CN101274967A - Catalyst for ethylene polymerization and components thereof - Google Patents
Catalyst for ethylene polymerization and components thereof Download PDFInfo
- Publication number
- CN101274967A CN101274967A CNA2007100648851A CN200710064885A CN101274967A CN 101274967 A CN101274967 A CN 101274967A CN A2007100648851 A CNA2007100648851 A CN A2007100648851A CN 200710064885 A CN200710064885 A CN 200710064885A CN 101274967 A CN101274967 A CN 101274967A
- Authority
- CN
- China
- Prior art keywords
- compound
- carbonatoms
- ethylene polymerization
- polymerization catalysts
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a catalyst component that is used in ethane homopolymerization or copolymerization of ethane with other alpha-alkene and a preparation method thereof, wherein, the catalyst component comprises a magnesium complex substance, at least a titanium compound, at least an organic alcoholic compound with carbon atom number more than 5 and at least a reaction product of an organic silicon compound; the magnesium complex substance is prepared by dissolving a magnesium compound in a system of organic epoxy compounds and organic phosphorous compounds. The catalyst of the invention has the advantages of relatively high catalytic activity, relatively good hydrogen modulation sensibility, polymer with narrow particle diameter distribution, polymer with high stacking density, etc., and is extremely applicable to slurry polymerization technique of ethane.
Description
Technical field
The present invention relates to a kind of catalyst component that is used for vinyl polymerization or copolymerization, the preparation method of this catalyst component and the catalyzer of this catalyst component.
Technical background
As everyone knows, the catalyst body that contains the Ti/Mg mixture ties up in the poly suitability for industrialized production occupies an leading position, and its research core is nothing more than the hydrogen response of the particle form of the polymerization activity that is catalyzer, catalyzer and size distribution, catalyzer and copolymerization performance or the like.And in slurry polymerization process of ethylene, except that requiring catalyzer should have the advantages of high catalytic activity, polyvinyl size and size distribution that control is produced are crucial.At vinyl polymerization, particularly in the slurry polymerization process of ethene, be easy to produce thinner polymer particle, this fine powder easily produces static, causes " airborne dust " phenomenon, easily lumps sometimes, causes the obstruction of equipment pipe.And the effective means of the size of controlling polymers and size distribution is the particle diameter and the size distribution of control catalyst.
In the prior art, in order to obtain having the catalyzer of single-size diameter and better particle form, people adopt two following class methods to prepare catalyzer usually.
First kind is magnesium compounds such as magnesium chloride to be dissolved in obtain homogeneous solution in some solvent, and then with this solution and titanium compound and randomly electron donor mix, obtain containing the solids of magnesium, titanium and optional electron donor by sedimentary method.Obtain granules of catalyst after this solids further handled with liquid titanium compound.For example disclosed among Chinese patent CN1099041A, CN1229092A, the CN1112373A 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 Chinese patent CN1112373, magnesium compounds such as magnesium chloride are reacted with isooctyl alcohol in decane, form homogeneous solution, and then this solution mixed with titanium compound and organosilane electron donor, obtain containing the solids catalyzer of magnesium, titanium by sedimentary method, this catalyst ethylene polymerization activity is higher, hydrogen regulation performance sensitivity, polymkeric substance particle diameter narrow distribution.But this preparation method needs a large amount of titanium tetrachlorides, and the preparation cost height also can cause a large amount of wastes and pollution.Catalyzer is difficult to washing simultaneously, needs a large amount of alkane, and the polymer bulk density of its preparation simultaneously is lower, is unfavorable for the high loaded process of production equipment, and fine powder content is also higher.
Among the Chinese patent CN1229092, be carrier with the magnesium chloride and for example, titanium tetrachloride is an active ingredient, and the Preparation of catalysts method is as follows: earlier with MgCl
2Be dissolved in the solvent system, form homogeneous transparent solution, then under existence such as precipitation additive phthalic anhydride and low temperature with TiCl
4Reaction is separated out solid catalyst by slow intensification.When the catalyst component that makes was used for vinyl polymerization, though the particle form of polymkeric substance is better, the hydrogen response of catalyzer and catalytic activity were also unsatisfactory.Simultaneously, when synthetic this catalyzer, need adopt organism such as phthalic anhydride to promote sedimentary separating out, and need to add a large amount of titanium tetrachlorides as precipitation additive.Therefore not only the existence of acid anhydrides produces adverse influence to catalyzer, and the use of simultaneously a large amount of titanium tetrachlorides also can cause a large amount of wastes and pollution.This kind catalyzer more easily is clamminess in building-up process simultaneously, brings certain degree of difficulty for the control of whole preparation process, and the hydrogen response of described catalyst system is yet unsatisfactory in addition.
Second kind is that the catalyst activity component directly is carried on inert support, on silica gel etc.Because the particle diameter of silica gel is controlled 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: disclosing with magnesium chloride, silicon-dioxide in patent CN1268520 is carrier, and titanium tetrachloride is the catalyzer of active ingredient, and its preparation method is as follows: with MgCl
2In THF with TiCl
4Reaction is again with the SiO that handled through aluminum alkyls
2Mix, make catalyst component after removing THF, when being used for vinyl polymerization, because the titanium content in the catalyzer is lower, so polymerization activity is lower.Therefore, though this catalyst system can be used for the gas-phase fluidized bed polymerization process of ethene, because lower catalytic activity is difficult to be applicable in the slurry polymerization process of ethylene.
As everyone knows, in slurry polymerization process of ethylene, except that requiring catalyzer should have advantages of high catalytic activity and preferably the size distribution, in order to produce Alathon or multipolymer with better performance, also require catalyzer should have better hydrogen regulation sensitivity, i.e. melting index of regulating final polymkeric substance by hydrogen dividing potential drop in the polymerization process at an easy rate is to obtain the polyvinyl resin of the different commercial trades mark.And the hydrogen response of above-mentioned catalyst system is also unsatisfactory.
Therefore, be starved of the catalyzer that a kind of vinyl polymerization that is applicable to, particularly slurry polymerization are provided, it not only should the catalytic activity height, particle diameter evenly, narrow diameter distribution, and should have better hydrogen regulation sensitivity.
Summary of the invention
The present invention is that catalyst component and preparation method further improve and obtain in the Chinese patent application 200510117428.5.
The invention provides a kind of catalyst component that is used for vinyl polymerization or copolymerization, it comprises a kind of magnesium mixture, at least a titanium compound, at least a carbonatoms greater than 5 the organic alcohol compound and the reaction product of at least a silicoorganic compound.Catalyzer of the present invention is being used for the ethene slurry polymerization processes, showed better comprehensive performance, it has advantages of high catalytic activity, better hydrogen response and narrower advantages such as polymkeric substance particle diameter distribution, is highly suitable for slurry polymerization process of ethylene and needs in the polymerization mix technology of high activated catalyst.
Wherein said magnesium mixture is that magnesium halide is dissolved in resulting product in the solvent system that contains organic epoxy compounds and organo phosphorous compounds.
Wherein said carbonatoms can adopt general formula R greater than 5 organic alcohol compound
5CHOH represents, wherein R
5For carbonatoms greater than 4 straight chained alkyl, secondary alkyl, tertiary alkyl or cycloalkyl.Particularly, can be selected from 2-methyl amyl alcohol, 2-ethylpentanol, 2-ethyl butanol, 2-Ethylhexyl Alcohol, benzylalcohol, the xylyl alcohol one or more.Preferred R
5Be secondary alkyl or tertiary alkyl.Preferred especially 2-Ethylhexyl Alcohol compound.In every mole of magnesium halide, carbonatoms greater than 5 organic alcohol compound organic alcohol compound is: 0.1-10 mole, preferred 1-4 mole.
Also can be with the organic alcohol compound of above-mentioned higher carbon atom number and than the compound use of the organic alcohol compound of low carbon atom number.Described organic alcohol compound than low carbon atom number is that carbonatoms is the alcohol of straight chain, side chain or the cycloalkyl of 1-4.Concrete as: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol etc.Wherein preferred alcohol, butanols.The organic alcohol compound of higher carbon atom number is 1: 0.25～1: 4 with mol ratio than the organic alcohol compound of low carbon atom number.
Comparatively preferably ethanol or butanols and 2-Ethylhexyl Alcohol is composite, and in every mole of magnesium, wherein consumption of ethanol is 0～2.0 mole, and the consumption of 2-Ethylhexyl Alcohol is 0.2～3.0 mole.The organic alcohol compound of higher carbon atom number can add simultaneously or separately add with than the compound use of organic alcohol compound of low carbon atom number the time.The preferred organic alcohol compound that adds earlier than low carbon atom number is so that more effectively carry out the dissolving of magnesium halide.
Described silicoorganic compound, its general formula are R
1 xR
2 ySi (OR
3)
z, R wherein
1And R
2Be respectively alkyl or halogen, R
3Be alkyl, 0≤x≤2,0≤y≤2 and 0≤z≤4.Silicoorganic compound are 0.05～1 mole, be preferably?Concrete as tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four (2-ethyl hexyl oxy) silane, ethyl trimethoxy silane, ethyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, the n-propyl triethoxyl silane, the n-propyl Trimethoxy silane, the decyl Trimethoxy silane, the decyl triethoxyl silane, the cyclopentyl Trimethoxy silane, the cyclopentyl triethoxyl silane, 2-methylcyclopentyl Trimethoxy silane, 2,3-dimethylcyclopentyl Trimethoxy silane, cyclohexyl trimethoxy silane, the cyclohexyl triethoxyl silane, methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, tertiary butyl triethoxyl silane, the normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, the isobutyl-Trimethoxy silane, the isobutyl-triethoxyl silane, the cyclohexyl triethoxyl silane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, one chlorine Trimethoxy silane, one chlorine triethoxyl silane, ethyl three isopropoxy silane, vinyl three butoxy silanes, trimethyl phenoxysilane, methyl three allyloxy silane, vinyl nitrilotriacetic base silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diisopropyl dimethoxy silane, the di-isopropyl diethoxy silane, tertiary butyl methyl dimethoxysilane, tertiary butyl methyldiethoxysilane, the tert-pentyl methyldiethoxysilane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, the methylcyclopentyl diethoxy silane, methylcyclopentyl dimethoxy silane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, the aminomethyl phenyl diethoxy silane, aminomethyl phenyl dimethoxy silane, two o-tolyl dimethoxy silane, two o-tolyl diethoxy silanes, tolyl dimethoxy silane between two, tolyl diethoxy silane between two, biconjugate tolyl dimethoxy silane, biconjugate tolyl diethoxy silane, the trimethylammonium methoxy silane, trimethylethoxysilane, three cyclopentyl methoxy silane, three cyclopentyl Ethoxysilanes, one or more mixing wherein such as two cyclopentyl-methyl methoxy silane and cyclopentyl dimethyl methyl TMOS are used.Wherein be preferably tetramethoxy-silicane, tetraethoxysilane and four butoxy silanes.
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, and silicoorganic compound also play the effect of the precipitation additive that promotes the moulding of granules of catalyst precipitating simultaneously.Therefore, preparation also can adopt during solid catalyst other compound in preparation process to generate above-mentioned silicon compound.
Described titanium compound general formula is Ti (OR)
aX
b, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen, a is 0,1 or 2, b is 1 to 4 integer, a+b=3 or 4.A kind of or its mixture in preferred titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, titanous chloride, dichloro diethoxy titanium, trichlorine one ethanolato-titanium.In every mole of magnesium halide, titanium compound is 1～15 mole, preferred 2～10 moles.
Can also randomly include machine aluminium compound in the reactant of the catalyst component that the present invention is above-mentioned, its general formula is AlR
4 nX
1 3-n, R in the formula
4For hydrogen or carbonatoms are 1～20 alkyl, X
1Be halogen, n is the number of 1＜n≤3.
Magnesium mixture of the present invention is that magnesium dihalide is dissolved in the mixture that forms in the solvent system that contains organic epoxy compounds and organo phosphorous compounds.Common this mixture should be the solution of a homogeneous transparent.
Wherein said magnesium halide is selected from the complex compound, magnesium dihalide molecular formula of the water of magnesium dihalide, magnesium dihalide or alcohol one of them or two halogen atoms by alkyl or halogen-oxyl institute metathetical derivative.Concrete compound is as magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium etc., wherein preferred magnesium dichloride.Described halogenated magnesium compound can be used alone or as a mixture.
Organic epoxy compounds described in the solvent system is selected from least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halo fat group alkene or diolefine of carbonatoms.Such as, but be not limited to: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether.
Organo phosphorous compounds described in the solvent system is the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.Concrete as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or phosphorous acid benzene methyl.Wherein in every mole of magnesium halide: organic epoxy compounds: 0.2-10mol, preferred 0.3～4mol; Organo phosphorous compounds: 0.1～10mol, preferred 0.2～4mol mol.
In order to make dissolving more abundant, in this solvent system, can randomly add inert diluent, common this inert diluent comprises arene compounds or alkane derivative, and arene compounds comprises benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, monochlorotoluene and derivative thereof; Alkane comprises a kind of in straight-chain paraffin, branched paraffin or the naphthenic hydrocarbon of 3～20 carbon or their mixture, as butane, and pentane, hexane, hexanaphthene, heptane etc. are as long as help the magnesium halide dissolved to use.Above-mentioned inert diluent can use separately, use also capable of being combined.
At the catalyst component that is used for vinyl polymerization or copolymerization of the present invention, in every mole of magnesium halide, organic alcohol compound is: 0.1-10 mole, preferred 1-4 mole; Silicoorganic compound are 0.05～1 mole, preferred 0.1-0.5 mole; Titanium compound is 1～15 mole, preferred 2～10 moles.
The above-mentioned catalyst component of the present invention can adopt following method preparation:
(1) magnesium halide is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, preferably in solvent system, adds inert diluent, form homogeneous solution, the preferred 50-90 of solvent temperature ℃; In forming the process of described homogeneous solution or add alkylol cpd afterwards, with a kind of solution of final formation;
(2) under lower temperature, under the temperature in preferred-40 ℃ of-20 ℃ of scopes, the solution that step (i) is obtained contacts with titanium compound, before this contact, in the process or add silicon compound afterwards, obtains a kind of mixture;
(3) described mixture slowly is warming up to 60 ℃-110 ℃, particle is separated out and formed to solids gradually; With
(4) reclaim catalyst component of the present invention; After the reaction regular hour, remove unreacted reactant and solvent, and adopt the inert diluent washing, obtain catalyst component of the present invention.
Other content range of the branch of the composition of gained catalyst component of the present invention: Ti, Mg, Cl, Si, OEt, P: Ti=4.5～7.5% (wt); Mg=14～19% (wt); Cl=58～68% (wt); Si=0.2～1.2% (wt); OEt=4.0～8.5% (wt); P=0.1～3.0% (wt).
The present invention also provides a kind of ethylene polymerization catalysts that is used for, and it is AlR with (2) general formula that this catalyzer comprises (1) above-mentioned catalyst component of the present invention
6 nX
2 3-nThe reaction product of organoaluminum promotor, R in the formula
6Can be 1～20 alkyl, particularly alkyl, aralkyl, aryl for hydrogen, carbonatoms; X
2Be halogen, particularly chlorine and bromine; N is the number of 0＜n≤3.
The example of described organoaluminum promotor comprises: 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 dichloride etc., wherein preferred trialkyl aluminium compound, especially with triethyl aluminum, triisobutyl aluminium for well.Described organoaluminum promotor can be used in combination separately or mutually.
In catalyzer of the present invention, the mol ratio of the middle titanium of aluminium and component (1) is 5～500 in the component (2), preferred 20～200.
In addition, the invention provides a kind of ethene polymerization method, this method comprises:
(i) ethene and optional at least a comonomer are contacted under polymerizing condition with catalyzer of the present invention, to form polymkeric substance; With
The (ii) polymkeric substance that forms in the recycling step (i).
Described comonomer can be selected from the alpha-olefin and the diolefine of 3-20 carbon atom.The example of described alpha-olefin comprises propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, vinylbenzene, vinyl toluene etc.The example of described diolefine comprises Dicyclopentadiene (DCPD), vinyl norbornene, 5-ethylidene-2-norbornene etc.
Described polymerization process can carry out in liquid phase or gas phase.Catalyzer of the present invention is particularly suitable for slurry polymerization processes, perhaps comprises the polymerization mix technology of slurry polymerization, for example slurry addition gas-phase polymerization process.
The example of the medium that liquid polymerization is adopted comprises: propane, 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 separated out granules of catalyst in the preparation at an easy rate, does not need to use a large amount of titanium tetrachlorides to impel sedimentary separating out, and also do not need repeatedly to use titanium tetrachloride to handle precipitation, so the add-on of titanium tetrachloride significantly reduces.The catalyzer that this invention simultaneously prepares has improved the particle of catalyzer and has advised the particle form of just spending and further improving polymkeric substance.When catalyzer is used for vinyl polymerization, shown better hydrogen regulation sensitivity.
Embodiment
With embodiment the present invention is described below, but and unrestricted invention scope.
Embodiment 1
(1) preparation of catalyst component: in the reactor of fully replacing through high pure nitrogen, add the 4.0g magnesium dichloride successively, toluene 60ml, epoxy chloropropane 2.0ml, tributyl phosphate 6.0ml, ethanol 3.4ml, be warming up to 65 ℃ under stirring, dissolve the solution of formation homogeneous fully when solid after, drip 2-Ethylhexyl Alcohol 5.5ml (ethanol and 2-Ethylhexyl Alcohol mol ratio are 1.4: 1.0).
Reaction is 1 hour under 65 ℃ of conditions.This system is cooled to-5 ℃, slowly drips the 60ml titanium tetrachloride, add the 3ml tetraethoxysilane then, reacted 0.5 hour.Slowly be warming up to 85 ℃, reacted 2 hours.Stop to stir, leave standstill, the very fast layering of suspension extracts the upper strata stillness of night, uses the hexane wash solid, with high pure nitrogen it is dried up again, obtains good fluidity, the narrower solid catalyst solid particulate of size distribution.The catalyzer composition sees Table 1.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M adds catalyzer (containing 0.3 milligram of titanium) the solid hexane solution of above-mentioned preparation, is warming up to 70 ℃, feeding hydrogen makes the still internal pressure reach 0.28Mpa, feed ethene again and make the interior stagnation pressure of still reach 0.73Mpa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 2
(1) catalyzer is synthetic with embodiment 1.Just change the 2-Ethylhexyl Alcohol consumption into 7.7ml (ethanol and 2-Ethylhexyl Alcohol mol ratio are 1.4: 1.4) by 5.5ml.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1.
Embodiment 3
(1) catalyzer is synthetic with embodiment 2.Just change the 2-Ethylhexyl Alcohol consumption into 3.3ml (ethanol and 2-Ethylhexyl Alcohol mol ratio are 1.4: 0.6).
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1.
Embodiment 4
(1) catalyzer is synthetic with embodiment 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 0.5 milligram of titanium) the solid hexane solution of above-mentioned preparation, is warming up to 70 ℃, feeding hydrogen makes the still internal pressure reach 0.38Mpa, feed ethene again and make the interior stagnation pressure of still reach 0.73Mpa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 5
(1) catalyzer is synthetic with embodiment 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 0.8 milligram of titanium) the solid hexane solution of above-mentioned preparation, is warming up to 70 ℃, feeding hydrogen makes the still internal pressure reach 0.48Mpa, feed ethene again and make the interior stagnation pressure of still reach 0.73Mpa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 6
(1) catalyzer is synthetic with embodiment 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 1.3 milligrams of titaniums) the solid hexane solution of above-mentioned preparation, is warming up to 70 ℃, feeding hydrogen makes the still internal pressure reach 0.58Mpa, feed ethene again and make the interior stagnation pressure of still reach 0.73Mpa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Embodiment 7
(1) catalyzer is synthetic with embodiment 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 1.8 milligrams of titaniums) the solid hexane solution of above-mentioned preparation, is warming up to 70 ℃, feeding hydrogen makes the still internal pressure reach 0.68Mpa, feed ethene again and make the interior stagnation pressure of still reach 0.73Mpa (gauge pressure), polymerization is 2 hours under 80 ℃ of conditions, and polymerization result sees Table 1.
Comparative Examples 1
(1) preparation of catalyst component: with the 4 Preparation of catalysts methods of embodiment among the Chinese patent application Appl.200510117428.5.In the reactor of fully replacing through high pure nitrogen, add the 4.03g magnesium dichloride successively, toluene 50ml, epoxy chloropropane 4.0ml, tributyl phosphate 4ml, ethanol 6.4ml stir down and are warming up to 70 ℃, dissolve fully when solid behind the solution that forms homogeneous to react 1 hour under 70 ℃ of conditions.This system is cooled to-5 ℃, slowly drips the 40ml titanium tetrachloride, add the 3ml tetraethoxysilane then, reacted 1 hour.Slowly be warming up to 80 ℃, reacted 2 hours.Stop to stir, leave standstill, the very fast layering of suspension extracts the upper strata stillness of night, twice of toluene wash, hexane wash four times, and high pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution.
(2) vinyl polymerization is with embodiment 1.Polymerization result sees Table 1.
Comparative Examples 2～5
(1) catalyzer is synthetic with Comparative Examples 1.
(2) vinyl polymerization is respectively with embodiment 4～7, and catalyzer is formed and polymerization result sees Table 1.
Comparative Examples 6
(1) preparation of catalyst component is with embodiment 1 Preparation of catalysts method in the Chinese patent CN1112373 patent.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result sees Table 1.
Table 1
As can be seen from Table 1, compare China and apply for a patent Appl.200510117428.5 and the described catalyzer of Chinese patent CN1112373, the catalyst vinyl polymerization of the present invention's preparation has higher activity.Apply for a patent Appl.200510117428.5 with China and compare, the catalyzer of the present invention's preparation has better hydrogen response energy; CN1112373 compares with Chinese patent, and the polymkeric substance of the present invention's preparation has concentrated more size distribution and the polymer bulk density of Geng Gao.Therefore, catalyst component over-all properties of the present invention is comparatively good.
Claims (13)
1. be used for the ethylene polymerization catalysts component, it comprises a kind of magnesium mixture, at least a titanium compound, at least a carbonatoms greater than 5 the organic alcohol compound and the reaction product of at least a silicoorganic compound,
Wherein said magnesium mixture is that magnesium halide is dissolved in resulting product in the solvent system that contains organic epoxy compounds and organo phosphorous compounds;
Described titanium compound general formula is Ti (OR)
aX
b, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen, a is 0,1 or 2, b is 1 to 4 integer, a+b=3 or 4;
Described silicon compound is for being R as general formula
1 xR
2 ySi (OR
3)
zShown silicoorganic compound, wherein R
1And R
2Be respectively alkyl or halogen, R
3Be alkyl, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4.
2. the ethylene polymerization catalysts component that is used for according to claim 1, wherein said carbonatoms adopts general formula R greater than 5 organic alcohol compound
5CHOH represents, wherein R
5For carbonatoms greater than 4 straight chained alkyl, secondary alkyl, tertiary alkyl or cycloalkyl.
3. ethylene polymerization catalysts component, the wherein general formula R of being used for according to claim 1
1 xR
2 ySi (OR
3)
zIn, R
1And R
2Be respectively alkyl or halogen that carbonatoms is 1-10, R
3For carbonatoms is the 1-10 alkyl, x wherein, y, z are positive integer.
4. the ethylene polymerization catalysts component that is used for according to claim 1, wherein said silicoorganic compound are selected from least a in tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes and four (2-ethyl hexyl oxy) silane.
5. according to the described ethylene polymerization catalysts component that is used for of one of claim 1-4, wherein the consumption of each reactant is in every mole of magnesium halide in the magnesium mixture, organic alcohol compound is the 0.1-10 mole, and silicoorganic compound are 0.05～1 mole, and titanium compound is 1～15 mole.
6. according to the described ethylene polymerization catalysts component that is used for of one of claim 1-4, wherein, described solvent system contains the organic epoxy compounds of 0.3～4mol and 0.2～4mol organo phosphorous compounds, with respect to every mole of magnesium halide.
7. the described ethylene polymerization catalysts component that is used for of claim 6, wherein, described solvent system also contains at least a inert diluent that is selected from arene compounds or the alkane derivative, and its consumption is the described magnesium halide of 0.2-10L/mol.
8. according to the described ethylene polymerization catalysts component that is used for of one of claim 1-4, also add the alcohol of straight chain, side chain or cycloalkyl that carbonatoms is 1-4.
9. the described ethylene polymerization catalysts component that is used for of claim 8, wherein the mol ratio of the alcohol of the carbonatoms straight chain, side chain or the cycloalkyl that are 1-4 greater than 5 organic alcohol compound and carbonatoms is 1: 0.25～1: 4.
10. one kind prepares the method that is used for the ethylene polymerization catalysts component, this method comprises the steps: that (1) is dissolved in magnesium halide in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, preferably in solvent system, add inert diluent, form homogeneous solution, the preferred 50-90 of solvent temperature ℃; In forming the process of described homogeneous solution or add alkylol cpd afterwards, with a kind of solution of final formation; (2) under lower temperature, under the temperature in preferred-40 ℃ of-20 ℃ of scopes, the solution that step (i) is obtained contacts with titanium compound, before this contact, in the process or add silicon compound afterwards, obtains a kind of mixture;
(3) described mixture slowly is warming up to 60 ℃-110 ℃, particle is separated out and formed to solids gradually; With
(4) reclaim catalyst component of the present invention;
Wherein: described alkylol cpd is at least a carbonatoms greater than 5 organic alcohol compound, and randomly comprises the alcohol of straight chain, side chain or cycloalkyl that carbonatoms is 1-4;
Described titanium compound general formula is Ti (OR)
aX
b, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen, a is 0,1 or 2, b is 1 to 4 integer, a+b=3 or 4; With
Described silicon compound is for being R as general formula
1 xR
2 ySi (OR
3)
zShown silicoorganic compound, wherein R
1And R
2Be respectively alkyl or halogen, R
3Be alkyl, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4.
11. one kind is used for ethylene polymerization catalysts, it comprises the reaction product of following component:
(1) the described catalyst component of one of claim 1-9; With
(2) general formula is AlR
6 nX
2 3-nOrgano-aluminium compound, R in the formula
6For hydrogen or carbonatoms are 1～20 alkyl, X
2Be halogen, 0＜n≤3.
12. the ethylene polymerization catalysts that is used for according to claim 11, wherein the mol ratio of the middle titanium of aluminium and component (1) is 20-200 in the component (2).
13. an ethene polymerization method, this method comprises:
(i) ethene and optional comonomers are contacted under polymerizing condition with claim 11 or 12 described catalyzer, to form polymkeric substance; With
The (ii) polymkeric substance that forms in the recycling step (i).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710064885A CN101274967B (en) | 2007-03-28 | 2007-03-28 | Catalyst for ethylene polymerization and components thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710064885A CN101274967B (en) | 2007-03-28 | 2007-03-28 | Catalyst for ethylene polymerization and components thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101274967A true CN101274967A (en) | 2008-10-01 |
| CN101274967B CN101274967B (en) | 2010-05-19 |
Family
ID=39994852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710064885A Active CN101274967B (en) | 2007-03-28 | 2007-03-28 | Catalyst for ethylene polymerization and components thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101274967B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880342A (en) * | 2010-07-06 | 2010-11-10 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst and preparation and application thereof |
| CN102464733A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and preparation method thereof as well as olefin polymerization method |
| CN101724106B (en) * | 2008-10-31 | 2012-05-30 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization reaction and catalyst thereof |
| CN101864009B (en) * | 2009-04-17 | 2012-07-04 | 中国石油化工股份有限公司 | Preparation method of catalyst component for polymerization reaction of olefins and catalyst thereof |
| CN102030845B (en) * | 2009-09-29 | 2013-02-27 | 中国石油化工股份有限公司 | Catalyst component used for vinyl polymerization reaction and catalyst thereof |
| CN102040685B (en) * | 2009-10-16 | 2013-09-25 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization and catalyst |
| CN103772554A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ingredients of catalyst for vinyl polymerization and catalyst |
| CN103772555A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ingredients of catalyst for vinyl polymerization and catalyst |
| CN104229817A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of small grain molecular sieve with EUO structure |
| CN104277157A (en) * | 2013-07-05 | 2015-01-14 | 中国石油天然气股份有限公司 | Load type titanium aluminum modified chromium series catalyst and preparation and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1006071B (en) * | 1985-04-01 | 1989-12-13 | 中国石油化工总公司 | Catalyst system for olefin polymerization and copolymerization |
| TW302375B (en) * | 1992-10-05 | 1997-04-11 | Mitsui Petroleum Chemicals Ind | |
| KR100496776B1 (en) * | 2001-06-21 | 2005-06-22 | 삼성토탈 주식회사 | Catalyst for polymerization and copolymerization of ethylene |
| CN100363389C (en) * | 2004-09-23 | 2008-01-23 | 中国石油化工股份有限公司 | Catalyst used for ethylene polymerization or copolymerization and its preparation method |
-
2007
- 2007-03-28 CN CN200710064885A patent/CN101274967B/en active Active
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724106B (en) * | 2008-10-31 | 2012-05-30 | 中国石油化工股份有限公司 | Catalyst component for vinyl polymerization reaction and catalyst thereof |
| CN101864009B (en) * | 2009-04-17 | 2012-07-04 | 中国石油化工股份有限公司 | Preparation method of catalyst component for polymerization reaction of olefins and catalyst thereof |
| CN102030845B (en) * | 2009-09-29 | 2013-02-27 | 中国石油化工股份有限公司 | Catalyst component used for vinyl polymerization reaction and catalyst thereof |
| CN102040685B (en) * | 2009-10-16 | 2013-09-25 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization and catalyst |
| CN101880342A (en) * | 2010-07-06 | 2010-11-10 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst and preparation and application thereof |
| CN101880342B (en) * | 2010-07-06 | 2012-10-17 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst and preparation and application thereof |
| CN102464733B (en) * | 2010-11-18 | 2013-09-25 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and preparation method thereof as well as olefin polymerization method |
| CN102464733A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and preparation method thereof as well as olefin polymerization method |
| CN103772554A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ingredients of catalyst for vinyl polymerization and catalyst |
| CN103772555A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ingredients of catalyst for vinyl polymerization and catalyst |
| CN103772554B (en) * | 2012-10-25 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of catalyst component for polymerization of ethylene and catalyst thereof |
| CN104229817A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of small grain molecular sieve with EUO structure |
| CN104277157A (en) * | 2013-07-05 | 2015-01-14 | 中国石油天然气股份有限公司 | Load type titanium aluminum modified chromium series catalyst and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101274967B (en) | 2010-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100513433C (en) | Catalyst components in use for polymerizing ethylene, and catalyst | |
| CN101274967B (en) | Catalyst for ethylene polymerization and components thereof | |
| CN101633704B (en) | Catalyst component used for ethylene polymerization reaction and catalyst thereof | |
| CN101838353A (en) | Catalyst component for vinyl polymerization and catalyst thereof | |
| CN102295717B (en) | Catalyst compound used for vinyl polymerization reaction and catalyst thereof | |
| CN102875707A (en) | Preparation method of catalyst component for ethylene polymerization or copolymerization and catalyst thereof | |
| CN102295715B (en) | Catalyst component used for vinyl polymerization reaction and catalyst thereof | |
| CN100532406C (en) | Catalyst components in use for polymerizing ethylene, and catalyst | |
| CN102993343B (en) | Catalyst component for ethylene polymerization, and catalyst thereof | |
| CN102040686B (en) | Catalyst component and catalyst for vinyl polymerization | |
| CN103130931B (en) | A kind of Ball shape ethylene polymerization solid titanium catalytic and Synthesis and applications thereof | |
| CN101633705B (en) | Catalyst component used for ethylene polymerization reaction and catalyst thereof | |
| CN102040685B (en) | Catalyst component for ethylene polymerization and catalyst | |
| CN105384854A (en) | Catalyst component and catalyst for ethylene polymerization, and preparation method of catalyst component for ethylene polymerization | |
| CN102453172A (en) | Method for homopolymerizing or copolymerizing ethylene | |
| CN102060945B (en) | Preparation and application of solid titanium catalyst component for vinyl polymerization | |
| CN101838352B (en) | Catalyst component for vinyl polymerization or copolymerization and catalyst thereof | |
| CN105199024A (en) | Catalyst component for vinyl polymerization, catalyst and preparation method thereof | |
| CN102286119A (en) | Catalyst component and catalyst for polymerization of ethylene | |
| CN102344515B (en) | Catalyst component for ethylene polymerization and catalyst thereof | |
| CN102993344B (en) | A kind of catalyst component for vinyl polymerization and catalyzer | |
| CN102020730A (en) | Catalyst component used for vinyl polymerization and catalyst | |
| CN102329400A (en) | Olefin polymerization catalyst containing silane compound, preparation and application thereof | |
| CN101519463A (en) | Preparation method of catalyst for ethylene polymerization and copolymerization | |
| CN102875709B (en) | Preparation method of catalyst component for ethylene polymerization reaction and catalyst thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |