CN1123552A - Method for polymerising or copolymerising propylene in liquid propylene, solid catalytic component, and method for making same - Google Patents

Method for polymerising or copolymerising propylene in liquid propylene, solid catalytic component, and method for making same Download PDF

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CN1123552A
CN1123552A CN95190097A CN95190097A CN1123552A CN 1123552 A CN1123552 A CN 1123552A CN 95190097 A CN95190097 A CN 95190097A CN 95190097 A CN95190097 A CN 95190097A CN 1123552 A CN1123552 A CN 1123552A
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propylene
hydrocarbon
contact
carbon atom
ingredient
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科琳·戈梅斯-朱诺德
让-米歇尔·布鲁森
罗杰·斯皮茨
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Appryl SNC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/602—Component covered by group C08F4/60 with an organo-aluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/61—Pretreating the metal or compound covered by group C08F4/60 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/612—Pretreating with metals or metal-containing compounds
    • C08F4/614—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C08F4/6143—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/61—Pretreating the metal or compound covered by group C08F4/60 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/612—Pretreating with metals or metal-containing compounds
    • C08F4/616—Pretreating with metals or metal-containing compounds with silicon or compounds thereof

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The present invention relates to a method for polymerising or copolymerising propylene in liquid propylene in the presence of a cocatalyst and a solid catalytic component prepared by contacting (a) a solid compound containing magnesium, halogen and transition metal atoms, with (b) an organic aluminium derivative, and (c) a dialkoxysilane of formula R<1>R<2>Si(OR<3>)(OR<4>), wherein R<3> and R<4> are hydrocarbon groupings containing 1-12 carbon atoms and preferably methyl or ethyl groupings, and R<1> and R<2> are hydrocarbon groupings, where one or both of R<1> and R<2> contains at least three carbon atoms. A novel solid catalytic component for polymerising olefins, and a method for making same are also disclosed.

Description

The polymerization of propylene or copolymerization process, ingredient of solid catalyst and production method thereof in propylene liquid
The application relates at promotor and containing in the presence of the ingredient of solid catalyst of magnesium, halogen, aluminium, transition metal and Siliciumatom, in propylene liquid the polymerization of propylene or in propylene liquid the copolymerization process of propylene and α-alkene.
The application also relates to new ingredient of solid catalyst and the production method thereof that is particularly useful for aforesaid method.
Propylene polymerization can carry out in suspension or gas phase or propylene liquid.Polymerization is generally carried out in the presence of promotor, ingredient of solid catalyst and external electronic donor (being that electron donor(ED) does not add in the ingredient of solid catalyst), wherein, promotor is generally the organoaluminum derivative, ingredient of solid catalyst contains magnesium, halogen, aluminium and transition metal atoms and arbitrariness ground contains interior electron donor(ED), and external electronic donor plays the effect that improves synthetic polyacrylic isotactic index.High isotactic exponential polypropylene manifests improved mechanical property, especially improved rigidity.
Now carried out organoalkoxysilane is added in the ingredient of solid catalyst to avoid external electronic donor to be added the trial in the polymerization.United States Patent (USP) 4,442 has been described the component that contains trialkoxy silane in 276.These components make and might obtain to have high isotactic exponential polymkeric substance with medium relatively productive rate by the polymerization of propylene in suspension.The application company has been found that the polymerization for propylene in the propylene liquid, can not get high isotactic exponential polymkeric substance with these components.
Document EP 0582943 discloses the polymerization of propylene in the presence of the solid ingredient of siliceous and titanium, and wherein, the ratio of silicon and titanium is 0.5 to 100 mole of silicon of every gram titanium atom, is equivalent to 24 to 4800 moles of silicon of every mole of titanium.On other composition of this component, after the propylene prepolymerization, silicon is mixed in the solid ingredient.This component needn't be washed before being used for polymerization.
Document EP 0501741 discloses in suspension, between 150-300 ℃ of the temperature, and on the one hand in the presence of the solid ingredient that contains titanium and silane, the polymerization of propylene in the presence of organoaluminum derivative (wherein the Al/Ti mol ratio is not higher than 1) on the other hand.
The application company finds, when catalyst component is used in the polymerization process of propylene liquid propylene, organoalkoxysilane is added in the described catalyst component, and isotactic index and polymerization yield rate for the polymkeric substance that obtains demonstrate unexpected effect.
In fact, organoalkoxysilane adds ingredient of solid catalyst will not have identical influence, and this depends on that this ingredient of solid catalyst is the polymerization process that is used at the propylene liquid propylene, still is used for the polymerization process at the suspension propylene.In addition, polymerization for propylene in propylene liquid, organoalkoxysilane adds the influence of solid catalyst, as if can not be easily from when identical organoalkoxysilane is present in the polymerization as external electronic donor (promptly not adding the ingredient of solid catalyst), and observe its influence and infer out.
Have been found that now, the special organoalkoxysilane of choosing can add and contain magnesium, halogen, aluminium and transition metal atoms, and contain to arbitrariness in the ingredient of solid catalyst of interior electron donor(ED), described ingredient of solid catalyst brings the high isotactic exponential polymkeric substance that has good yield usually for the polymerization of propylene in propylene liquid, and needn't necessarily be present in the polyblend by external electronic donor.
If these organoalkoxysilanes must play the routine effect of their external electronic donors, the amount that they can be added in the just in question ingredient of solid catalyst is compared with the amount that must add polyblend outside ingredient of solid catalyst, much less.
With organoalkoxysilane role of the present invention belong to conventional in the effect of electron donor(ED) identical be inappropriate because the latter is always before adding transition metal or add in the ingredient of solid catalyst simultaneously.
The present invention relates to a kind of in the presence of promotor and ingredient of solid catalyst, in propylene liquid the polymerization process of propylene or in propylene liquid propylene and ethene or with the process for copolymerization of the α-alkene that contains 4 to 12 carbon atoms, wherein ingredient of solid catalyst is in contact with one another (mixing) by following ingredients and gets:
A. the solid chemical compound (a) that contains magnesium, halogen and transition metal atoms,
B. organoaluminum derivative (b),
C. general formula is R 1R 2Si (OR 3) (OR 4) dialkoxy silicane (c), R wherein 3And R 4Can be identical or different, expression contains the hydrocarbyl group of 1 to 12 carbon atom, is preferably methyl or ethyl group, R 1And R 2Can be identical or different, expression hydrocarbyl group, R 1For saturated and contain at least three carbon atoms.R 1And R 2But each self-contained 1 to 20 carbon atom.
For given R 2Group is bonded to the R on the silicon 1Carbon atom preferably be bonded on two carbon atoms.
For given R 1Group, R 2Be preferably saturated and contain at least three carbon atoms.R 2Preferred also is saturated and it is bonded to carbon atom and two carbon atom bondings on the Siliciumatom.
The halogen that is present in the solid chemical compound (a) is preferably chlorine.Being present in the middle transition metal of solid chemical compound (a) can be zirconium, hafnium, vanadium or be preferably titanium.
Solid chemical compound (a) can be ziegler-natta type (Ziegler-Natta) catalyst component.The ziegler-natta catalyst component is generally the complex form that contains Mg, Ti and Cl at least, and (Ti is Ti IVAnd/or Ti IIIChloride form) and arbitrariness ground contain electron donor(ED).
Electron donor(ED) and any other that the ziegler-natta type catalyst component is generally at least a magnesium compound, titanium compound, chlorine and arbitrariness can be used for the result of the compound combination of this component.
It is Mg (OR) nCl that magnesium compound is selected from general formula usually 2-nCompound, wherein R represents hydrogen or linearity or cyclic alkyl, n represents 0 to 2 integer.It is Ti (OR) xCl that titanium compound is selected from general formula usually 4-xMuriate, wherein R represents to contain aliphatic series or the aromatic hydrocarbyl or the expression COR of 1 to 14 carbon atom 1, R 1Representative contains the aliphatic series or the aromatic hydrocarbyl of 1 to 14 carbon atom, and X represents 0 to 3 integer.
The chlorine that is present in the Ziegler-natta catalyst component can be directed to titanium compound and/or magnesium compound, also can derive from independent chlorizating agent, as spirit of salt or organic chloride such as Butyryl Chloride.
The electron donor(ED) that is present in to arbitrariness in the Ziegler-natta catalyst component is the liquid or solid-state organic compound of the part of these catalyst component compositions of known formation.This electron donor(ED) is simple function or the polyfunctional compound who is preferably selected from aliphatic series or aromatic carboxylic acid and alkyl ester, aliphatic series or cyclic ethers, ketone, vinyl ester, acrylic acid derivative class, particularly alkyl acrylate or alkyl methacrylate and silicane.The compound that is suitable as electron donor(ED) is also just like methyl p toluate, ethyl benzoate, vinyl acetic monomer or N-BUTYL ACETATE, ether, paraanisic acid ethyl ester, dibutyl phthalate, dioctyl phthalate (DOP), diisobutyl phthalate, tetrahydrofuran (THF), diox, acetone, methyl iso-butyl ketone (MIBK), vinyl acetate and methyl methacrylate.
Organoaluminum derivative (b) can be that general formula is R 1R 2R 3The derivative of Al, wherein R 1, R 2And R 3Can be identical or different, expression hydrogen atom or halogen atom or contain the alkyl group of 1 to 20 carbon atom, R at least 1, R 2And R 3One of the expression alkyl group.The example of the suitable compound of mentioning is ethylaluminium dichloride or dibrominated aluminium triethyl or dibydroethyl aluminium, aluminium isobutyl dichloride or dibrominated aluminium isobutyl or dihydro aluminium isobutyl, diethylaluminum chloride or bromination diethyl aluminum or diethyl aluminium hydride, chlorination di aluminium or bromination di aluminium or hydrogenation di aluminium and di-isobutyl aluminum chloride or bromination diisobutyl aluminum or diisobutylaluminium hydride.
The organoaluminum derivative can also be the linear aluminium that general formula is
Figure A9519009700091
Linear Lv oxane, or general formula is
Figure A9519009700092
Huan Lv oxane, in these two general formulas, R represents to contain 1 to 6 carbon atom alkyl, n represents 2 to 40, preferred 10 to 20 integer.The Lv oxane can contain R group of different nature.Radicals R is preferably all represented methyl group.
For above-claimed cpd, preferably use trialkylaluminium, as tri-n-hexyl aluminum, triisobutyl aluminium, trimethyl aluminium or triethyl aluminum, especially preferably use last compound.
Before making the composition (a) and (b) and (c) contacts, preferably do not carry out prepolymerization.
With compound (a) and (b) and, be preferably representative examples of saturated aliphatic or saturated alicyclic hydrocarbon such as hexane, heptane or hexanaphthene and contact under existing (c) at hydrocarbon H.Compound (b) and (c) can join (a) in pure mode in the suspension of hydrocarbon H, or in the solution mode, on the one hand in (b) the solution mode in hydrocarbon H, join in (a) suspension in hydrocarbon H in (c) solution mode in hydrocarbon H on the other hand.The suspension of (a) preferably contains enough hydrocarbon H for described suspension in hydrocarbon H, so that can stir under the situation that does not wear away (a).
The total amount of the final hydrocarbon H that exists with (a) and (b) and (c) mixture generally is lower than 100 liters of every kg solid chemical compounds (a).
In (a) and (b) and slurry compositions (c), the add-on of general (b) should make [Al]/[M] mol ratio, and promptly the ratio by (b) aluminium that provides and transition metal M that is provided by (a) is 0.5 to 100, and preferred 1 to 50.
In (a) and (b) and the slurry compositions (c), the add-on of general (c) should make [Si]/[M] mol ratio, and promptly the ratio by (c) silicon that provides and transition metal M that (a) provides is 0.5 to 20, is preferably 1 to 10.
Well balanced for the productive rate of the isotactic index that obtains this base polymer and these polymkeric substance, preferred earlier compound (b) contact with (c) contacts it then with compound (a).For this reason, at first preferred preparation (b) and (c) solution in hydrocarbon H are mixed (b) and solution (c) then with (a) suspension in hydrocarbon H.(a) suspension in hydrocarbon H preferably contains enough hydrocarbon H to described suspension, does not wear away so that can be stirred (a).
Next step can filter and with hydrocarbon H washing and drying to contact the ingredient of solid catalyst that obtains with (c) by (a) and (b).When before being used for polymerization, needing to store especially, this solid ingredient of suggestion washing.Its stability has been promoted in this washing.
Used according to the invention in propylene liquid the polymerization or the copolymerization process of propylene, must in polyblend, add promotor, it is selected from above-mentioned general formula is R 1R 2R 3The compound of Al, for the organoaluminum derivative of choosing (b), it is 100 to 3000 that the amount of its adding makes promotor and the mol ratio that is present in the transition metal M in the ingredient of solid catalyst.The ratio that is present in the promotor in the polyblend is generally every liter of propylene liquid 0.5 to 10 mmole.
The polymerization of propylene or copolymerization can be carried out continuously or intermittently in propylene liquid, and polymerization temperature can be near critical temperature, and promptly about 92 ℃, pressure can be between normal atmosphere and emergent pressure.
For using propylene of the present invention and ethene or containing the copolymerization process of the α-alkene of 4 to 12 carbon atoms, preferably to adjust monomeric amount, make last polymkeric substance contain the polypropylene of 85-100% (weight).
Polymerization in propylene liquid can be carried out in the presence of chain-transfer agent, so that the polymkeric substance that control is produced or the melt index of multipolymer.
Preferred chain-transfer agent is a hydrogen, its add-on be alkene and hydrogen mixture 0.01 to 5mol%.
Polymerization in propylene liquid can be carried out in the presence of inert diluent or under the inertialess thinner continuously or intermittently, and inert diluent can be aliphatic hydrocrbon such as hexane, or clicyclic hydrocarbon such as hexanaphthene.
With the ingredient of solid catalyst of method for preparing, and, in the case, compound wherein (b) and (c) at first be in contact with one another, contacting with compound (a) then also is content of the present invention.Their preparation method also is a content of the present invention.These components are used in inert diluent or the inertialess thinner exists down, in the liquid phase or gas-phase polymerization processes of ethene, propylene, the α-alkene that contains 4 to 12 carbon atoms or these monomeric some mixtures.For the polymerization process in liquid phase, can use at emulsion or the polymerization technique in solution.Inert diluent can be aliphatic hydrocrbon such as hexane or clicyclic hydrocarbon such as hexanaphthene.
Polymerization can be carried out continuously or intermittently.The ordinary skill of these polymerization processs is well-known to the one skilled in the art.Usually these are aggregated in promotor (can be organoaluminum derivative such as above-named wherein a kind of) and exist down, if suitably the time, carry out in the presence of transfer agent (can be hydrogen).
Embodiment 1,2 and 9 to 19 is used to illustrate the present invention, and in these embodiments, polymerization process of the present invention has not existed under the external electronic donor in polyblend and uses.Embodiment 4 to 8 and 20 to 22 is in the presence of as the organoalkoxysilane of external electronic donor and describes the comparative example of polymerization in the presence of the catalyst component that does not contain organoalkoxysilane.Embodiment 3 is comparative examples, and is used for illustrating that the phenyl trialkoxy silane is added ingredient of solid catalyst can not get satisfied result.Yet, if dicyclopentadienyl dimethoxy silane (comparative example 6) or cyclohexyl methyl dimethoxy silane (comparative example 7) are added as external electronic donor, obtained good result (comparative example 8) with the same manner.
Embodiment 23 explanations method of the present invention wherein, contacted compound (a) before contacting with (b) in advance with (c).This embodiment more should be especially and embodiment 1 and with embodiment 12 relatively, in embodiment 1,, in advance (a) contacted with (b) with before (c) contacts, with before (a) contacts, oneself contacts (b) in advance with (c) in embodiment 12.
Embodiment 24 is comparative examples, and explanation joins dimethoxydiphenylsilane and can not get the result in the catalyst component.
Embodiment 25 is comparative examples, and explanation promotor and the mol ratio that is present in the titanium in the solid ingredient are that 1 polymerization can not get the result.
In table 1, %Ti, %Mg, %Al and %Si represent to be present in the weight percent of titanium, magnesium, aluminium and silicon in the ingredient of solid catalyst respectively.In table 1, Si/Ti represents to be present in the silicon and the mol ratio that is present in the titanium in the ingredient of solid catalyst in the polyblend, and this does not comprise the situation of organoalkoxysilane as the comparative example of external electronic donor that relate to certainly.
In table 1, II represents the isotactic index of the polymkeric substance that obtains, and this index determines by measuring the heptane index, and it equals to be insoluble in the above-mentioned polymkeric substance weight percent of the polymkeric substance in the heptane of seething with excitement.It is by measuring in 2 hours with boiling heptane extraction soluble fractions in Kumagawa type instrument.For virgin pp (homopolymer), isotactic index is equivalent to be present in the weight percentage of the isotactic polymer in the stock polymer.
Melt index among the embodiment is measured by ASTMD1238 method 2.
Polymerization yield rate in the table 1 shows with the gram numerical table of the polymkeric substance of the every gram ingredient of solid catalyst in the adding polymerization.
The connotation of the abbreviation of using among the embodiment is as follows:
DCPDMS: dicyclopentyl dimethoxyl silane
CHMDMS: cyclohexyl methyl dimethoxy silane
PTES: phenyl triethoxysilane
CPHDMS: cyclopentyl hexyl dimethoxy silane
IBiPDMS: isobutyl-sec.-propyl dimethoxy silane
CPMDMS: cyclopentyl-methyl dimethoxy silane
IBCHDMS: isobutyl-cyclohexyl dimethoxy silane
DiBDMS: second, isobutyl dimethoxy silane
DPDMS: dimethoxydiphenylsilane
DBP: dibutyl phthalate
TEA: triethyl aluminum
Embodiment 1
A) preparation of catalyst component carrier
The mean diameter that 30g is commercially available is the granular anhydrous MgCl of about 2mm 2, 4.5g1,2,4,5-tetramethyl-benzene and 200ml tetrahydrofuran (THF) (THF) add in the 300-ml reactor of crossing with nitrogen purge, have mechanical blade agitator and temperature control chuck.Temperature is risen to 60 ℃ and stirred 16 hours.Then solid filtering is come out and in the time of 60 ℃ in 15 minutes with 100ml hexane wash three times, then 60 ℃ in stream of nitrogen gas dry two hours, obtain the solid that 54.2g comprises 11.7% (weight) magnesium and 54.3% (weight) THF.
B) preparation of catalyst component
With the solid that 6.4g obtains in a) going on foot, the pure TiCl of 21ml toluene and 62ml 4Under 50 ℃, add in the 300-ml reactor of the agitators of crossing with nitrogen purge and per minute rotation 100 commentaries on classics are housed.Temperature is risen to 90 ℃ and add 1.05ml dibutyl phthalate (DBP).Stirred 2 hours.After the filtration, by adding 4ml TiCl 4Carrying out second series with 79ml toluene handles.Temperature is risen to 100 ℃ with 1 hour, filter again, and use TiCl 4Carry out 4 this processing under the same conditions again with the mixture of toluene.Next wash solids 10 minutes with the 64ml hexane at 60 ℃, filter out solid then.Resuspending goes out solid and makes temperature be back to 20 ℃ in the 200ml hexane.Add the solution that contains 1 mmole triethyl aluminum (TEA) in every milliliter of hexane of 7.5ml then, then add the solution that contains 1 mmole dicyclopentyl dimethoxyl silane (DCPDMS) in every milliliter of hexane of 2.5ml, this amount divided four parts to add at interval every 15 minutes.After last part adds, allow reaction carry out again 15 minutes.The amount of TEA that adds in the reason process and DCPDMS is observed following mol ratio herein: [Al]/[Ti]=6 and [Si]/[Ti]=2.The amount of titanium is 1.7% (weight) in the solid.Then solid filtering is come out, and use 100ml hexane wash four times down at 20 ℃.At last, solid 20 ℃ under stream of nitrogen gas dry 2 hours.It is the powder of photo 5 disclosed powder identical particles sizes and form in the patent application of FR2669915 that catalyst component presents with publication number.This catalyst component contains the silicon of aluminium and 1.3% (weight) of magnesium, 1.7% (weight) of the titanium, 19.4% (weight) of 1.5% (weight).
C) polymerization in the presence of catalyst component
With 2.5Sl hydrogen, 2.4 liters of propylene liquids and 12 mmole triethyl aluminums, in the time of 30 ℃, add in this order in 3.5 liters of stainless steel reactors that magnetic stirrer and control thermal jacket are housed.
Behind the stir about 10 minutes, with 20mg at b) in the preparation the catalyst component injecting reactor.Temperature was risen to 70 ℃ with more than 10 minutes, and keep 70 ℃ one hour.
Reduce to normal atmosphere with reactor cooling and with pressure then, obtain the powder that the 634g isotactic index is 97.7% (weight).The melt index of the polymkeric substance that makes is 2.1g/10min.Other result lists in the table 1 together.
Embodiment 2
Operate according to embodiment 1, different is when the preparation catalyst component, contains the DCPDMS solution of the solution replacement embodiment 1 of 1 mmole cyclohexyl methyl dimethoxy silane (CHMDMS) in every ml hexane with 2.5ml.When this catalyst component polymerization, the amount of the hydrogen that uses is 0.1Sl.The melt index of the polymkeric substance that obtains is 4.7g/min.The result lists in the table 1 together.
Embodiment 3
Operate according to embodiment 1, different is when the preparation catalyst component contains the solution of DCPDMS of the solution replacement embodiment 1 of 1 mmole phenyl triethoxysilane (PTES) with 2.5ml in every ml.The amounts of hydrogen of using between this catalyst component polymerization period is 0.7Sl, and the melt index of the polymkeric substance that obtains is 10.6g/10min.The result lists in the table 1 together.
Embodiment 4 (comparative example)
A) preparation of catalyst component
With 6.4g embodiment 1 a) in the solid that makes, the pure TiCl of 21ml toluene and 62ml 4Under 50 ℃, add in the 300-ml reactor of the agitators of crossing with nitrogen purge, per minute rotation 100 commentaries on classics are housed.Temperature is risen to 90 ℃, add 1.05ml dibutyl phthalate (DBP) then.Stirred 2 hours.After the filtration, add 4mlTiCl 4Carrying out second series with 79ml toluene handles.Temperature was risen to 100 ℃ in 1 hour.Filter and use TiCl then 4With the mixture of toluene under the same conditions, carry out 4 this processing again.Then washed 3 times with 10 minutes down at 60 ℃ at every turn, filter out then with the 64ml hexane.At last, with solid under stream of nitrogen gas 60 ℃ of dryings 2 hours.Catalyst component be with publication number be the powder identical particle size described of the photo 5 in the patent application of FR2669915 and the powder of form.This catalyst component contains 2% (weight) titanium and 19.6% (weight) magnesium.
B) polymerization in the presence of catalyst component
With 1.05Sl hydrogen, 2.4 liters of propylene liquids, 12 mmole triethyl aluminums and 0.017 mmoles in this order, add down at 30 ℃ and have in 3.5 liters of stainless steel reactors of magnetic stirrer and thermal control chuck as the dicyclopentyl dimethoxyl silane (DCPDMS) of external electronic donor.Determine to add the amount of the DCPDMS in the reactor so that [Si]/[Ti] mol ratio is 2.
Behind the stir about 10 minutes, in 20mg catalyst component (its preparation method was just described) injecting reactor, temperature was risen to 70 ℃ with 10 minutes in the above, and keep 70 ℃ one hour.
Reaction is reduced to normal atmosphere with reactor cooling to room temperature and with pressure after finishing.Obtaining 700 g isotactic indexes is the powder of 89.3% (weight).The melt index of the polymkeric substance that makes is 2.8g/10min.Other result lists in the table 1 together.
Embodiment 5 (comparative example)
Repeat comparative example 4, different is do not add dicyclopentyl dimethoxyl silane in polymerization process, and the hydrogen add-on to be 0.4Sl.The melt index of the polymkeric substance that makes is 8.1g/10min.Other result lists in the table 1 together.
Embodiment 6 (comparative example)
With 3.2Sl hydrogen, 6 liters of propylene liquids, 30 mmole triethyl aluminums and 3 mmoles dicyclopentyl dimethoxyl silane (DCPDMS) as external electronic donor, under 30 ℃, adding has in 8 liters of stainless steel reactors of magnetic stirrer and thermal control chuck in this order.
Stir after 10 minutes, with 40mg comparing embodiment 4 a) in the catalyst component injecting reactor that makes.Temperature was risen to 70 ℃ in more than 10 minutes, and keep 70 ℃ one hour.
Then reactor is chilled to room temperature, and pressure is reduced to normal atmosphere.Obtain the powder that the 2150g isotactic index is 97.8% (weight).The melt index of the polymkeric substance that makes is 3.8g/10min.The results are shown in Table 1 for other.
Embodiment 7 (comparative example)
Repeat comparative example 6, different is to replace 3 mmole DCPDMS with 3 mmole CHMDMS.The amounts of hydrogen of using in the case is 1.6Sl.The melt index of the polymkeric substance that makes is 4.6g/10min.The result lists in the table 1 together.
Embodiment 8 (comparative example)
Repeat comparative example 6, different is to replace 3 moles of DCPDMS with 3 mmole PTES.In the case, the amounts of hydrogen of using is 1.2Sl.The melt index of the polymkeric substance that makes is 7.2g/10min.The result lists in the table 1 together.
Embodiment 9
Operate according to embodiment 1, different is in the catalyst component preparation process, adds the triethyl aluminum (and no longer being 7.5ml) that the every ml of 15ml contains 1mmol.In addition, the 15 minutes branches in every again interval add the DCPDMS solution that 5ml concentration is 1mmol/ml (and no longer be among the embodiment 1 2.5ml) for four times.Here the amount of TEA of Jia Ruing and DCPDM is observed mol ratio: [Al]/[Ti]=2 and [Si]/[Ti]=4, the amount of titanium is 1.7% (weight) in the solid.The melt index of the polymkeric substance that makes is 1.4g/10min.The result lists in the table 1 together.
Embodiment 10
Operate according to embodiment 1, different is adds the triethyl aluminum that 30ml concentration is 1mmol/ml (and only no longer be 7.5ml) in preparation catalyst component process.In addition, every again interval 15 minutes divides four parts to add the DCPDMS solution that 10ml concentration is 1mmol/ml (and no longer be among the embodiment 1 2.5ml).Here the amount of TEA of Jia Ruing and DCPDMS is observed mol ratio: [Al]/[Ti]=24 and [Si]/[Ti]=8, the amount of titanium is 1.7% (weight) in the solid.The melt index of the polymkeric substance that makes is 1.2g/10min.The result who obtains lists in the table 1 together.
Embodiment 11
Operate according to embodiment 10, different is to add the CHMDMS solution replacement DCPDMS solution that 10ml concentration is 1mmol/ml.The melt index of the polymkeric substance that makes is 5.3g/10min.The result lists in the table 1 together.
Embodiment 12
Operate according to embodiment 1, different is being prepared as follows of catalyst component:
With a) solid of middle preparation of 6.4g embodiment 1, the pure TiCl of 21ml toluene and 62ml 4, in the 300-ml reactor of the agitator of crossing with nitrogen purge 50 ℃ of addings, per minute rotation 100 commentaries on classics are housed.Temperature is risen to 90 ℃, add 1.05ml dibutyl phthalate (DBP) then.Stirred 2 hours.After the filtration, by adding 4mlTiCl 4Carrying out second series with 79ml toluene handles.Temperature was risen to 100 ℃ with 1 hour.Filter then, and carry out 4 times under the same conditions again and handle.Then washed solid 10 minutes down at 60 ℃, refilter out with the 64ml hexane.With the solid resuspending that so obtains in the 200ml hexane.In the time of 20 ℃, preparation contains the mixture of dicyclopentyl dimethoxyl silane (DCPDMS) solution that triethyl aluminum (TEA) solution that 7.5ml concentration in hexane is lmmol/ml and 2.5ml concentration in hexane is 1mmol/ml.This mixture was at room temperature stirred 10 minutes.Then this mixture of 10ml is added every 15 minutes branch 4 parts.Last part makes reaction proceed 15 minutes again after adding.The amount of TEA that adds in the reason process and DCPDMS is observed following mol ratio herein: [Al]/[Ti]=6 and [Si]/[Ti]=2, the content of titanium is 1.7% (weight) in the solid.Then this solid filtering is come out, and then wash 4 times down at 20 ℃ with the 100ml hexane.At last, with this solid in stream of nitrogen gas 20 ℃ of dryings 2 hours, this catalyst component be with publication number be powder identical particle size and the form pulverulence that the photo 5 in the FR2669915 patent application is described.This catalyst component contains the silicon of aluminium and 1.1% (weight) of magnesium, 1.5% (weight) of the titanium, 17.5% (weight) of 1.8% (weight).The melt index of the polymkeric substance that makes is 2.2g/10min.The result lists in the table 1 together.
Embodiment 13
Operate according to embodiment 12, different is with 15ml concentration is the triethyl aluminum of 1mmol/ml and the TEA of the DCPDMS preparation that 5ml concentration is 1mmol/ml and the mixture of DCPDMS.These two kinds of compounds were at room temperature reacted 10 minutes.15 minutes branch four parts in every then interval add this mixture of 20ml.Here the amount of TEA of Jia Ruing and DCPDMS is observed mol ratio: [Al]/[Ti]=12 and [Si]/[Ti]=4, the amount of titanium is 1.7% (weight) in the solid.The melt index of the polymkeric substance that makes is 1.3 g/10min.The result who obtains lists in the table 1 together.
Embodiment 14
Operate according to embodiment 12, different is with 3.75ml concentration is the triethyl aluminum of 1mmol/ml and the TEA of the DCPDMS preparation that 1.25ml concentration is 1mmol/ml and the mixture of DCPDMS.These two kinds of compounds were at room temperature reacted 10 minutes.15 minutes branch 4 parts in every then interval add this mixture of 5ml.Here the amount of TEA of Jia Ruing and DCPDMS is observed mol ratio: [Al]/[Ti]=3 and [Si]/[Ti]=1, the amount of titanium is 1.7% (weight) in the solid.The melt index of the polymkeric substance that makes is 2g/10min.The result who obtains lists in the table 1 together.
Embodiment 15
Operate according to embodiment 1, different is to add 2.5ml cyclopentyl n-hexyl dimethoxy silane (CPHDMS) to replace DCPDMS solution in preparation catalyst component process.The amounts of hydrogen of using when the catalyst component polymerization that so obtains is 0.9Sl.The melt index of the polymkeric substance that makes is 3.2g/10min.The result lists in the table 1 together.
Embodiment 16
Operate according to embodiment 1, different is to add 2.5ml isobutyl-sec.-propyl dimethoxy silane (iBiPDMS) to replace DCPDMS solution in the catalyst component preparation process.The amounts of hydrogen of using in the catalyst component polymerization process that so obtains is 1.2Sl.The melt index of the polymkeric substance that makes is 3.6g/10min.The result lists in the table 1 together.
Embodiment 17
Operate according to embodiment 1, different is to add 2.5ml cyclopentyl-methyl dimethoxy silane (CPMDMS) to replace DCPDMS solution in the catalyst component preparation process.The amounts of hydrogen of using when the catalyst component polymerization that so obtains is 0.7Sl.The melt index of the polymkeric substance that makes is 4.8g/10min.The result lists in the table 1 together.
Embodiment 18
Operate according to embodiment 1, different is to add 2.5ml isobutyl-cyclohexyl dimethoxy silane (iBCHDMS) solution to replace DCPDMS solution when the preparation catalyst component.The amounts of hydrogen of using when the catalyst component polymerization that so obtains is 0.9Sl.The melt index of the polymkeric substance that makes is 3.7g/10min.The result lists in the table 1 together.
Embodiment 19
Operate according to embodiment 1, different is to add 2.5ml second, isobutyl dimethoxy silane (DiBDMS) solution to replace DCPDMS solution when the preparation catalyst component prepares.The amounts of hydrogen of using when the catalyst component polymerization that so obtains is 1.2Sl.The melt index of the polymkeric substance that makes is 7.2g/10min.The result lists in the table 1 together.
Embodiment 20 (comparative example)
A) preparation of catalyst component carrier
With the commercially available anhydrous MgCl of 30g 2, 4.5g 1 and 200ml tetrahydrofuran (THF) (THF) add in the 300-ml reactor that cross with nitrogen purge, that have mechanical blade agitator and temperature control chuck.Temperature is risen to 60 ℃ and stirred 16 hours.Washed 3 times with 15 minutes at 60 ℃ then with solid filtering, and with the 100ml hexane, under stream of nitrogen gas, drying is 2 hours under 60 ℃ then.Obtain the solid that 54.2g comprises 11.7% (weight) magnesium and 54.3% (weight) THF, its form is identical that photo 3 is described in the FR2669915 patent application with publication number.
B) preparation of catalyst component
With 6.4g carrier (its preparation method was just described), 21ml toluene and the pure TiCl of 62ml 4Under 50 ℃, add in the 300-ml reactor of the agitators of crossing with nitrogen purge, have per minute rotation 100 commentaries on classics.When temperature rises to 90 ℃, add 1.05ml dibutyl phthalate (DBP) and also stirred 2 hours.After the filtration, add 4mlTiCl 4Carrying out second series with 79ml toluene handles.Temperature was risen to 100 ℃ with 1 hour.Filter then and also carry out 4 this processing under the same conditions again.Then use the 64ml hexane, in 10 minutes, wash solid three times, filter out then at 60 ℃.At last, this solid under stream of nitrogen gas 60 ℃ of dryings 2 hours.This catalyst component be with publication number be the powder identical particle size described of the photo 5 in the patent application of FR2669915 and the powder of form.
Catalyst component contains the magnesium of the titanium and 19.6% (weight) of 2% (weight).
C) polymerization in the presence of catalyst component
With 0.9Sl hydrogen, 2.4 liters of propylene liquids, 12 mmole triethyl aluminums and 0.017 mmoles cyclopentyl-n-hexyl dimethoxy silane (CPHDMS) as external electronic donor, in this order under 30 ℃, add and have 3.5 of magnetic stirrer and thermal control chuck-rise in the stainless steel reactor.Determining to add the amount of the CPHDMS in the reactor, is 2 to observe [Si]/[Ti] mol ratio.
Stir after 10 minutes the catalyst component injecting reactor that 20mg is prepared previously.Temperature was risen to 70 ℃ with 10 minutes, and when keeping 70 ℃ 1 hour.
After reaction finishes, with reactor cooling and make pressure reduce to normal atmosphere.Obtain the powder that the 519g isotactic index is 63.1% (weight).The melt index of the polymkeric substance that makes is 24.1g/10min.Other result lists in the table 1 together.
Embodiment 21 (comparative example)
Operate according to comparative example 20, different is to add 0.017 mmole isobutyl-sec.-propyl dimethoxy silane (iBiPDMS) to replace cyclopentyl-n-hexyl dimethoxy silane when polymerization.The amounts of hydrogen of using in the polymerization process in the presence of the catalyst component that so obtains is 1.2Sl.The melt index of the polymkeric substance that makes is 7.1g/10min.The result who obtains lists in the table 1 together.
Embodiment 22 (comparative example)
Operate according to comparative example 20, different is to add 0.017 mmole isobutyl-cyclohexyl dimethoxy silane (iBCHDMS) to replace cyclopentyl-n-hexyl dimethoxy silane in polymerization process.The amounts of hydrogen of using in the catalyst component polymerization process that so obtains is 0.9Sl.The melt index of polymkeric substance is 10.9g/10min.The result lists in the table 1 together.
Embodiment 23
A) preparation of catalyst component
With 6.4g embodiment 1 a) in the solid, 21ml toluene and the pure TiCl of 62ml that make 4Under 50 ℃, add in the 300-ml reactor of the agitator of crossing with nitrogen purge, have per minute rotation 100 commentaries on classics.
Temperature is risen to 90 ℃, add 1.05ml dibutyl phthalate (DBP) then.Stirred two hours.After the filtration, add 4ml TiCl 4Carrying out second series with 79ml toluene handles.Temperature was risen to 100 ℃ with 1 hour.Then filter and carry out 4 this processing under the same conditions again.Washed solids 10 minutes with the 64ml hexane at 60 ℃ then, again it is filtered out.With this solid resuspending in the 200ml hexane.When temperature has been reduced to 20 ℃, add the solution that contains 1 mmole (DCPDMS) in the every ml hexane of 2.5ml, this measures the 15 minutes branches in every interval and adds for 4 times.After last part adds, restir 15 minutes.
Next, be that the TEA solution of 1 mmole/ml adds and stirred 15 minutes with 7.5ml concentration in hexane.The amount of TEA that adds in the reason process and DCPDMS is observed following mol ratio herein: [Al]/[Ti]=6 and [Si]/[Ti]=2, the amount of titanium is 1.7% (weight) in the solid.Then solid filtering is come out, wash 4 times at 20 ℃ with the 100ml hexane again.At last, with this solid under stream of nitrogen gas 20 ℃ of dryings 2 hours.The catalyst component that so makes is powder morphology, and it is the identical of photo 5 in the patent application of FR2669915 with publication number.This catalyst component contains the silicon of aluminium and 1% (weight) of magnesium, 1.3% (weight) of the titanium, 18.2% (weight) of 1.8% (weight).
B) polymerization in the presence of catalyst component
According to c among the embodiment 1) step, different be to use the catalyst component that its preparation just described and add 2.4Sl hydrogen replace 2.5Sl among the embodiment 1.The melt index of the polymkeric substance that makes is 2.8g/10min.Other result lists in the table 1 together.
Embodiment 24 (comparative example)
According to the step among the embodiment 1, different is in order to prepare catalyst component, replace 2.5ml DCPDMS solution with 2.5ml every liter of solution that contains the dimethoxydiphenylsilane of 1 mmole in hexane, and the amounts of hydrogen of using to be 0.7Sl in polymerization.The melt index of the polymkeric substance that makes is 12.5g/10min.Other result lists in the table 1 together.
Embodiment 25 (comparative example)
According to the step of embodiment 1, different is 12 mmoles that add among the 0.048 mmole triethyl aluminum replacement embodiment 1, and adds the 20mg among the 100mg ingredient of solid catalyst replacement embodiment 1 in polymerization.Obtain the 10g polypropylene at last, being equivalent to productive rate is every g solid ingredient 100g polypropylene.
Table 1
Ingredient of solid catalyst embodiment alkoxy silane kind %Ti %Mg %Al %Si 1 DCPDMS 1.5 19.4 1.7 1.3 2 CHMDMS 1.6 19.5 1.7 1.33 (comparative example) PTES 1.8 19 1.4 1.24 (comparative examples) 2 19.65 (comparative example) 2 19.66 (comparative examples) 2 19.67 (comparative example) 2 19.68 (comparative example) 2 19.6 9 DCPDMS 1.6 18.5 1.7 1.6 10 DCPDMS 1.6 17.8 1.6 1.7 11 CHMDMS 1.6 18.4 1.5 1.8 12 DCPDMS 1.8 17.5 1.5 1.1 13 DCPDMS 1.8 14 1.5 1.4 14 DCPDMS 1.9 17.7 1.2 1 15 CPHDMS 1.6 17.3 2 2.1 16 iBiPDMS 1.8 18.4 1.5 1.1 17 CPMDMS 2 18.4 1.6 1.2
Table 1 (continuing)
Ingredient of solid catalyst embodiment alkoxy silane kind %Ti %Mg %Al %Si 18 iBCHDMS 1.8 18.4 1.5 0.9 19 DiBDMS 1.5 18.8 1.5 120 (comparative example) 2 19.621 (comparative examples) 2 19.622 (comparative example) 2 19.6 23 DCPDMS 1.8 18.3 1.3 124 (comparative example) DPDMS 1.9 20.1 1.6 2.0
Table 1 (continuing)
Polymerizing condition and acetonideexample external electronic donor kind Si/Ti II productive rate (g/g) 1 97.7 31,700 2 93.4 199003 (comparative example) 87.8 126004 (comparative example) DCPDMS 2 89.3 350005 (comparative example) 64.9 157006 (comparative example) DCPDMS 350 97.8 537007 (comparative example) CHMDMS 350 96.8 297008 (comparative example) PTES 350 97.2 20,800 9 98.5 26,400 10 98.5 27,300 11 94.6 16,500 12 97.6 37,500 13 98.4 34,200 14 96 38,600 15 94.9 15,500 16 94.9 21,400 17 90.1 26300
Table 1 (continuing)
Polymerizing condition and acetonideexample external electronic donor kind Si/Ti II productive rate (g/g) 18 95.1 20,100 19 91.6 3085020 (comparative example) CPHDMS 2 63.1 2595021 (comparative example) iBiPDMS 2 92.1 3660022 (comparative example) iBCHDMS 2 84.9 32,800 23 95.8 3635024 (comparative examples) 83.7 21500

Claims (19)

1, in the presence of promotor and ingredient of solid catalyst in propylene liquid the polymerization of propylene or in propylene liquid propylene and ethene or contain 4 process for copolymerization to the α-alkene of twelve carbon atom, described catalyst component obtains after by following composition contact:
A. solid chemical compound (a) that contains magnesium, halogen and transition metal atoms
B. an organoaluminum derivative (b)
C. a general formula is R 1R 2Si (OR 3) (OR 4) dialkoxy silicane (c), R wherein 3And R 4Can be identical or different, expression hydrocarbyl group, R 1And R 2Can be identical or different, expression hydrocarbyl group, R 1Be saturated and contain at least 3 carbon atoms; It is characterized in that (a) and (b) do not carry out prepolymerization before contacting with (c), and promotor and the mol ratio that is present in the transition metal M in the ingredient of solid catalyst are 100 to 3000.
2,, it is characterized in that being bonded to R according to the method for claim 1 1Siliciumatom on carbon atom and two carbon atom bondings.
3, according to the method for claim 1 or 2, it is characterized in that radicals R 2Be saturated, and be bonded to R 2Silicon on carbon atom and two carbon atom bondings.
4, according to the method one of in the claim 1 to 3, it is characterized in that (b) and (c) at first be in contact with one another, contact with (a) then.
5,, it is characterized in that (a) and (b) and (c) in hydrocarbon, be in contact with one another according to the method one of in the claim 1 to 4.
6, according to the method one of in the claim 1 to 5, it is characterized in that (b) and (c) at first in hydrocarbon solution, mix, mix with (a) suspension in hydrocarbon then.
7,, it is characterized in that hydrocarbon is radical of saturated aliphatic or saturated clicyclic hydrocarbon according to the method for claim 5 or 6.
8, according to the method one of in the claim 1 to 7, it is characterized in that (a) and (b) and (c) between contact by aluminium that provides by (b) and the transition metal mol ratio that provides by (a) be 0.5 to 100 and preferred 1 to 50 mode carry out.
9, according to the method one of in the claim 1 to 8, it is characterized in that (a) and (b) and (c) between contact by the mol ratio of the silicon that provides by (c) and the transition metal that provides by (a) be 0.5 to 20 and 1 to 10 the mode of being preferably carry out.
10,, it is characterized in that ingredient of solid catalyst is with radical of saturated aliphatic or the washing of saturated clicyclic hydrocarbon and be dried to arbitrariness before propylene polymerization or copolymerization according to the method one of in the claim 1 to 9.
11, according to the method one of in the claim 1 to 10, it is characterized in that promotor is that general formula is R 1R 2R 3The organoaluminum derivative of Al, wherein each R 1, R 2And R 3Can be identical or different, expression hydrogen atom or halogen atom or contain the alkyl group of 1 to 20 carbon atom, R 1, R 2And R 3In at least one the expression alkyl group.
12, produce the method for the ingredient of solid catalyst that contains magnesium, halogen, aluminium, transition metal and Siliciumatom, described ingredient of solid catalyst makes after the following ingredients contact:
A. solid chemical compound (a) that contains magnesium, halogen and transition metal atoms
B. an organoaluminum derivative (b)
C. a general formula is R 1R 2Si (OR 3) (OR 4) dialkoxy silicane, R wherein 3And R 4Can be identical or different, expression hydrocarbyl group, R 1And R 2Can be identical or different, expression hydrocarbyl group, R 1Be saturated 3 carbon atoms that also contain at least; It is characterized in that (b) and (c) at first be in contact with one another, contact with (a) then.
13, according to the method for claim 12, it is characterized in that (b) and (c) at first in hydrocarbon solution, mix, mix with (a) suspension in hydrocarbon then.
14,, it is characterized in that hydrocarbon is radical of saturated aliphatic or saturated clicyclic hydrocarbon according to the method for claim 13.
15, according to the method one of in the claim 12 to 14, it is characterized in that (a) and (b) and (c) between contact by aluminium that provides by (b) and the transition metal mol ratio that provides by (a) be 0.5 to 100 and preferred 1 to 50 mode carry out.
16, according to the method one of in the claim 12 to 15, it is characterized in that (a) and (b) and (c) between contact by the mol ratio of the silicon that provides by (c) and the transition metal that provides by (a) be 0.5 to 20 and 1 to 10 the mode of being preferably carry out.
17, according to the method one of in the claim 12 to 16, it is characterized in that being bonded to R 1Silicon on carbon atom and two carbon atom bondings.
18, according to the method one of in the claim 12 to 17, it is characterized in that radicals R 2Be saturated and be bonded to R 2Silicon on carbon atom and two carbon atom bondings.
19, the ingredient of solid catalyst that can make according to the method one of in the claim 12 to 18.
CN95190097A 1994-02-18 1995-02-08 Method for polymerising or copolymerising propylene in liquid propylene, solid catalytic component, and method for making same Pending CN1123552A (en)

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