 1,1,3,3-tetraethoxy-dimethyl sily oxide, 1,1,3,3-tetramethoxy-dipropyl sily oxide, 1,1,3,3-tetraethoxy-dipropyl sily oxide, 1,1,3,3-four butoxy-dipropyl sily oxide, 1,1,3,3-four octyloxies-dipropyl sily oxide, 1,1,3,3-tetramethoxy-two chloropropyl sily oxide, 1,1,3,3-tetraethoxy-two chloropropyl sily oxide, 1,1,3,3-four butoxy-two chloropropyl sily oxide, 1,1,3,3-four octyloxies-two chloropropyl sily oxide, 1,1,3,3-tetramethoxy-dibutyl sily oxide, 1,1,3,3-tetraethoxy-dibutyl sily oxide, 1,1,3,3-four butoxy-dibutyl sily oxide, 1,1,3,3-four octyloxies-dibutyl sily oxide, 1,1,3,3-tetramethoxy-di-t-butyl sily oxide, 1,1,3,3-tetraethoxy-di-t-butyl sily oxide, 1,1,3,3-four butoxy-di-t-butyl sily oxide, 1,1,3,3-four octyloxies-di-t-butyl sily oxide, 1,1,3,3-tetramethoxy-two cyclopentyl sily oxide, 1,1,3,3-tetraethoxy-two cyclopentyl sily oxide, 1,1,3,3-four butoxy-two cyclopentyl sily oxide, 1,1,3,3-four octyloxies-two cyclopentyl sily oxide, 1,1,3,3-tetramethoxy-dicyclohexyl sily oxide, 1,1,3,3-tetraethoxy-dicyclohexyl sily oxide, 1,1,3,3-four butoxy-dicyclohexyl sily oxide, 1,1,3,3-four octyloxies-dicyclohexyl sily oxide, 1,1,3,3-tetramethoxy-phenylbenzene sily oxide, 1,1,3,3-tetraethoxy-phenylbenzene sily oxide, 1,1,3,3-four butoxy-phenylbenzene sily oxide, 1,1,3,3-four octyloxies-phenylbenzene sily oxide, 1,1,3,3-tetramethoxy-methylethyl sily oxide, 1,1,3,3-tetramethoxy-methyl chloride propyl group sily oxide, 1,1,3,3-tetramethoxy-methyl-propyl sily oxide, 1,1,3,3-tetramethoxy-methyl butyl sily oxide, 1,1,3,3-tetramethoxy-methyl tertbutyl sily oxide, 1,1,3,3-tetramethoxy-methylcyclopentyl sily oxide, 1,1,3,3-tetramethoxy-methylcyclohexyl sily oxide, 1,1,3,3-tetramethoxy-aminomethyl phenyl sily oxide, 1,1,3,3-tetraethoxy-methylethyl sily oxide, 1,1,3,3-tetraethoxy-methyl chloride propyl group sily oxide, 1,1,3,3-tetraethoxy-methyl-propyl sily oxide, 1,1,3,3-tetraethoxy-methyl butyl sily oxide, 1,1,3,3-tetraethoxy-methyl tertbutyl sily oxide, 1,1,3,3-tetraethoxy-methylcyclopentyl sily oxide, 1,1,3,3-tetraethoxy-methylcyclohexyl sily oxide, 1,1,3,3-tetraethoxy-aminomethyl phenyl sily oxide, 1,1,3,3-four butoxy-methylethyl sily oxide, 1,1,3,3-four butoxy-methyl chloride propyl group sily oxide, 1,1,3,3-four butoxy-methyl-propyl sily oxide, 1,1,3,3-four butoxy-methyl butyl sily oxide, 1,1,3,3-four butoxy-methyl tertbutyl sily oxide, 1,1,3,3-four butoxy-methylcyclopentyl sily oxide, 1,1,3,3-four butoxy-methylcyclohexyl sily oxide, 1,1,3,3-four butoxy-aminomethyl phenyl sily oxide, 1,1,3,3-four octyloxies-methylethyl sily oxide, 1,1,3,3-four octyloxies-methyl chloride propyl group sily oxide, 1,1,3,3-four octyloxies-methyl-propyl sily oxide, 1,1,3,3-four octyloxies-methyl butyl sily oxide, 1,1,3,3-four octyloxies-methyl tertbutyl sily oxide, 1,1,3,3-four octyloxies-methylcyclopentyl sily oxide, 1,1,3,3-four octyloxies-methylcyclohexyl sily oxide, 1,1,3, one or more mixing wherein such as 3-four octyloxies-aminomethyl phenyl sily oxide are used.
Wherein be preferably six alkoxyl group sily oxide and four alkoxyl group dialkyl group sily oxide, as six oxyethyl group sily oxide, six butoxy sily oxide, 1,1,3,3-tetraethoxy-dimethyl sily oxide, 1,1,3,3-four butoxy-dimethyl sily oxide, 1,1,3,3-tetraethoxy-methylcyclohexyl sily oxide etc., best is six oxyethyl group sily oxide.
Among the present invention, the silicoorganic compound that should contain q.s in the solid titanium catalyst component that finally obtains are to improve the over-all properties of catalyzer, silicoorganic compound also play the effect of the precipitation additive that promotes the moulding of granules of catalyst precipitating simultaneously, do not need to add in addition normally used precipitation additive in the industry.
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 1＜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 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 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 silicide 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%, Si:0.2～1.2%wt%, OR:4.0～8.5wt%, P:0.1～1.0wt%, Al:0～0.6wt%.
The above-mentioned catalyst component of the present invention can adopt following method preparation:
A, magnesium halide is dissolved in the magnesium mixture that forms component (1) in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, solvent temperature is 40～100 ℃; 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, obtain reaction soln.
B, in the presence of component (4) silicoorganic compound, at-40 ℃～10 ℃, above-mentioned reaction soln and component (2) titanium compound are carried out contact reacts, and mixture slowly is warming up to 40～120 ℃, 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.
The present invention also provides a kind of catalyzer that is used for ethylene polymerization, 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 the polyreaction of ethene, 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, 0＜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.
Because the boiling point and the titanium tetrachloride of the sily oxide that adopts differ bigger, be difficult for forming azeotrope in the catalyzer of the present invention, the recovery process of Catalyst Production is simple.Simultaneously, this catalyzer is being used for vinyl polymerization, particularly during the ethene slurry polymerization, catalytic activity height, particle diameter evenly, narrow diameter distribution, and have 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 are warming up to 70 ℃, dissolve fully when solid behind the solution that forms homogeneous to react 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 3.0ml six oxyethyl group sily oxide 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 4.5ml1 then, 1,3,3-tetraethoxy-divinyl disiloxane 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 4.Be 1,1,3,3-tetraethoxy-divinyl disiloxane 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 4.Be 1,1,3,3-tetraethoxy-divinyl disiloxane consumption changes 7.5ml 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 six oxyethyl group sily oxide consumptions change 8.6ml 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 six oxyethyl group sily oxide replace with six butoxy sily oxide.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1 and table 2.
Embodiment 9
(1) catalyzer is synthetic with embodiment 1.Just six oxyethyl group sily oxide replace with 1,1,3,3-tetraethoxy-methylcyclohexyl sily oxide.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1 and table 2.
Embodiment 10
(1) catalyzer is synthetic with embodiment 1.Just six oxyethyl group sily oxide replace with 1,1,3,3-four butoxy-dimethyl sily oxide.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1 and table 2.
Embodiment 11
(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 68 ℃, dissolve fully when solid behind the solution that forms homogeneous and reacted 1 hour under 68 ℃ of conditions.This system is cooled to-5 ℃, slowly drips the 60ml titanium tetrachloride, add 4.5ml six oxyethyl group sily oxide 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.
Comparative Examples 1
(1) catalyzer is synthetic with embodiment 1.Just six oxyethyl group sily oxide change 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
Synthesizing of catalyzer with embodiment 1.Just do not add six oxyethyl group sily oxide.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.
Comparative Examples 3
(1) catalyzer is synthetic with embodiment 1.Just six oxyethyl group sily oxide change tetraethoxysilane into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1 and table 2.
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 silicoorganic compound with special construction, 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％) | ??Si ??(wt％) | ??OR ??(wt％) |
| Example 1 | ??6.3 | ??16.0 | ??58.8 | ??0.2 | ??6.7 |
| Example 2 | ??5.8 | ??16.0 | ??58.0 | ??0.2 | ??6.4 |
| Example 3 | ??6.2 | ??15.6 | ??59.0 | ??0.3 | ??6.5 |
| Example 4 | ??5.7 | ??16.1 | ??60.8 | ??0.3 | ??6.3 |
| Example 5 | ??5.9 | ??17.0 | ??59.0 | ??0.2 | ??6.1 |
| Example 6 | ??5.8 | ??16.2 | ??61.0 | ??0.3 | ??5.9 |
| Example 7 | ??6.0 | ??16.0 | ??60.0 | ??0.4 | ??6.4 |
| Example 8 | ??6.1 | ??16.8 | ??62.0 | ??0.2 | ??6.3 |
| Example 9 | ??5.9 | ??16.0 | ??60.0 | ??0.4 | ??6.3 |
| Example 10 | ??6.2 | ??16.0 | ??60.0 | ??0.3 | ??6.3 |
| Example 11 | ??6.0 | ??16.0 | ??59.9 | ??0.3 | ??6.2 |
| Contrast 1 | ??5.5 | ??16.0 | ??60.0 | ??/ | ??/ |
| Contrast 3 | ??4.8 | ??15.0 | ??58.6 | ??0.3 | ??6.4 |
Table 2 polymer performance
Claims (10)
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) silicoorganic 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 alkyl alcohol of 1-10, branched alkyl alcohol that carbonatoms is 3-10 or cycloalkanol or 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;
Silicoorganic compound described in the component (4) are selected from least a among following structural formula A, structural formula B and the structural formula C:
In structural formula A, R
1, R
2, R
3And R
4Be respectively carbonatoms and be 1～10 aliphatic group, carbonatoms and be 3～10 alicyclic hydrocarbon radical, carbonatoms and be 6～10 aryl and derivative thereof, R
5And R
6It for carbonatoms 1～10 aliphatic group;
In structural formula B, R
1, R
2, R
3And R
4For carbonatoms is 1～10 aliphatic group, R
5And R
6Be respectively carbonatoms and be 1～10 aliphatic group, carbonatoms and be 3～10 alicyclic hydrocarbon radical, carbonatoms and be 6～10 aryl and derivative thereof;
In structural formula C, R
1, R
2, R
3, R
4, R
5And R
6It for carbonatoms 1～10 aliphatic group.
2, the catalyst component that is used for ethylene polymerization according to claim 1 is characterized in that described component (4) silicoorganic compound are selected from least a in structural formula B and the described compound of structural formula C.
3, the catalyst component that is used for ethylene polymerization according to claim 2, it is characterized in that described silicoorganic compound are selected from six oxyethyl group sily oxide, six butoxy sily oxide, 1,1,3,3-tetraethoxy-dimethyl sily oxide, 1,1,3,3-four butoxy-dimethyl sily oxide and 1,1,3, at least a in 3-tetraethoxy-methylcyclohexyl sily oxide.
4, the catalyst component that is used for ethylene polymerization according to claim 3 is characterized in that described silicoorganic compound are six oxyethyl group sily oxide.
5, the catalyst component that is used for ethylene polymerization according to claim 1 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.
6, the catalyst component that is used for ethylene polymerization according to claim 1 is characterized in that, also comprises 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.
7, 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.
8, the catalyst component that is used for ethylene polymerization according to claim 7 is characterized in that in component (1) in every mole of magnesium halide, organic epoxy compounds is 0.3mol～4.0mol, and organo phosphorous compounds is 0.2～4.0mol.
9, the preparation method of the described catalyst component of a kind of claim 1, it may further comprise the steps:
A, magnesium halide is dissolved in the magnesium mixture that forms component (1) in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, solvent temperature is 40～100 ℃; In the process that forms component (1) magnesium mixture or at component (1) magnesium mixture, form back adding component (3) organic alcohol compound, the reaction regular hour, obtain reaction soln.
B, in the presence of component (4) silicoorganic compound, at-40 ℃～10 ℃, above-mentioned reaction soln and component (2) titanium compound are carried out contact reacts, and mixture slowly is warming up to 40～120 ℃, 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.
10, 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 1-8;
(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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| CN101845104A (en) * | 2010-05-21 | 2010-09-29 | 北京化工大学 | Olefin polymerization catalyst and preparation method thereof |
| CN101880341A (en) * | 2010-06-21 | 2010-11-10 | 中国石油天然气股份有限公司 | Ethylene homopolymerization or copolymerization catalyst, preparation and application thereof |
| CN102993343A (en) * | 2011-09-13 | 2013-03-27 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, and catalyst thereof |
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| CN101845104A (en) * | 2010-05-21 | 2010-09-29 | 北京化工大学 | Olefin polymerization catalyst and preparation method thereof |
| CN101880341A (en) * | 2010-06-21 | 2010-11-10 | 中国石油天然气股份有限公司 | Ethylene homopolymerization or copolymerization catalyst, preparation and application thereof |
| CN101880341B (en) * | 2010-06-21 | 2012-05-30 | 中国石油天然气股份有限公司 | Ethylene homopolymerization or copolymerization catalyst, preparation and application thereof |
| CN102993343A (en) * | 2011-09-13 | 2013-03-27 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, and catalyst thereof |
| CN102993343B (en) * | 2011-09-13 | 2015-05-13 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, and catalyst thereof |
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