CN104277145B - For catalyst component, its preparation method and the application of olefinic polymerization - Google Patents
For catalyst component, its preparation method and the application of olefinic polymerization Download PDFInfo
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Abstract
The invention provides a kind of catalytic component for olefinic polymerization, it is the product that comprises at least one organo-magnesium compound, at least one titanium-containing compound, at least one hydroxyl compounds, at least one chloride organo-aluminum compound, at least one silane compound and at least one furtherance shape dispersant; Described silane compound is as general formula (V) Si (OR5)gCl4-gShown in, R in formula5C2～C20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0 ﹤ g≤4; And described furtherance shape dispersant is polystyrene block polyisoprene base polymer. Used catalyst component of the present invention, not only its catalytic activity is good, catalyst hydrogen response is good and resulting polymers bulk density is high, and the control of the particle shape of corresponding catalyst to olefinic polymerization product and granular size can be better, thereby be more conducive to the use of catalyst on the polymerization technique such as gas phase, slurry device.
Description
Technical field
The present invention relates to a kind of catalytic component for olefinic polymerization or combined polymerization and catalyst thereof, and this catalytic componentPreparation method and purposes.
Background technology
Over nearly more than 20 years, follow the development of olefin polymetiation process, the catalyst matching with polymerization technique has also been got considerableProgress, wherein effective catalyst relies on its good polymerization and ripe application technology in polyolefin catalyst fieldStill occupy an important position. Through exploratory development for many years, Mg-Ti is preparation method's adopts at present of effective catalyst moreChemical reaction method.
In chemical reaction method, many patents of invention relate to employing organic metal magnesium compound, chlorinating agent and transition metal titanizingThe chemical raw materials such as compound, have prepared the catalyst of number of different types with this class reactant, they are disclosed in Chinese patentCN1158136, CN1299375, CN1795213 and US Patent No. 3787384, US4148754, US4173547,In US4508843 and 5124296. In such Mg-Ti catalyst, having a fatal shortcoming is to be difficult to controlForming step processed, thus be difficult to control the form of prepared catalyst particle, and recent development is to comprise magnesium at catalyst precarsorIn the wind prose style free from parallelism system of/titanium compound, add the material of some similar emulsifying agents, make it to form emulsion, and then reaction precipitation goes outCatalyst granules, can improve the particle shape of gained catalyst, as what adopt in the EP-A-258089 of MontedisonPFPE is mentioned employing PFO in Chinese patent CN1537118A, and these method forming step complexity are difficult toControl, gained catalyst granules form is also wayward, and the material price adopting is high, is difficult to obtain.
Although done a large amount of research work in Ziegler-Natta catalyst field, for preparing high performance requirements moreZN catalyst, still needs some new or improved methods.
The inventor, by experiment discovery repeatedly, selects suitable furtherance shape dispersant, just can make process for synthetic catalyst simpleYi Hang, and it is better to obtain form, as catalyst granules spherical, narrow size distribution, has higher catalysis simultaneouslyActivity and hydrogen response.
Summary of the invention
Applicant of the present invention formerly provides (WO2012/022127) a kind of catalytic component for olefinic polymerization, its bagDraw together at least one organo-magnesium compound, at least one titanium-containing compound, at least one hydroxyl compounds, at least one containsChlorine organo-aluminum compound, at least one silane compound and at least one polystyrene block polybutadiene analog copolymer anti-Answer product. Use this catalytic component and corresponding catalyst catalysis in olefine polymerization, can obtain higher catalytic activity and goodHydrogen response. Although this catalytic component can be for olefinic polymerization brings good catalytic effect, inventor is also from formerMaterial price and catalytic effect equal angles attempt to seek other different dispersing aiies, for example, in the poly-fourth of existing polystyrene blockOn dienes copolymer basis, consider to redesign its molecular structure, particularly, as increased again one or more comonomer shapesCopolymer, change copolymer chain or a chain length of Cheng Xin or Similarity Between Line Segments, partly or entirely common with other comonomer replacementPolystyrene part in polymers and/or polybutadiene part, used halogen, alkyl or other hetero atom to replace main chain or side chainOn hydrogen atom etc. mode, this new copolymer as dispersing aid can at least be reached in the time participating in olefinic polymerization catalysisWith the similar catalytic effect of polystyrene block polybutadiene analog copolymer.
But the inventor is surprised to find that in experimentation, is using polystyrene block polyisoprene base polymerWhile substituting the polystyrene block polybutadiene analog copolymer of former use, the not only catalytic activity of corresponding catalyst and hydrogen responseWithout obviously declining; And the particle of corresponding catalyst component is more even, size distribution obviously narrows, it produces olefinic polymerizationThe particle size of product and the control of form can be better.
Therefore, the invention provides a kind of catalytic component for olefinic polymerization, its be comprise at least one organo-magnesium compound,At least one titanium-containing compound, at least one hydroxyl compounds, at least one chloride organo-aluminum compound, at least oneThe product of silane compound and at least one furtherance shape dispersant; Described silane compound is as general formula (V)Si(OR5)gCl4-gShown in, R in formula5C2～C20Alkyl, can be saturated or undersaturated straight chain, side chain or ring-typeChain, 0 ﹤ g≤4; And described furtherance shape dispersant is polystyrene block polyisoprene base polymer.
Catalytic component prepared by the present invention has good hydrogen regulation performance, also has good particle shape and distribution simultaneously,Thereby be more conducive to its use on the polymerization technique such as gas phase, slurry device.
Described organo-magnesium compound is as general formula (I) MgR1 nCl2-nShown in, R in formula1C2～C20Alkyl, canSaturated or undersaturated straight chain, side chain or closed chain, 0 < n≤2. Concrete compound is as being selected from dibutylmagnesium, two isobutylsBase magnesium, dioctyl magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride, butyl magnesium chloride etc.
Wherein said titanium-containing compound is as general formula (II) Ti (OR2)mCl4-mShown in, R in formula2C2～C20Alkyl,Can be saturated or undersaturated straight chain, side chain or closed chain, 0≤m≤4; Preferably wherein m=4 or m=0, because titanicCompound is in a liquid state conventionally at normal temperatures, and also fine with the compatibility of some solvents; Particular compound can be selected from tetrachloroAt least one in titanium, tetraethyl titanate and butyl titanate, preferably titanium tetrachloride.
Wherein said hydroxyl compounds is as general formula (III) HOR3Shown in, R in formula3C2～C20Alkyl, canTo be saturated or undersaturated straight chain, side chain or closed chain; Hydroxyl compounds is preferably fatty alcohol or aromatic alcohol, more excellentSelect at least one in n-butanol, n-hexyl alcohol, isooctanol, phenmethylol and benzyl carbinol. Preferably described chloride organo-aluminum compoundFor as general formula (IV) AlR4 fCl3-fShown in compound, R in general formula (IV)4C2～C20Alkyl, 0.5≤f≤2.5.
In the present invention, concrete described chloride organo-aluminum compound is selected from ethyl aluminum dichloride, sesquialter ethylaluminium chloride, chlorinationAt least one in diethyl aluminum and dichloro aluminium isobutyl.
In the present invention, described silane compound is preferably from a chlorine trimethoxy silane, a chlorine triethoxysilane, a chlorine threeButoxy silane, dichloro dimethoxy silane, dichloro diethoxy silane, dichloro dibutoxy silane, tetraethyl orthosilicate andAt least one in silicic acid four butyl esters.
Described furtherance shape dispersant polystyrene block polyisoprene class (SI) polymer comprise diblock and three blocks (SIS,And derivative ISI); The block type of optional of preferred described polymer is linear, band chain or star form. DescribedIn polystyrene block polyisoprene base polymer, the content of polyisoprene is 3～97wt%, preferably 10～90wt%.
The present invention also provides the corresponding preparation method of above-mentioned catalytic component, comprises the steps,
A: organo-magnesium compound is reacted with hydroxyl compounds, obtain clear solution;
B: furtherance shape dispersant is dispersed in to C4～C20In alkane or aromatic solvent, form solution, then with described silanesThe clear solution reaction that compound and step a obtain, obtains mixed liquor;
C: chloride organo-aluminum compound and titanium-containing compound are joined in the mixed liquor that step b obtains successively, obtain catalystIngredients suspension liquid, the solid particle reclaiming wherein obtains described catalytic component.
Preferably in above-mentioned preparation method in every mole of organo-magnesium compound, titanium-containing compound is 0.01～10 mole; Containing hydroxylBase class compound is 0.1～20 mole; Chloride organo-aluminum compound is 0.1～50 mole; Silane compound is 0.001～20 moles; The concentration of furtherance shape dispersant in reaction system is controlled at 0.001～100 grams per liter. Preferably titaniferous chemical combination whereinThing is 0.05～5 mole; Hydroxyl compounds is 0.2～10 mole; Chloride organo-aluminum compound is 0.5～20 mole;Silane compound is 0.01～10 mole; The concentration of furtherance shape dispersant in reaction system is controlled at 0.01～50 grams per liter.
In step a, the reaction temperature of organo-magnesium compound and hydroxyl compounds is typically chosen in relatively high temperatureUnder carry out comparatively favourablely, preferably, below the boiling temperature of reactant, temperature is not conventionally higher than 90 DEG C, generally not higher than 70 DEG C.The time of reaction is depended on character and the operating condition of reactant, and required time is generally at 5 minutes to 2 hours, preferably 10Minute to 1 hour. After the reaction of organo-magnesium compound and hydroxyl compounds, the solution of formation can with inert diluentMix use, inert diluent is selected from aliphatic hydrocarbon conventionally, for example iso-butane, pentane, hexane, heptane or cyclohexane andIts mixture, general hexane or heptane are proper atent solvents.
In step b, furtherance shape dispersant is dispersed in to C4～C20In alkane or aromatic solvent, be preferably dispersed in hexane,In heptane or toluene and composition thereof solvent, form solution, then with silane compound and with step a in obtain transparent moltenLiquid fully mixes, according to kind and the different in kind of furtherance shape dispersant, its C4～C20The configuration of alkane or aromatic hydrocarbons solution is denseDegree is controlled at 0.1～100 grams per liter, preferably 1～50 grams per liter, the amount adding so that furtherance shape dispersant in reaction systemConcentration is 0.001～100 grams per liter, preferably 0.01～50 grams per liter. Mixing temperature generally will be lower than the boiling temperature of system, forFor the purpose of convenient, be typically chosen between 0～90 DEG C, preferably between 10～50 DEG C. Both general selections 0.5 of incorporation timeMinute to 5 hours, preferably 10 minutes to 1 hour.
In step c, complete at a certain temperature the even mixing of all substances, the solution system first first two steps being obtainedBe reduced to uniform temperature, at this temperature, solution still keeps clear, is unlikely to become turbid or precipitate, and temperature canBe controlled between-90～30 DEG C, preferably between-70～0 DEG C, then by chloride organo-aluminum compound and titanium-containing compound successivelyProgressively slowly add, conventionally carry out fully stirring the abundant mixing that is beneficial to various materials in reinforced process, charging rate is logicalNormal selection obviously heats up and is as the criterion not cause significant reaction or system. After fully mixing, it is any known suitable to adoptMethod heats up, and as slowly, progressively, rapidly or temperature programming, it is totally different that different temperature-rising methods can obtain performance characteristicsCatalyst, in temperature-rise period, system can change muddiness into by clarification, separates out precipitation, in this precipitation reaction step,The reaction time of settling step should be long enough to obtain precipitation completely, and the reaction time can be lasted 1 minute to 10 hours,Preferably 3 minutes～5 hours.
Experiment is found, after settling step, reacts at a certain temperature a period of time and carries out the grain of maturation process to catalystShape is more favourable, and it can improve the intensity of catalyst particle, thereby it is existing to reduce the particle fragmentation of catalyst in polymerization processResemble. The temperature of maturation process is generally equal to or higher than the final temperature of precipitation reaction, and the time of slaking reaction can be controlled at0.5～10 hour, preferably 1～5 hour.
After carrying out maturation process, generally to wash, form in excessive reactant and preparation process to removeAccessory substance, any atent solvent all can be used for this washing step, for example can select iso-butane, pentane, hexane, heptane,Cyclohexane, toluene or various aromatic hydrocarbons and composition thereof etc., conventionally select with after twice of toluene wash in experiment, then fill with hexaneDivide washing. After washing, under catalyst suspension nitrogen protection, be dried, to obtain catalyst fines.
In addition, the invention still further relates to a kind of catalyst for the equal polymerization of alkene or combined polymerization, it contains above-mentioned the present invention and urgesThe product of agent component and alkyl aluminum compound, wherein the general formula of alkyl aluminum compound used is AlRhX3-hOrganicAluminium compound, in formula, R is the alkyl that hydrogen or carbon number are 1～20, X is halogen, 1 < h≤3. Preferably AlEt3、Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3、AlEt2Cl etc.
Catalytic component of the present invention can make according to the well-known way of this area olefinic polymerization Ziegler-Natta catalystWith, as used together with another kind of co-catalyst or electron donor, can also be by catalytic component of the present invention with a kind of or manyPlant Ziegler-Natta catalyst or non-Ziegler-Natta catalyst and mix use.
The present invention also provides the catalytic component that described catalytic component or described method prepare to close or be total at ethylene homoApplication in polymerisation.
Catalytic component of the present invention is applicable to various any alkene that can carry out coordination polymerization reaction, comprises a kind of alkeneThe equal polymerization of hydrocarbon or the combined polymerization of multiple alkene, the alpha-olefin such as optimal ethylene, propylene, butylene in alkene, or ethene, propylene,The mixture of butylene and one or more alpha-olefins. Comonomer is C2-C12 alkene preferably, preferably C4-C10 alkene,As 1-butylene, isobutene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 4-methylpentene-1,Diene is as butadiene, Isosorbide-5-Nitrae-hexadiene and 1,7-octadiene, and cyclenes is as ENB, and their any mixture.
It is anti-that catalyst of the present invention can adopt conventional polymerization technique to carry out polymerization in one or more polymer reactorsShould, can be gas phase, slurry or bulk polymerization, polymerisation can be intermittence or continuous polymerization process.
To slurry or bulk reaction device, reaction temperature is generally at 40-130 DEG C, preferably 60-110 DEG C, and reactor pressure generally exists0.1-8MPa, preferably 0.3-6MPa, the time of staying is generally at 0.2-6 hour, preferably 0.5-3 hour. The general boiling point of selecting existsThe aliphatic hydrocarbon of-70-100 DEG C of scope uses as diluent; If needed, polymerisation can be carried out under super critical condition.
For Gas-phase reactor, reaction temperature is generally at 60-130 DEG C, preferably 70-110 DEG C, and reactor pressure generally exists0.5-4MPa, preferably 1-3MPa, the time of staying is generally at 0.5-10 hour, preferably 1-8 hour. If need, select to closeSuitable aliphatic hydrocarbon uses as diluent, and polymerisation can be carried out under frozen state condition.
Catalyst amount generally depends on character, type of reactor and the operating condition of catalyst and to polymerizate performanceRequirement, can be used conventional catalyst consumption.
Adopt catalyst of the present invention, can obtain the catalyst system and catalyzing with good form, and catalyst has higher urgingChange active and good hydrogen response, polymerizate form can copy the particle shape of catalyst preferably, so-called" print effect ", therefore this catalyst has good combination property.
Detailed description of the invention
The method of testing using in the present invention:
The size distribution of carrier and catalyst is used MASTERSIZE particles distribution instrument, and n-hexane, as dispersant, is measuredScope 0.02～2000 μ m; Wherein particle diameter breadth coefficient is by (d90-d10)/d50Calculate, particle diameter breadth coefficient value is less,Illustrate that catalytic component granular size is more even.
The relative weight percentage of metal in catalyst system (being mainly titanium, magnesium) uses plasma emission spectrum (ICP)Measure. The pattern of catalyst and polymer uses ESEM (SEM) to measure. Melt index is used ASTM-D1238Measure. Bulk density is used DIN-53194 to measure.
Embodiment given below is for the present invention is described, instead of limits the invention.
Embodiment 1
The preparation of catalytic component: the dibutylmagnesium hexane solution (1M) and the 10.0ml that get successively 310ml hexane, 31.5mlIsooctanol, is warming up to 50 DEG C and maintains stirring reaction half an hour, obtains clear solution, then add 7ml tetraethyl orthosilicate andThe linear polystyrene polyisoprene of the D1119P(triblock copolymer SIS of Kraton, its polyisoprene content isHexane solution (10g/L) 100ml 76wt%), is cooled to-20 DEG C, adds successively the hexane of 10.5 milliliters of ethyl aluminum dichloridesSolution (3M) and 3.5ml titanium tetrachloride, maintained after low-temp reaction half an hour, naturally slowly heats up, and rises to after room temperature, addsHeat maintains 50 DEG C of reactions 2 hours. Catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexane washing three times,The consumption of each hexane is 300 milliliters, after having washed, dry that brown solid mobility powder is catalytic component, itsAverage grain diameter is 9.8 microns; Particle diameter breadth coefficient is 0.65. Elementary analysis (ICP): Ti:12.26%(weight), Mg:13.75%(weight).
Vinyl polymerization is evaluated A: 1L hexane, 1mmol triethyl aluminum and a certain amount of catalytic component are joined to 2L stainlessIn steel stirred tank, then temperature is brought up to 80 DEG C, the disposable hydrogen that adds 0.18MPa, then with ethene by systemGross pressure maintains 0.73MPa and carries out polymerisation, reacts after 2 hours, stops adding ethene, cooling, pressure release, poly-secondAlkene powder material weighing, the activity of calculating catalyst, the bulk density of test polyethylene powder and the melting under 2.16Kg load refer toNumber, result is as shown in table 1.
Vinyl polymerization is evaluated B: 1L hexane, 1mmol triethyl aluminum and a certain amount of catalytic component are joined to 2L stainlessIn steel stirred tank, then temperature is brought up to 90 DEG C, the disposable hydrogen that adds 0.4MPa, then with ethene by systemGross pressure maintains 1.0MPa and carries out polymerisation, reacts after 2 hours, stops adding ethene, cooling, pressure release, poly-secondAlkene powder material weighing, the activity of calculating catalyst, the bulk density of test polyethylene powder and the melting under 2.16Kg load refer toNumber, result is as shown in table 1.
Embodiment 2
" 7ml tetraethyl orthosilicate " is adjusted into " 10ml tetraethyl orthosilicate ", other conditions of catalytic component preparation processWith embodiment 1. The average grain diameter of products obtained therefrom is 14.4 microns. Elementary analysis (ICP): Ti:13.76%(weight), Mg:12.68%(weight).
The ethene slurry polymerization of catalyst is evaluated the condition of A and B with embodiment 1, and polymerization result is in table 1.
Embodiment 3
" 10ml isooctanol " is adjusted into " 5ml isooctanol ", " 7ml tetraethyl orthosilicate " changed into " 10ml silicic acid fourEthyl ester ", other conditions of catalytic component preparation process are with embodiment 1. The average grain diameter of products obtained therefrom is 12.1 microns.Elementary analysis (ICP): Ti:9.03%(weight), Mg:12.17%(weight).
The ethene slurry polymerization of catalyst is evaluated the condition of A and B with embodiment 1, and polymerization result is in table 1.
Comparative example 1
To add " hexane solution (10g/L) 100ml of the D1119P of Kraton " step to remove, not add furtheranceShape dispersant, other conditions of catalytic component preparation process are with embodiment 1. The average grain diameter of products obtained therefrom is 83.49 micro-Rice; Its particle diameter distribution map presents wider multimodal and distributes. Elementary analysis (ICP): Ti:8.19%(weight), Mg:13.34%(weight).
The ethene slurry polymerization of catalyst is evaluated the condition of A and B with embodiment 1, and polymerization result is in table 1.
Comparative example 2
The preparation of catalytic component: the dibutylmagnesium hexane solution (1M) and the 10.0ml that get successively 310ml hexane, 31.5mlIsooctanol, is warming up to 50 DEG C and maintains stirring reaction half an hour, obtains clear solution, then add 7ml tetraethyl orthosilicate andThe FG1901(polystyrene polybutadiene triblock copolymer of Kraton, wherein polybutadiene content 70wt%) hexaneSolution (10g/L) 100ml, is cooled to-20 DEG C, add successively 10.5 milliliters of ethyl aluminum dichlorides hexane solution (3M) and3.5ml titanium tetrachloride, maintained after low-temp reaction half an hour, naturally slowly heated up, rise to after room temperature, heating maintain 50 DEG C anti-Answer 2 hours. Catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, by hexane washing three times, the use of each hexaneAmount is 300 milliliters, after having washed, is dried to obtain brown solid mobility powder, and its average grain diameter is 12.2 microns; Particle diameterBreadth coefficient is 0.79. Elementary analysis (ICP): Ti:11.33%(weight), Mg:14.18%(weight).
The ethene slurry polymerization of catalyst is evaluated the condition of A and B with embodiment 1, and polymerization result is in table 1.
Table 1
Can find out from the experimental data of table 1 embodiment and comparative example, in the preparation process of catalyst, use the furtherance of SIS classShape dispersant and use silane compound, the catalytic component obtaining and the particle shape of polymer are good, narrow particle size distribution,The bulk density (BD) of polymer resin is higher, catalyst high comprehensive performance. Especially the embodiment of the present invention 1 and comparative exampleIn 2, compare by polystyrene block polybutadiene copolymer, it is active all suitable with melt index, the accumulation of its polymer resinDensity is higher; More make inventor feel surprised, the embodiment of the present invention 1 is compared with comparative example 2, at least from catalyst groupDivide the size distribution of particle diameter breadth coefficient and vinyl polymerization product to find out, technical scheme of the present invention is to vinyl polymerization productParticle shape and the control of granular size better.
Claims (13)
1. for the catalytic component of olefinic polymerization, it is to comprise at least one organo-magnesium compound, at least one titaniferous chemical combinationThing, at least one hydroxyl compounds, at least one chloride organo-aluminum compound, at least one silane compound and extremelyThe product of few a kind of furtherance shape dispersant; Described silane compound is as general formula (V) Si (OR5)gCl4-gShown in, formulaMiddle R5The C of saturated or undersaturated straight chain, side chain or closed chain2～C20Alkyl, 0 ﹤ g≤4; And described furtherance shapeDispersant is polystyrene block polyisoprene base polymer.
2. catalytic component according to claim 1, is characterized in that, described organo-magnesium compound is as general formula (I)MgR1 nCl2-nShown in, R in formula1The C of saturated or undersaturated straight chain, side chain or closed chain2～C20Alkyl, 0 < n≤2。
3. catalytic component according to claim 1, is characterized in that, described titanium-containing compound is as general formula (II)Ti(OR2)mCl4-mShown in, R in formula2The C of saturated or undersaturated straight chain, side chain or closed chain2～C20Alkyl, 0≤m≤4。
4. catalytic component according to claim 1, is characterized in that, described hydroxyl compounds is as general formula (III)HOR3Shown in, R in formula3The C of saturated or undersaturated straight chain, side chain or closed chain2～C20Alkyl; Described chlorideOrgano-aluminum compound is as general formula (IV) AlR4 fCl3-fShown in compound, R in general formula (IV)4C2～C20Alkyl,0.5≤f≤2.5。
5. according to the catalytic component described in any one in claim 1～4, it is characterized in that described polystyrene blockPolyisoprene base polymer comprises diblock and three blocks and derivative thereof.
6. catalytic component according to claim 5, is characterized in that, described polystyrene block polyisoprene classThe block type of optional of polymer is linear, band chain or star form.
7. according to the catalytic component described in any one in claim 1～4, it is characterized in that described polystyrene blockIn polyisoprene base polymer, the content of polyisoprene is 3～97wt%.
8. catalytic component according to claim 7, is characterized in that, described polystyrene block polyisoprene classIn polymer, the content of polyisoprene is 10～90wt%.
9. according to the preparation method of catalytic component described in any one in claim 1～8, comprise the steps,
A: organo-magnesium compound is reacted with hydroxyl compounds, obtain clear solution;
B: furtherance shape dispersant is dispersed in to C4～C20In alkane or aromatic solvent, form solution, then with described silaneThe clear solution reaction that compounds and step a obtain, obtains mixed liquor;
C: chloride organo-aluminum compound and titanium-containing compound are joined in the mixed liquor that step b obtains successively, urgedAgent ingredients suspension liquid, the solid particle reclaiming wherein obtains described catalytic component.
10. preparation method according to claim 9, is characterized in that, in every mole of organo-magnesium compound, titaniferousCompound is 0.01～10 mole; Hydroxyl compounds is 0.1～20 mole; Chloride organo-aluminum compound is 0.1～50Mole; Silane compound is 0.001～20 mole; The concentration of furtherance shape dispersant in reaction system is controlled at 0.001～100 grams per liters.
11. preparation methods according to claim 9, is characterized in that, in every mole of organo-magnesium compound, titaniferousCompound is 0.05～5 mole; Hydroxyl compounds is 0.2～10 mole; Chloride organo-aluminum compound is 0.5～20 to rubYou; Silane compound is 0.01～10 mole; The concentration of furtherance shape dispersant in reaction system is controlled at 0.01～50Grams per liter.
12. 1 kinds of catalyst for the equal polymerization of alkene or combined polymerization, it comprises in claim 1～8 urges described in any oneThe catalytic component that in agent component or claim 9～11, described in any one, method prepares, and at least one general formulaFor AlRhX3-hOrgano-aluminum compound, in formula, R is the alkyl that hydrogen or carbon number are 1～20, X is halogen, 1 < h≤3。
Method system described in any one in catalytic component or claim 9～11 described in any one in 13. claims 1～8The standby catalytic component obtaining ethylene homo close or copolymerization in application.
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| CN1247625C (en) * | 2001-06-20 | 2006-03-29 | 玻利阿黎斯聚合物有限公司 | Process for preparing olefin polymerisation catalyst component |
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