CN103772554B - A kind of catalyst component for polymerization of ethylene and catalyst thereof - Google Patents
A kind of catalyst component for polymerization of ethylene and catalyst thereof Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst component for polymerization of ethylene, comprise the product of following component: (1) magnesium compound (2) organic alcohol compound (3) organo-silicon compound (4) nonionic class surfactants (5) titanium compound, it is R that wherein said organo-silicon compound are selected from general formula1 xR2 ySi(OR3)zIn at least one, wherein R1And R2Be respectively carbon number and be 1～10 alkyl or halogen, R3For the carbon number alkyl that is 1～10, x, y, z is integer, 0≤x≤2,0≤y≤2,0≤z≤4, and x+y+z=4; Described nonionic class surfactant is at least one in the block copolymer of APEO compounds, carbon oxo alcohol ethoxy compound and epoxide; This catalyst has higher catalytic activity, good copolymerization performance, and polymer has higher bulk density and narrower particle diameter distributes, and is applicable to the equal polymerization of ethene or the combined polymerization of ethene and other alpha-olefin.
Description
Technical field
The present invention relates to a kind of catalytic component and preparation side thereof for vinyl polymerization or copolymerizationMethod and containing the catalyst of this catalytic component. More particularly, relate to one adds non-in preparation processCatalytic component of ionic species surfactant and preparation method thereof and its catalyst.
Background technology
As everyone knows, tie up in poly suitability for industrialized production and occupy containing the caltalyst of Ti/Mg compoundLeading position, the polymerization activity, hydrogen response, copolymerization performance that its research focus concentrates on catalyst withAnd the particle shape of catalyst and particle diameter distribution etc. And in the slurry polymerization processes of ethene, except requiring to urgeAgent should have outside higher catalytic activity, and the copolymerization performance of catalyst is most important. Suitable in controlUnder the condition of density, the copolymerization performance of catalyst excellence will reduce the addition of comonomer greatly, reducesThe probability that in polymerization process, polymer is clamminess, the long-term operation of raising device. Along with polyolefin entirety cityThe increase of the various costs of material such as depression and ethene of field, high added value is fallen over each other to develop in each large petrochemical plant commercial cityThe PP Pipe Compound trade mark with increase benefit. And the copolymerization performances of these PP Pipe Compound trades mark to catalyst etc. require moreHigh, harsher, petrochemical industry manufacturer even can live for the above-mentioned performance sacrificial section catalysis that improves catalystProperty.
Copolymerization performance, its essence is the energy of the access of comonomer coordination in ethylene polymerisation process ethylene molecule chainPower. Desirable copolymerization performance is the strand of comonomer access higher molecular weight, and does not enter low moleculeThe strand of amount. In actual research and production, conventionally in catalyst, introduce various components and improveThe copolymerization performance of catalyst. In the slurry polymerization processes of ethene, higher except requiring catalyst to haveOutside the hydrogen tonality of catalytic activity, sensitivity and preferably distribution of particles, quite a few trade mark---especiallyThe copolymerization trade mark of some high added values needs catalyst to provide excellent copolymerization performance to meet its demand.
In Chinese patent CN1229092A, disclose a kind of catalytic component, it is taking magnesium chloride as carrier,Titanium tetrachloride is active component, and the preparation method of catalyst is as follows: first by MgCl2Be dissolved in dicyandiamide solutionIn, form homogeneous transparent solution, then precipitation additive phthalic anhydride exist and low temperature under with TiCl4Reaction, logicalCross slowly and heat up and separate out solid catalyst. The catalytic component making is during for vinyl polymerization, with catalystCatalytic activity be representative combination property is unsatisfactory. Meanwhile, in the time of synthetic this catalyst, need adoptWhat precipitate with promotion as precipitation additive with organic matters such as phthalic anhydrides separates out, and need to add a large amount of tetrachlorosTitanium. Therefore not only the existence of acid anhydrides produces adverse influence to catalyst, simultaneously a large amount of titanium tetrachloridesUse, also can cause a large amount of wastes and pollution.
In Chinese patent CN1958620A, it is taking magnesium chloride as carrier, and titanium tetrachloride is active component,The preparation method of catalyst is as follows: first by MgCl2Be dissolved in dicyandiamide solution, form homogeneous transparent solution,Then precipitation additive silicon ester compound and TiCl at low temperatures4Reagentia, separates out solid by slow intensificationBody catalyst. The catalytic component making is during for vinyl polymerization, and the catalytic activity of catalyst is higher, itsAlthough combination property also has clear improvement compared with the catalyst in Chinese patent CN1229092A, be total toThe aspects such as poly-performance are still difficult to meet completely some PP Pipe Compound that copolymerization performance is had relatively high expectations of industrial productionThe demand of the trade mark.
Therefore, be necessary very much to provide a kind of and close or the catalyst of copolymerization for ethylene homo, spyBe not applicable to ethene slurry polymerization processes, its not only catalytic activity higher, there is good copolymerization performance,And resulting polymers has narrower particle diameter distribution.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalyst component for polymerization of ethylene and catalysis thereofAgent, this solid catalyst has higher catalytic activity, good copolymerization performance, and polymer has narrowerParticle diameter distribute.
A kind of catalyst component for polymerization of ethylene, comprises the product of following component:
(1) magnesium compound
(2) organic alcohol compound
(3) organo-silicon compound
(4) nonionic class surfactant
(5) titanium compound
Wherein said magnesium compound is that magnesium halide is dissolved in to organic epoxide and organophosphor chemical combinationThe product obtaining in the dicyandiamide solution of thing;
Described organic alcohol compound be carbon number be 1～10 straight chain, side chain or cycloalkyl alcohol,Carbon number is 6～20 the alcohol that contains aryl or halohydrin;
It is R that described organo-silicon compound are selected from general formula1 xR2 ySi(OR3)zIn at least one, wherein R1WithR2Be respectively carbon number and be 1～10 alkyl or halogen, R3For the carbon number alkyl that is 1～10,X, y, z is integer, 0≤x≤2,0≤y≤2,0≤z≤4, and x+y+z=4;
Described nonionic class surfactant is selected from APEO compounds, carbon oxo alcohol secondAt least one in the block copolymer of oxo-compound or epoxide;
It is Ti (OR) that described titanium compound is selected from general formulaaXbIn at least one, wherein R is C1～C14Aliphatic group or aryl, X is halogen, a is integer, 0≤a≤4, b is integer, 0≤b≤4,A+b=3 or 4.
Detailed description of the present invention:
The preparation of magnesium compound: be that magnesium halide is dissolved in to organic epoxide and organic phosphorus compound groupThe homogeneous solution that the dicyandiamide solution becoming obtains, the dicyandiamide solution of indication comprises use or does not use lazy hereProperty diluent.
Above-mentioned magnesium halide comprises that the complex compound such as water or alcohol, the magnesium dihalide of magnesium dihalide, magnesium dihalide divideA kind of in the derivative that in minor, one of them halogen atom is replaced by oxyl or halogen oxyl or itsMixture, particular compound is magnesium dichloride, dibrominated magnesium, two magnesium iodides, chlorination phenoxy group magnesium, chlorineChange isopropoxy magnesium, chlorination butoxy magnesium etc. Wherein taking magnesium dichloride as best.
Organic epoxide described in dicyandiamide solution comprise carbon number be 2～8 aliphatic alkene,The compounds such as the oxide of alkadienes, halogenated aliphatic alkene or alkadienes, glycidol ether, inner ether.Particular compound is shunk sweet as: oxirane, expoxy propane, epoxy butane, epoxychloropropane, methylOil ether, diglycidyl ether, oxolane etc. Wherein, be preferably oxirane, expoxy propane,Epoxychloropropane, oxolane, taking oxolane, epoxychloropropane as best.
Organic phosphorus compound described in dicyandiamide solution comprises hydrocarbyl carbonate or the halogenation of orthophosphoric acid or phosphorous acidHydrocarbyl carbonate. Concrete as: orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, tricresyl phosphitePhenyl ester, Trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite, sub-phosphorusAcid benzene methyl etc. Wherein be preferably orthophosphoric acid trimethyl, orthophosphoric acid triethyl and orthophosphoric acid tributyl,Orthophosphoric acid tributyl is best.
In order to make dissolving more abundant, in this dicyandiamide solution, optionally add inert diluent, conventionallyThis inert diluent comprises arene compounds or alkane derivative, arene compounds comprise benzene,Toluene, dimethylbenzene, monochlor-benzene, dichlorobenzene, trichloro-benzene, monochlorotoluene and derivative thereof; AlkaneHydrocarbon comprises a kind of in linear paraffin, branched paraffin or the cycloalkane of 3～20 carbon atoms or theirs is mixedCompound, as butane, pentane, hexane, cyclohexane, heptane etc., as long as contribute to magnesium halide to dissolve allCan use. Above-mentioned inert diluent can be used alone, also use capable of being combined.
Organic alcohol compound of the present invention comprises that carbon number is 1～10 straight chain, side chain or cycloalkanesThe alcohol of base, carbon number are 6～20 alcohol that contains aryl or halohydrins. The example of alcohol comprises fatty alcohol:Methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, glycerine, hexanol, 2-methyl anyl alcohol,2-ethyl butanol, n-heptanol, n-octyl alcohol, decyl alcohol etc.; Cyclic alkanol, as cyclohexanol, methyl cyclohexanol etc.;Aromatic alcohol, as phenmethylol, methylbenzyl alcohol, ɑ-methylbenzyl alcohol, ɑ, ɑ-dimethylphenylcarbinol etc.Preferred alcohol, butanols, 2-Ethylhexyl Alcohol, glycerine.
The compound general formula of titanium of the present invention is Ti (OR)aXb, wherein R is C1～C14Aliphatic hydrocarbonBase or aryl, X is halogen, a is integer, 0≤a≤4, b is integer, 0≤b≤4, a+b=3 or 4,Particular compound comprises: TiCl4、TiBr4、TiCl4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC2H5)Br3、Ti(OC2H5)2Cl2、Ti(OCH3)2Cl2、Ti(OCH3)2I2、Ti(OC2H5)3Cl、Ti(OCH3)3Cl、Ti(OC2H5)3I、Ti(OC2H5)4、Ti(OC3H7)4、Ti(OC4H9)4Deng. Preferably TiCl4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC4H9)4. With TiCl4For the best.
General formula without active hydrogen organo-silicon compound of the present invention is R1 xR2 ySi(OR3)z, wherein R1WithR2Be respectively carbon number and be 1～10 alkyl or halogen, R3For the carbon number alkyl that is 1～10,X, y, z is integer, 0≤x≤2,0≤y≤2,0≤z≤4, and x+y+z=4, concrete chemical combinationThing comprises: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four(2-ethyl hexyl oxy) silane, ethyl trimethoxy silane, ethyl triethoxysilane, methyl trimethoxyTMOS, MTES, n-pro-pyl triethoxysilane, n-pro-pyl trimethoxy silane,Decyl trimethoxy silane, decyl triethoxysilane, cyclopentyl-trimethoxy-silane, cyclopenta three secondTMOS, 2-methylcyclopentyl trimethoxy silane, 2,3-dimethylcyclopentyl trimethoxy silane,Cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, MTMS, methyl three secondTMOS, ethyl triethoxysilane, vinyltrimethoxy silane, VTES,Tert-butyl group triethoxysilane, normal-butyl trimethoxy silane, ne-butyltriethoxysilaneand, isobutyl groupTrimethoxy silane, isobutyl triethoxy silane, cyclohexyltriethyloxysilane, cyclohexyl trimethoxyBase silane, phenyltrimethoxysila,e, phenyl triethoxysilane, a chlorine trimethoxy silane, a chlorineTriethoxysilane, ethyl three isopropoxy silane, vinyl three butoxy silanes, trimethyl phenoxy groupSilane, methyl three allyloxy silane, vinyl triacetic acid base silane, dimethyldimethoxysil,ne,Dimethyldiethoxysilane, diisopropyl dimethoxy silane, diisopropyl diethoxy silane, uncleButyl methyl dimethoxy silane, tert-butyl group methyldiethoxysilane, tertiary pentyl methyl diethoxy siliconAlkane, dicyclopentyl dimethoxyl silane, two cyclopenta diethoxy silanes, methylcyclopentyl diethoxySilane, methylcyclopentyl dimethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy siliconAlkane, aminomethyl phenyl diethoxy silane, aminomethyl phenyl dimethoxy silane, two o-tolyl dimethoxySilane, two o-tolyl diethoxy silane, two between tolyl dimethoxy silane, two between tolyl twoEthoxysilane, biconjugate tolyl dimethoxy silane, biconjugate tolyl diethoxy silane, trimethylMethoxy silane, trimethylethoxysilane, three cyclopenta methoxy silane, three cyclopenta ethyoxyl siliconWherein a kind of or several such as alkane, two cyclopentyl-methyl methoxy silane and cyclopenta dimethyl methyl TMOSPlant to mix and use. Preferably tetramethoxy-silicane, tetraethoxysilane and four butoxy silanes. In the present invention,Organo-silicon compound are except using as precipitation additive, in the solid titanium catalyst component finally obtainingShould contain the organo-silicon compound of q.s to improve the combination property of catalyst.
Nonionic class surfactant of the present invention is that APEO compounds, carbon carbonyl are syntheticAt least one in the block copolymer of alcohol ethoxylates and epoxide, particular compound andPhysical data sees the following form, and wherein APEO compounds is that the open loop of fatty alcohol and epoxide is anti-Answer thing, the block copolymer of epoxide is ethylene oxide-propylene oxide block copolymer. Preferably 10Carbon APEO (XP70) and ethylene oxide-propylene oxide block copolymer (PE3100).
In catalyst component for polymerization of ethylene of the present invention, the ratio between each reactant is with every moleMagnesium halide meter, organic epoxide: 0.5～5.0mol, preferably 0.3～4.0mol; OrganophosphorCompound: 0.1～4.0mol, preferably 1.0～4.0mol; Organic alcohol compound: 0.1～10.0mol,Preferably 0.5～2.0mol; Surfactant: 1.0～10.0ml, preferably 1.0～5.0ml; OrganicSilicon compound: 0.05～1.0 mole, preferably 0.1～0.5mol; Titanium compound: 1.0～15.0 rubYou, preferably 2.0～5.0mol; .
In the catalytic component obtaining in the present invention, Ti:4.0～8.0wt%, Mg:15.0～20.0wt%，Cl：60.0～70.0wt%，Si：0.2～1.2wt%，OR：4.0～8.5wt%：0.1～1.0wt%，Al：0～0.6wt%。
The present invention also provides a kind of preparation method of catalyst component for polymerization of ethylene, comprises following stepIt is rapid: (1) is dissolved in magnesium halide in the dicyandiamide solution containing organic epoxide and organic phosphorus compound,In preferred dicyandiamide solution, add inert diluent, form homogeneous solution, solution temperature preferably 50～90 DEG C; Forming in the process of solution or solution adds alcoholic compound after forming, then add or be not added withMachine aluminium compound, the reaction regular hour. (2) at a lower temperature, preferably in-40 DEG C-20 DEG C,Above-mentioned solution and titanium compound are carried out to haptoreaction, add subsequently without active hydrogen organo-silicon compound and non-Ionic species surfactant, and mixture is slowly warming up to 50～120 DEG C, solids is separated out also graduallyForm particle, after the reaction regular hour, remove unreacted reactant and solvent, and adopt inert diluent to washWash, obtain catalytic component of the present invention.
It is a kind of for the equal polymerisation of ethene or being total to of ethene and other alpha-olefin that the present invention also providesThe catalyst of polymerisation, alpha-olefin wherein comprises propylene, butene-1,4-methylpentene-1, ownAlkene-1, octene-1, styrene, methyl styrene etc.; This catalyst comprises (1) above-mentioned the present inventionCatalytic component and (2) general formula be AlRnX3-nThe product of organo-aluminum compound, in formula, R canThink alkyl, particularly alkyl, aralkyl, aryl that hydrogen, carbon number are l～20; X is halogen,Particularly chlorine and bromine; N is the number of 0 < n≤3. Particular compound is as trimethyl aluminium, triethyl aluminum, threeAluminium isobutyl, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride,The aluminum alkyl halides such as chloro-di-isobutyl aluminum, sesquialter ethyl aluminium chloride, ethyl aluminum dichloride, wherein preferably threeAluminium ethide, triisobutyl aluminium. Wherein in component (2) aluminium and the mol ratio of the middle titanium of component (1) be 5～500, preferably 20～200.
When polymerization, can adopt liquid phase polymerization, also can adopt gas-phase polymerization.
Liquid polymerization medium comprises: iso-butane, hexane, heptane, cyclohexane, naphtha, raffinate oil,The atent solvents such as aliphatic saturated hydrocarbon or aromatic hydrocarbon such as hydrogasoline, kerosene, benzene,toluene,xylene.
In order to regulate the molecular weight of final polymer, adopt hydrogen to make molecular weight regulator.
Due to the acting in conjunction without active hydrogen organo-silicon compound and nonionic class surfactant, in catalysisTime prepared by agent component, separate out easily catalyst granules, improve bulk density, do not need to use a large amount ofTitanium tetrachloride impels separating out of precipitation, and therefore the addition of titanium tetrachloride greatly reduces. Organosilicon simultaneouslyCompound and nonionic class surfactant add the activity and the catalyst that also contribute to improve catalystThe improvement of particle shape, during for vinyl polymerization, show good copolymerization performance at catalyst.
Detailed description of the invention
With embodiment, the present invention is described below, but and unrestricted invention scope.
Method of testing:
The density of polymer: measure according to GB GB/T1033.2-2010
Embodiment 1
(1) preparation of catalytic component
In the reactor of fully replacing through high pure nitrogen, add successively 6.0g magnesium dichloride, toluene90ml, epoxychloropropane 5.0ml, tributyl phosphate 9.0ml, ethanol 6.0ml, is warming up to 70 DEG C under stirring,After dissolving the solution that forms homogeneous completely, solid reacts 1 hour under 70 DEG C of conditions. Then by cold this systemBut to-10 DEG C, slowly drip 60ml titanium tetrachloride, then add 4.0ml ethyl orthosilicate and 2.0ml10Carbon APEO (XP70), reacts 1 hour. Slowly be warming up to 80 DEG C, react 2 hours. StopStir, leave standstill, the very fast layering of suspension, extracts the upper strata stillness of night, twice of toluene wash, hexane washing fourTime, high pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution. CatalystThe composition of component is in table 1.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, adds hexane 1L, denseSpend the triethyl aluminum 1.0ml of 1M, add the ingredient of solid catalyst (containing 0.3 milligram of titanium) of above-mentioned preparation,Be warming up to 80 DEG C, pass into hydrogen and make still internal pressure reach 0.28Mpa, then pass into ethene stagnation pressure in still is reachedTo 0.73Mpa(gauge pressure), polymerization 2 hours under 80 DEG C of conditions, polymerization result is in table 2.
Embodiment 2
(1) catalyst is synthetic with embodiment 1. Ethyl orthosilicate consumption changes 3.0ml into, 10 carbon polyoxy secondAlkene ether (XP70) consumption changes 3.0ml into.
(2) vinyl polymerization is with embodiment 1. The composition of catalytic component and polymerization result are in table 1 and table 2.
Embodiment 3
(1) catalyst is synthetic with embodiment 1. 10 carbon APEO (XP70) consumptions change 4.0ml into.
(2) vinyl polymerization is with embodiment 1. The composition of catalytic component and polymerization result are in table 1 and table 2.
Embodiment 4
(1) preparation of catalytic component: in the reactor of fully replacing through high pure nitrogen, add successively6.0g magnesium dichloride, toluene 70ml, epoxychloropropane 6.0ml, tributyl phosphate 7ml, ethanol 5.0ml,Under stirring, be warming up to 70 DEG C, after solid dissolves the solution that forms homogeneous completely, under 70 DEG C of conditions, react 1Hour. Then this system is cooled to-10 DEG C, slowly drips 60ml titanium tetrachloride, then add 4.0mlEthyl orthosilicate and 3.0ml ethylene oxide-propylene oxide block copolymer (PE3100), react 1 hour,Slowly be warming up to 80 DEG C, react 2 hours. Stop stirring, leave standstill, the very fast layering of suspension, extractsThe layer stillness of night, twice of toluene wash, hexane washing four times, high pure nitrogen dries up, and obtains good fluidity, grainThe ingredient of solid catalyst of footpath narrowly distributing. The composition of catalytic component is in table 1.
(2) vinyl polymerization is with embodiment 1. The composition of catalytic component and polymerization result are in table 1 and table 2.
Embodiment 5
(1) catalyst is synthetic with embodiment 4. Just ethylene oxide-propylene oxide block copolymer (PE3100)Consumption changes 4.0ml into.
(2) vinyl polymerization is with embodiment 1. The composition of catalytic component and polymerization result are in table 1 and table 2.
Embodiment 6
(1) catalyst is synthetic with embodiment 4. Just ethylene oxide-propylene oxide block copolymer (PE3100)Amount changes 5.0ml into, and ethyl orthosilicate consumption changes 2.0ml into.
(2) vinyl polymerization is with embodiment 1. The composition of catalytic component and polymerization result are in table 1 and table 2.
Comparative example 1
(1) catalyst is synthetic with embodiment 1, and synthesizing with embodiment 1 of catalyst, does not add 10 carbon polyoxiesVinethene (XP70) or ethylene oxide-propylene oxide block copolymer (PE3100).
(2) vinyl polymerization condition is with embodiment 1. The composition of catalytic component and polymerization result are in table 1 and table 2.
The catalyst of investigating copolymerization performance employing is embodiment 1, embodiment 4 and comparative example 1. At volumeFor the stainless steel cauldron of 2L, after high pure nitrogen is fully replaced, add hexane 1L, three of concentration 1MAluminium ethide 1.0ml, adds the hexane solution of catalyst (containing the 0.3 milligram of titanium) solid of above-mentioned preparation,Be warming up to 70 DEG C, pass into the ethene and the 1-butylene gas-phase (co-) polymerisation that prepare according to fixed proportion, 1-butylene andThe volume ratio of ethene is 10/100, and passes into modifying polymerization with hydrogen thing molecular weight; When hexene is made comonomer,Add 10ml hexene, other is with the copolymerization of 1-butylene. Concrete investigation the results are shown in Table 3.
Table 1 catalyst composition
| Numbering | Ti(wt%) | Mg(wt%) | Cl(wt%) | OR(wt%) |
| Example 1 | 7.3 | 16.8 | 59.2 | 7.7 |
| Example 2 | 6.6 | 17.1 | 57.9 | 6.9 |
| Example 3 | 7.0 | 16.3 | 60.1 | 5.9 |
| Example 4 | 7.1 | 16.9 | 59.5 | 7.2 |
| Example 5 | 6.4 | 17.8 | 59.8 | 6.6 |
| Example 6 | 6.5 | 17.3 | 60.1 | 5.7 |
| Contrast 1 | 6.1 | 16.1 | 60.3 | 5.8 |
Table 2 polymer performance
Table 3 copolymerization performance
Can find out from the aggregated data of table 2, under same polymerizing condition, catalyst activity of the present inventionProperty is higher, and bulk density is higher, the centralized particle diameter of polymer.
Can find out from the data of table 3, catalyst is in 1-butylene and hexene its density during as comonomerHave to a certain degree and reduce, show that the copolymerization performance of catalyst improves.
Claims (10)
1. a catalyst component for polymerization of ethylene, comprises the product of following component:
(1) magnesium compound
(2) organic alcohol compound
(3) organo-silicon compound
(4) nonionic class surfactant
(5) titanium compound
Magnesium halide is dissolved in organic epoxide and organic phosphorus compound by wherein said magnesium compoundThe product obtaining in dicyandiamide solution;
Described organic alcohol compound is that carbon number is alcohol, the carbon of 1～10 straight chain, side chain or cycloalkylAtomicity is 6～20 the alcohol that contains aryl or halohydrin;
It is R that described organo-silicon compound are selected from general formula1 xR2 ySi(OR3)zIn at least one, wherein R1And R2Be respectively carbon number and be 1～10 alkyl or halogen, R3For the carbon number alkyl that is 1～10, x, y,Z is integer, 0≤x≤2,0≤y≤2,0≤z≤4, and x+y+z=4;
Described nonionic class surfactant be 10 carbon APEO XP70 or Huan Yang Yi Wan ?expoxy propaneBlock copolymer PE3100;
It is Ti (OR) that described titanium compound is selected from general formulaaXbIn at least one, wherein R is C1～C14FatFat alkyl or aryl, X is halogen, a is integer, 0≤a≤4, b is integer, 0≤b≤4, a+b=3 or 4.
2. catalyst component for polymerization of ethylene according to claim 1, is characterized in that with in magnesium compoundEvery mole of magnesium halide meter, organic epoxide is 0.5～5.0mol, organic phosphorus compound is 0.1～4.0Mol, organic alcohol compound is 0.1～10.0mol, organo-silicon compound are 0.05～1.0mol, non-fromSubclass surfactant is 1.0～10.0mol, and titanium compound is 1.0～15.0mol.
3. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described organic silicationCompound is at least one in tetramethoxy-silicane, tetraethoxysilane and four butoxy silanes.
4. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described organic epoxyCompound comprises that carbon number is 2～8 aliphatic alkene, alkadienes or halogenated aliphatic alkene or alkadienesOxide, glycidol ether and inner ether at least one.
5. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described organic phosphatizationCompound is hydrocarbyl carbonate or the halo hydrocarbyl carbonate of orthophosphoric acid or phosphorous acid.
6. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described organic alcoholizationCompound is ethanol, butanols, 2-Ethylhexyl Alcohol, glycerine.
7. catalyst component for polymerization of ethylene according to claim 1, is characterized in that described titanium compoundFor TiCl4。
8. the preparation method of the catalyst component for polymerization of ethylene described in one of claim 1～7, comprises following stepRapid: magnesium halide is dissolved in containing forming evenly in the dicyandiamide solution of organic epoxide and organic phosphorus compoundClear solution, solution temperature is 50～90 DEG C, forming in the process of solution or solution adds after forming organicAlcoholic compound, the reaction regular hour, obtains reaction solution; In-40 DEG C～20 DEG C, by above-mentioned solutionCarry out haptoreaction with titanium compound, add subsequently organo-silicon compound and nonionic class surfactant, andMixture is slowly warming up to 50～120 DEG C, and particle is separated out and formed to solids gradually, the reaction regular hourAfter, remove unreacted reactant and solvent, and adopt inert diluent washing, obtain catalytic component.
9. for the catalyst of ethylene polymerization, the product that it comprises following component:
(1) the described catalyst component for polymerization of ethylene of one of claim 1～7;
(2) general formula is AlRnX3-nOrgano-aluminum compound, in formula, R is the alkyl that hydrogen or carbon number are l～20,X is halogen, the number of 0 < n≤3.
10. catalyst claimed in claim 9 closes the application in reaction or copolymerization at ethylene homo.
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| CN105622801B (en) * | 2014-11-06 | 2018-08-17 | 中国石油化工股份有限公司 | A kind of catalytic component for vinyl polymerization, catalyst and preparation method thereof |
| CN107880185B (en) * | 2016-09-30 | 2020-02-18 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation and application thereof |
| CN107880173B (en) * | 2016-09-30 | 2020-12-18 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof and catalyst |
| CN108341902B (en) * | 2017-01-23 | 2021-07-02 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, preparation method thereof and catalyst for ethylene polymerization |
| CN108341900B (en) * | 2017-01-23 | 2021-05-11 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, preparation method thereof and catalyst for ethylene polymerization |
| CN114426609B (en) * | 2020-10-15 | 2023-05-12 | 中国石油化工股份有限公司 | Solid catalyst component and catalyst system for olefin polymerization |
| TW202231673A (en) * | 2020-10-15 | 2022-08-16 | 大陸商中國石油化工科技開發有限公司 | Magnesium-based solid and catalyst component having multimodal pore distribution, and preparation methods therefor |
| CN114426602B (en) * | 2020-10-15 | 2023-05-09 | 中国石油化工股份有限公司 | Preparation method of solid catalyst component for olefin polymerization |
| CN115043966B (en) * | 2022-06-17 | 2023-11-28 | 上海化工研究院有限公司 | Main catalyst and catalyst for preparing ultra-high molecular weight polypropylene, preparation method and application |
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| CN101274967A (en) * | 2007-03-28 | 2008-10-01 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization and components thereof |
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