CN104558288B

CN104558288B - A kind of olefin polymer and preparation method thereof

Info

Publication number: CN104558288B
Application number: CN201310509420.8A
Authority: CN
Inventors: 严立安; 谭忠; 周奇龙; 徐秀东; 宋维玮; 于金华; 李凤奎; 尹珊珊
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2013-10-25
Filing date: 2013-10-25
Publication date: 2017-09-29
Anticipated expiration: 2033-10-25
Also published as: CN104558288A

Abstract

The invention discloses a kind of olefin polymer and preparation method thereof, this method comprises the following steps：（1）The monomer of alhpa olefin and olefin polymerization catalysis are subjected to low-temp reaction, the temperature of the low-temp reaction is that, more than or equal to 0 DEG C and less than 50 DEG C, the time of the low-temp reaction is 1 60 minutes；（2）By step（1）Obtained low-temp reaction product carries out high temperature polymerization reaction, and the temperature of the high temperature polymerization reaction is 80 120 DEG C；And olefin polymerization catalysis contains the solid constituent A and specific organo-silicon compound C of particular step preparation.By method of the invention, it is possible to improve polymerization activity during alhpa olefin high temperature polymerization, and the olefin polymer obtained is while have high fusion index, can also there is high isotactic and wide molecular weight distribution.

Description

A kind of olefin polymer and preparation method thereof

Technical field

The present invention relates to a kind of olefin polymer and preparation method thereof, gather in particular it relates to which a kind of alpha-olefin carries out high temperature The method that conjunction prepares olefin polymer, and olefin polymer obtained by this method.

Background technology

Alpha-olefine polymers are important synthetic organic materials.The use of the material removes and has required suitable mechanical property Outside, also there is the performance for adapting to processed and applied.Wherein, the isotacticity of alpha-olefine polymers, melt index and molecular weight distribution Index（MWD）It is to influence the key factor of mechanical properties of polymer and processing characteristics.

The isotacticity of alpha-olefine polymers determines the rigidity of the polymer to a certain extent.In general, isotacticity The rigidity of higher alpha-olefine polymers also can be higher.Therefore, when requiring that alpha-olefine polymers have higher rigidity, α-alkene is improved The isotacticity of hydrocarbon polymer is favourable.The even isotacticity of some application requirements polymer（Heptane extraction process is determined, and sees this Inventive embodiments, following term " polymer " isotacticity " are all determined by heptane extraction process）Reach more than 99%.But prior art The production of alpha-olefine polymers relatively difficult to achieve with so high isotacticity.

Consider from processed and applied, the melt index of polymer is higher, and the mobility of polymer is better, is more conducive to polymer Processing.Therefore, when comprehensive polymer performance and processed and applied, while mechanical property needed for ensureing material, it is desirable to poly- The higher the better for polymer melt index.However, in existing alpha-olefine polymers technology of preparing, often improving the same of melt index When, the isotacticity of alpha-olefine polymers can decline, namely the rigidity of polymer declines.Especially when the melting of alpha-olefine polymers When index also requires that the even 5g/10min higher than 3, it more difficult to realize.Therefore, the alpha-olefin for taking into account melt index and isotacticity is realized The production of polymer is always what industrial production was pursued.

The molecular weight distributing index of polymer be also influence polymer mechanical performance and processing characteristics it is another it is important because Element.High molecular weight moieties largely determine the long term mechanical strength of polymer, and low molecular weight fraction part is in very great Cheng Its extrusion performance is determined on degree.When producing injection homopolymer or anti-impact polymer, it is often desirable to which polymer is to have high melt Melt index again while there is wide molecular weight distributing index.This polymer is considered as the intensity that existing good processing characteristics has also had And rigidity.However, molecular weight distributing index is closely related with melt index, generally, high fusion index it is poly- Compound hardly results in wider molecular weight distributing index.

As can be seen here, it is expected that alpha-olefine polymers can have high isotactic and wide point while high fusion index is obtained Son amount profile exponent.

Above-mentioned alpha-olefine polymers are obtained, polymerization is most important.In the synthetically produced research and development of alpha-olefine polymers In, it has been realised that improving polymeric reaction temperature, Ziegler-Natta catalyst（Alpha-olefine polymers are commonly used polymerization and urged Agent）More sensitive can be become to molecular weight regulator hydrogen, can have produce the α with high fusion index and isotacticity- The trend of olefin polymer.But when carrying out conventional olefine polymerizing process using conventional Ziegler-Natta catalyst, Polymerization temperature is improved, polymerization activity meeting rapid decay, polymerizate yield declines, it is difficult to realize the production of polymer, cannot Alpha-olefine polymers product.

As can be seen here, prior art can not be realized carries out alpha-olefine polymerizing at high temperature, cannot have high fusion index, The alpha-olefine polymers of high isotactic and wide molecular weight distributing index.Therefore one kind is needed to realize that there is high melting to refer to for acquisition The polymerization of the alpha-olefine polymers of number, high isotactic and wide molecular weight distributing index.

The content of the invention

The purpose of the present invention is to overcome prior art not realize to carry out alpha-olefine polymerizing at high temperature, cannot have height The problem of alpha-olefine polymers of melt index, high isotactic and wide molecular weight distributing index there is provided a kind of olefin polymer and Its preparation method.

To achieve these goals, the present invention provides a kind of method for preparing olefin polymer, and this method includes following step Suddenly：

（1）'alpha '-olefin monomers and olefin polymerization catalysis are subjected to low-temp reaction, the temperature of the low-temp reaction be more than Equal to 0 DEG C and less than 50 DEG C, the time of the low-temp reaction is 1-60 minutes；

（2）By step（1）Obtained low-temp reaction product carries out high temperature polymerization reaction, the temperature of the high temperature polymerization reaction For 80-120 DEG C；

The olefin polymerization catalysis contains solid constituent A and organo-silicon compound C containing magnesium and titanium；

The solid constituent A containing magnesium and titanium is prepared by following steps：

（a）Magnesium halide is dissolved in the solvent being made up of organic epoxy compound thing, organic phosphorus compound and inert diluent In system, homogeneous solution is formed, internal electron donor compound c is optionally added into；

（b）At -30 DEG C to 60 DEG C, first by titanium compound and step（a）Obtained solution mixing, then adds and helps precipitation Agent solution, forms mixture；Or precipitation additive solution is first added to step（a）In obtained solution, then at -30 DEG C extremely At 60 DEG C, mixed with titanium compound, form mixture；

（c）By step（b）In obtained mixture be warming up to 60-110 DEG C, temperature-rise period or to after temperature optionally plus Enter internal electron donor compound d, to temperature after stir 0.5-8 hour, filter off mother liquor, obtained after being washed through inert diluent containing magnesium with The solids of titanium；

（d）By step（c）In the obtained solids containing magnesium and titanium with containing titanium compound, inert diluent and optional Internal electron donor compound e mixture is handled 1 time, then handles 1-2 with the mixture containing titanium compound and inert diluent It is secondary, inert diluent washes clean then is used, the solid constituent A containing magnesium and titanium is made；

Wherein precipitation additive solution is the mixed solution containing precipitation additive a and precipitation additive b；With every mole of magnesium halide Meter, organic epoxy compound thing is 0.2-10 moles, and organic phosphorus compound is 0.1-3 moles, and titanium compound is 0.5-50 moles, is helped Precipitation agent A is 0.001-0.3 moles, and precipitation additive B is 0.001-0.5 moles, and internal electron donor compound c is 0-3 moles, interior Electron donor compound d and e are respectively 0-5 moles, and c+d+e is 0-5 moles；

The organo-silicon compound C is dicyclopentyl dimethoxyl silane, Cyclohexyl Methyl Dimethoxysilane and tetrem At least one of TMOS.

Present invention also offers olefin polymer prepared by method provided by the present invention.

The method that the present invention is provided can carry out alpha-olefin polymerization at high temperature and have polymerization activity, polymeric articles Can be while with higher melt index, also high isotactic and wide molecular weight distributing index.The side that the present invention is provided In method, the solid constituent A prepared containing ad hoc approach and the specific organo-silicon compound C as external electron donor alkene are used Polymerized hydrocarbon catalyst, while first to carry out high temperature polymerization again anti-by 'alpha '-olefin monomers progress low-temp reaction when carrying out polymerisation Should.For example contain solid constituent A1 and specific DCPMS in embodiment 1, olefin polymerization catalysis, first polymerize rare earth during polymerization Catalyst carries out complex reaction and carries out low-temp reaction, then carries out the high temperature polymerization reaction of propylene monomer at 95 DEG C again, can To obtain polymerization activity as 39.5Kg/gcat, the melt index of obtained polypropylene product（MI）For 5.4g/10min, isotacticity （II）For 99.5% and molecular weight distributing index（MWD）For 5.7.It polymerize in embodiment 2 at 110 DEG C, can still obtains 34.6Kg/gcat polymerization activity, obtained polypropylene product melt index（MI）For 8.1g/10min, isotacticity（II）For 99.0% and molecular weight distributing index（MWD）For 6.0.Although and using A1, DCPMS in comparative example 2, without low-temp reaction, Therefore the polymerization activity of pyroreaction only has 26.1Kg/gcat, the melt index of obtained polypropylene product（MI）For 5.2g/ 10min, isotacticity（II）For 99.0% and molecular weight distributing index（MWD）For 5.7.

Other features and advantages of the present invention will be described in detail in subsequent embodiment part.

Embodiment

The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The present invention provides a kind of method for preparing olefin polymer, and this method comprises the following steps：

In the method that the present invention is provided, before 'alpha '-olefin monomers high temperature polymerization reaction is carried out, first by olefin polymerization catalysis Low-temp reaction is carried out with 'alpha '-olefin monomers, then 'alpha '-olefin monomers are further subjected to high temperature polymerization reaction；Wherein olefinic polymerization is urged The solid constituent A that agent contains is prepared through specific step, and external electron donor is used as from specific organo-silicon compound C.Cause This, in the present invention, 'alpha '-olefin monomers can carry out high temperature polymerization and have high polymerization activity, and can obtain with high melting The olefin polymer product of index, high isotactic and wide molecular weight distributing index.

According to the present invention, low-temp reaction can be carried out under above-mentioned preferable case, and the prepolymerized polymerizate of acquisition can To there is high polymerization activity in being reacted in high temperature polymerization.Preferably, the temperature of the low-temp reaction is 10 DEG C to 30 DEG C, described low The time of temperature reaction is 1-20 minutes, and the pressure of the low-temp reaction is 0.1-3MPa；It is highly preferred that the low-temp reaction when Between be 5-15 minute, the pressure of the low-temp reaction is 0.2-2.5MPa.In the present invention, the low-temp reaction is controlled in above-mentioned bar Under part, the prepolymerization polymer for the high temperature polymerization reaction for being suitable for carrying out with high polymerization activity can be obtained.

According to the present invention, the olefin polymerization catalysis can include the solid containing magnesium and titanium prepared by specific step Component A.When the solid constituent A containing magnesium and titanium prepared by above-mentioned steps is in the method for the present invention, be conducive to entering Row high temperature polymerization reaction can obtain higher polymerization activity.The solid constituent A containing magnesium and titanium can be major catalyst.

In the present invention, among the process of the solid constituent A containing magnesium and titanium described in above-mentioned preparation, step（b）In described help It can be the mixed solution containing precipitation additive a and precipitation additive b to separate out agent solution, and the precipitation additive a can be under State formula（I）One kind in shown diol-lipid compound：

Formula（I）Middle R₁-R₆、R¹-R²ⁿGroup can be identical or different, and be each independently hydrogen, halogen or substitution or The C of unsubstituted straight or branched₁-C₂₀Alkyl, C₃-C₂₀Cycloalkyl, C₆-C₂₀Aryl, C₇-C₂₀Alkaryl, C₇-C₂₀Aralkyl, C₂-C₁₀Alkylene or C₁₀-C₂₀Fused ring aryl；But R₁And R₂It can not be hydrogen, optional R₃-R₆And R¹-R²ⁿAt least two in group It is individual to link up cyclization；N can be 0-10 integer；The precipitation additive b can be selected from formula（II）R^Ⅰ _aR^Ⅱ _bSi(OR^Ⅲ)_cInstitute One kind of the organosilicon alkyl compound shown, formula（II）Middle R^Ⅰ、R^ⅡAnd R^ⅢCan be with identical or different, and can be each independently C_l-C₁₀Alkyl, C₃-C₁₀Cycloalkyl or C₆-C₁₀Aromatic yl group, wherein a and b can be 0-2 integer, and c can be the whole of 1-4 Number, and（a+b+c）=4；It is preferred that R^Ⅰ、R^ⅡC can be each independently_l-C₈Alkyl, C₃-C₆Cycloalkyl or C₆-C₁₀Aromatic yl group, R^Ⅲ Can be C_l-C₁₀Alkyl, specifically organosilicon alkyl compound can be such as tetraethoxysilane（TEOS）, methylcyclohexyl diformazan TMOS（CHMMS）, dimethoxydiphenylsilane, dicyclopentyl dimethoxyl silane（DCPMS）, diisopropyl dimethoxy Base silane, second, isobutyl dimethoxy silane.

In the present invention, the precipitation additive a is disclosed in Chinese patent CN1436766A and CN1436796A, and the patent is public The related content opened is incorporated herein by reference.

In the present invention, the precipitation additive a is in above-mentioned formula（I）In shown dihydric alcohol ester type compound, preferred formula （IV）Shown compound：

Formula（IV）Middle R₁-R₆、R¹-R²Group such as formula（I）In definition, specifically can be as：2- ethyls -1,3- the third two Alcohol dibenzoate, 2- propyl group -1,3- propylene glycol dibenzoates, the dipropylene of 2- isopropyl -2- isopentyl -1,3 Ester, 1,3 butylene glycol mesitylenic acid ester, 2- methyl isophthalic acids, the m-chlorobenzoic acid ester of 3- butanediols two, 2,3- dimethyl -1,3- fourths Bisbenzoate, 1,3- pentanediols pivalate, 2,4-PD dibenzoate, 2,2- dimethyl -1,3- pentanediols Dibenzoate, 2,4- heptandiols dibenzoate, 2- methyl -3,5- heptandiols dibenzoate, 2,3- diisopropyls -1,4- Butanediol dibenzoate, 3,5 heptandiol dibenzoates or the heptandiol dibenzoate of 4- ethyls -3,5.Preferably, can be with Such as 2,4-PD dibenzoate, 3,5 heptandiol dibenzoates or the heptandiol dibenzoate of 4- ethyls -3,5.

In the present invention, formula（II）R^Ⅰ _aR^Ⅱ _bSi(OR^Ⅲ)_cShown precipitation additive b, specifically can be as：Tetraethoxy-silicane Alkane（TEOS）, Cyclohexylmethyldimethoxysilane, dimethoxydiphenylsilane（DDS）, methyl tertbutyl dimethoxy silicon Alkane, dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, 2- ethyl piperidines Base -2- t-butyldimethoxysilanes, (the fluoro- 2- propyl group of 1,1,1- tri-) -2- ethyl piperidine bases dimethoxysilane, (1,1,1- Three fluoro- 2- propyl group)-methyl dimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylbenzene epoxide Silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, diphenyl diethyl TMOS, phenyltrimethoxysila,e, phenyl triethoxysilane or vinyltrimethoxy silane.Preferably, Ke Yiru Tetraethoxysilane, Cyclohexylmethyldimethoxysilane, dimethoxydiphenylsilane, dicyclopentyl dimethoxyl silane, Diisopropyl dimethoxy silane or second, isobutyl dimethoxy silane.

Step（b）And step（d）Described in titanium compound can be able to be formula with identical（III）TiX_n(OR)_4-nIt is shown Compound, formula（III）Middle R can be C1-C20 alkyl, and X can be halogen, n=1-4；Specifically, the titanium compound can With from titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro two Ethanolato-titanium, one kind in the ethanolato-titanium of trichlorine one or their mixture, preferably titanium tetrachloride.

In the present invention, described internal electron donor compound c, d, e can select formula（I）Shown dihydric alcohol esters chemical combination Thing, aliphatic or the Arrcostab of aromatic monocarboxylate, the Arrcostab of aliphatic or aromatic polycarboxylic acid, fatty ether, ring grease At least one of fat race ether and aliphatic ketone；Preferred aliphat or aromatic binary carboxylic acid ester and/or diether compound；More It is preferred that phthalate, malonic acid esters, succinate compound, glutaric acid esters, pivalate or carbonates.Specifically may be used With such as：Diethyl phthalate（DEP）, diisobutyl phthalate, n-butyl phthalate（DNBP）, adjacent benzene two Formic acid di-isooctyl, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, 2,3- diisopropyl butanedioic acids Diethylester, 2,3- diisopropyls di-iso-octyl succinate, 2,3- diisopropyls dibutyl succinate, 2,3- diisopropyl ambers Sour dimethyl esters, 2,2- dimethyl succinates diisobutyl ester, 2- Ethyl-2-Methyls di-iso-octyl succinate, 2- Ethyl-2-Methyls Diethyl succinate, diethylene adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, maleic acid two Ethyl ester, maleic acid n-butyl, naphthalene dicarboxylic acids diethylester, naphthalene dicarboxylic acids dibutyl ester, triethyl trimellitate, trimellitic acid Tributyl, benzene-1,2,3-tricarboxylic acid triethyl, benzene-1,2,3-tricarboxylic acid tributyl, pyromellitic acid tetra-ethyl ester or the butyl ester of pyromellitic acid four.Selection is different Internal electron donor, catalyst will show to be differently directed performance and hydrogen regulation performance.Described internal electron donor compound c, d, e can With it is identical also can be different, it is preferably identical.

In the present invention, it is preferable that in terms of every mole of magnesium halide, organic epoxy compound thing can be 0.5-4 moles, organophosphor Compound can be 0.3-1.5 moles, and titanium compound can be 5-15 moles, and precipitation additive a can be 0.01-0.1 moles, help Precipitation agent b can be 0.01-0.3 moles, and electron donor compound c can be 0-0.3 moles, and electron donor compound d and e can To be respectively 0-1 moles；C+d+e can be 0.02-1 moles.

In the present invention, the magnesium halide can be magnesium dihalide, the complex compound of the water of magnesium dihalide and alcohol, magnesium dihalide point One kind or their mixture in the derivative that one of halogen atom is replaced by alkoxy or halogenated alkoxy in minor； It is preferred that the alcohol adduct of magnesium dihalide or magnesium dihalide, such as magnesium dichloride, dibrominated magnesium, magnesium diiodide and their alcohol are closed Thing.

In the present invention, the organic epoxy compound thing can include C2-C8 aliphatic olefins, alkadienes or halogenated aliphatic At least one of oxide, glycidol ether and inner ether of alkene or alkadienes.Particular compound can be as：Oxirane, Expoxy propane, epoxy butane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether or two contractings Water glycerin ether, preferably epoxychloropropane.

In the present invention, the organic phosphorus compound can include ortho-phosphoric hydrocarbyl carbonate or halogenated hydrocarbons base ester or phosphorous acid Hydrocarbyl carbonate or halogenated hydrocarbons base ester, specifically can be as：Orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, orthophosphoric acid Triphenylmethyl methacrylate, Trimethyl phosphite, triethyl phosphite, tributyl phosphite or phosphorous triphenyl phosphate methyl esters, the preferably fourth of orthophosphoric acid three Ester.

In the present invention, the inert diluent can be used in hexane, heptane, octane, decane, benzene,toluene,xylene A kind of or their mixture.

In the present invention, in the method for preparing the solid constituent A containing magnesium and titanium, step（a）It is preferred that can be by halogen Change magnesium to be dissolved in the dicyandiamide solution being made up of organic epoxy compound thing, organic phosphorus compound and inert diluent, form uniform After solution, internal electron donor compound c is continuously added, homogeneous solution is formed；Step（b）Can be preferably：At -30 DEG C to 60 DEG C Under, precipitation additive a and precipitation additive b is added into step（a）In obtained solution, then add in titanium compound, form mixing Thing.

According to the present invention, the organo-silicon compound C can be used as external electron donor component.It is described to have under preferable case Organic silicon compound C can be formula（VI）R¹''_m''R²''_n''Si(OR³'')_4-m''-n''Shown compound, formula（VI）In, R¹' ' and R²' ' can be identical or different, and can be each independently halogen, hydrogen atom, C1-C20 alkyl, C3-C20 cycloalkyl, One kind in C6-C20 aryl and C1-C20 haloalkyls；R³' ' can be C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 virtues One kind in base and C1-C20 haloalkyls；M'' and n'' can be 0-3 integer respectively, and m''+n''<4.Have as described Organic silicon compound C specific example can enumerate trimethylmethoxysilane, diisopropyl dimethoxy silane, diisobutyl two Methoxy silane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxy silicon Alkane, t-butylethyl dimethoxysilane, tert-butyl group propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, ring Hexyl methyl dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopenta first Base dimethoxysilane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane（DCPMS）, cyclopenta hexamethylene Base dimethoxysilane, double (2- methylcyclopentyls) dimethoxysilanes, dimethoxydiphenylsilane, diphenyl diethoxy Silane, phenyl triethoxysilane, MTMS, MTES, ethyl trimethoxy silane, propyl group Trimethoxy silane, isopropyltri-methoxysilane, butyl trimethoxy silane, butyl triethoxysilane, isobutyl group front three TMOS, amyltrimethoxysilane, isopentyl trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy Base silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyltriethoxy silane Alkane, n-propyl trimethoxy silane, vinyltrimethoxy silane, tetramethoxy-silicane, tetraethoxysilane and four butoxy Silane.These organo-silicon compound can be used individually, and two or more can also be applied in combination.More preferably The organo-silicon compound C can be dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, diisobutyl diformazan TMOS, Cyclohexyl Methyl Dimethoxysilane（CHMMS）, dimethoxydiphenylsilane, methyl tertbutyl dimethoxy Silane and tetraethoxysilane（TEOS）At least one of.

According to the present invention, the high temperature polymerization reaction can be carried out under above-mentioned preferable case, can also be further preferably The temperature of the high temperature polymerization reaction is 85-110 DEG C.High temperature polymerization be conducive to obtain with high fusion index, high isotactic and The olefin polymer of wide molecular weight distributing index, but too high temperature can influence the yield of the polymer obtained, therefore can be with Control the high temperature polymerization of the present invention within the above range.

According to the present invention, the other conditions of the high temperature polymerization reaction can be the normal condition of this area.Preferable case Under, the pressure of the high temperature polymerization reaction is 0.1-6MPa, and the time of the high temperature polymerization reaction is 0.1-5 hours；It is preferred that institute The pressure for stating high temperature polymerization reaction is 0.5-5MPa, and the time of the high temperature polymerization reaction is 0.5-4 hours.

According to the present invention, polymerisation can be the homopolymerization of alpha-olefin or the combined polymerization of a variety of alpha-olefins.Institute As long as the consumption for stating the monomer of alpha-olefin disclosure satisfy that the requirement of polymerisation, desired olefin polymer is obtained；It is described The consumption of olefin polymerization catalysis can be that can realize the consumption of catalytic action.Under preferable case, the monomer and the alkene The weight ratio of polymerized hydrocarbon catalyst is 50000-200000.In the present invention, olefinic polyreaction gathers according to above-mentioned monomer and alkene The weight of catalyst is closed than carrying out, is mutually fitted with the low-temp reaction with the olefin polymerization catalysis first carried out in the method for the present invention Should, so as to realize the purpose of the present invention.

According to the present invention, the 'alpha '-olefin monomers for the present invention can be by formula CH₂The alkene that=CHR is represented, R can be with For hydrogen or C1-C6 alkyl.Under preferable case, the monomer is ethene, propylene, 1- n-butenes, 1- n-pentenes, 1- n-hexylenes, 1- Positive at least one of octene and 4-methyl-1-pentene；It is preferred that the monomer is at least one in ethene, propylene and 1- butylene Kind；Still more preferably described monomer is propylene.

According to the present invention, although can be real containing the solid constituent A containing magnesium and titanium in the olefin polymerization catalysis The goal of the invention of the existing present invention, but be not excluded in the olefin polymerization catalysis that other materials can also be included, for example can be with Further improve the material of the olefin polymerization catalysis performance.Under preferable case, the olefin polymerization catalysis also includes Machine aluminium compound B.

According to the present invention, the olefin polymerization catalysis can contain solid constituent A, organo-aluminum compound containing magnesium and titanium B and organo-silicon compound C.Under preferable case, aluminium element and the solid group containing magnesium and titanium in the organo-aluminum compound B The mol ratio of the titanium elements divided in A is 5-5000：Aluminium element in 1, preferably described organo-aluminum compound B contains magnesium and titanium with described Solid constituent A in titanium elements mol ratio be 20-1000：1；It is highly preferred that the aluminium element in the organo-aluminum compound B Mol ratio with the titanium elements in the solid constituent A containing magnesium and titanium is 50-500：1；Aluminium in the organo-aluminum compound B Element and the organo-silicon compound C mol ratio are 0.1-500:Aluminium element in 1, preferably described organo-aluminum compound B and The mol ratio 1-300 of the organo-silicon compound C:Aluminium element in 1, more preferably described organo-aluminum compound B and described organic Silicon compound C mol ratio 3-100:1.

In the present invention, the organo-aluminum compound B can be as co-catalyst, and what can be commonly used for field of olefin polymerisation is each Plant the organo-aluminum compound for the co-catalyst that can act as Ziegler-natta catalyst.In situations where it is preferred, described organic Aluminium compound B can be formula（V）AlR'_n'X'_3-n'Shown compound, formula（V）In, R' can be hydrogen, C1-C20 alkyl or C6- C20 aryl, X' can be halogen, and n' can be 1-3 integer.It is preferred that the specific example of the organo-aluminum compound B can be Trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, a chlorine diethyl At least one of aluminium, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride.It is further preferred that organic calorize Compound B can be triethyl aluminum and/or triisobutyl aluminium.

, can when the olefin high-temperature polymerization that the present invention is carried out using the olefin polymerization catalysis is reacted according to the present invention So that the solid constituent A containing magnesium and titanium, organo-aluminum compound B and organo-silicon compound C to be added separately in system monomer to be gathered Reaction is closed, but the method for the olefinic polymerization of the present invention can also first connect above-mentioned A, B and component C before being contacted with olefinic monomer Touch and carry out complex reaction.Under preferable case, methods described is additionally included in the olefin polymerization catalysis and monomer progress is low Before temperature reaction, the solid constituent A containing magnesium and titanium, the organo-aluminum compound B and the organo-silicon compound C are subjected to network Reaction is closed, the temperature of the complex reaction is 0 DEG C to 50 DEG C, the time of the complex reaction is 0.1-30 minutes, the complexing The pressure of reaction is normal pressure；It is preferred that the temperature of the complex reaction is 10-30 DEG C, the time of the complex reaction is 0.1-10 points Clock, the pressure of the complex reaction is 0.1-0.2MPa.The method of the present invention includes the complex reaction, can further carry The polymerization activity of high olefin high-temperature polymerization so that polymerization can obtain polymeric articles with higher yield at high temperature, and more Be conducive to obtaining melt index and isotacticity height and the wide polymeric articles of molecular weight distributing index.

In the preferred embodiment of the present invention, preferably olefin high-temperature polymerization is carried out in following method：Alkene gathers Close catalyst and contain the magnesium of particular step preparation and the solid constituent A of titanium；By the solid constituent A of magnesium and titanium, organo-aluminum compound B Complex reaction is carried out with organo-silicon compound C；Obtained complex reaction product carries out low-temp reaction with olefinic monomer；By what is obtained The low-temp reaction product for having certain extent of polymerization carries out high temperature polymerization reaction.The preferred embodiment can obtain higher polymerization Activity, is more beneficial for obtaining melt index and isotacticity height and the wide polymeric articles of molecular weight distributing index.

In the present invention, the olefin polymer can be by formula CH₂The aggregated reaction of olefinic monomer that=CHR is represented and , wherein R can be hydrogen or C1-C6 alkyl.Under preferable case, the olefinic monomer be ethene, propylene, 1- n-butenes, 1- just At least one of amylene, 1- n-hexylenes, the positive octenes of 1- and 4-methyl-1-pentene；It is preferred that the olefinic monomer is ethene, propylene At least one of with 1- butylene；Still more preferably described olefinic monomer is propylene.

, according to the invention it is preferred in the case of, the melt index of the olefin polymer is 1-300g/10min, and isotacticity is 94-99.8%, molecular weight distributing index is 4-15；Preferably, melt index is 4-150g/10min, and isotacticity is 95- 99.5%, molecular weight distributing index is 5.5-10.

The present invention will be described in detail by way of examples below.In following examples, melt index according to GB/T3682-2000 is determined.

Polymer isotacticity is determined using heptane extraction process, is specially：2 grams of dry polymer samples, are placed on extractor After the middle heptane with boiling is extracted 6 hours, by the polymer weight obtained by residue drying to constant weight（g）With 2（g）Ratio be For isotacticity.

Polymer molecular weight profile exponent MWD（MWD=Mw/Mn）Measure using Waters companies PL-GPC220 instrument Device, is measured by solvent of trichloro-benzenes at 150 DEG C（Standard specimen：Polystyrene, flow velocity：1.0ml/min, pillar： 3xPlgel10um MlxED-B300x7.5nm）.

In following preparation example, embodiment and comparative example, the content of each component presses inventory in the solid constituent A containing magnesium and titanium Calculate, the content of each component is calculated by inventory in obtained olefin polymerization catalysis.

Polymerization activity is obtained by polymerizeing the ratio calculation of resulting polymers quality and used catalyst quality.

The compound that following examples are used is commercially available chemical pure commodity.

Preparation example 1

This preparation example is used for the preparation for illustrating the solid constituent A containing magnesium and titanium that the present invention is used.

（a）In the reactor of displacement is repeated by high pure nitrogen, sequentially add 0.05 mole of anhydrous magnesium chloride, 0.75 and rub That toluene, 0.1 moles of epichlorohydrin, 0.033 mole of phosphoric acid tributyl, in speed of agitator 450rpm, the bar that temperature is 60 DEG C Under part, react 1.5 hours, add 1.9 mMs of diethyl phthalates（DEP）, react 1.0 hours to obtain solution；

（b）Will（a）Obtained solution is cooled to -28 DEG C, and 0.51 mole of titanium tetrachloride is added dropwise, and then adds 0.1 mole of first The 1.4 mM of 3,5 heptandiol dibenzoate and 4.4 mMs of dimethoxydiphenylsilanes of benzene dilution（DDS）, continue anti- Answer 1 hour and form mixture；

（c）Will（b）The mixture of formation is gradually heating to 85 DEG C, and solid particulate matter is separated out in temperature-rise period.Add to 85 DEG C Enter 2.6 mMs of diethyl phthalates（DEP）, constant temperature one hour, filter off mother liquor, repeatedly washed through inert diluent toluene Filter out after liquid, obtain the solids containing magnesium and titanium；

（d）Will（c）The obtained solids containing magnesium and titanium adds 0.7 mole of 0.44 mole of titanium tetrachloride and toluene 110 DEG C constant temperature 2 hours, repeats processing twice, is then washed with hexane 5 times, remaining solid product is vacuum dried to be obtained after filtering Solid constituent A1 containing magnesium and titanium.

Preparation example 2

According to the method for preparation example 1, unlike：

（a）It is middle to use " 1.9 mMs of n-butyl phthalates（DNBP）" replacement " 1.9 mMs of phthalic acids two Ethyl ester（DEP）”；

（c）In " 2.6 mMs of n-butyl phthalates（DNBP）" replacement " 2.6 mMs of phthalic acid diethyls Ester（DEP）”.Obtain the solid constituent A2 containing magnesium and titanium.

Preparation example 3

This preparation example is used for the preparation for illustrating the solid constituent of prior art.

By 0.05 mole of anhydrous magnesium chloride, 0.88 mole toluene, 0.05 moles of epichlorohydrin, the fourth of 0.05 mole of phosphoric acid three Ester is added in reactor, under conditions of speed of agitator 450rpm, temperature is 60 DEG C, is reacted 2 hours, is added 0.01 mole of neighbour Phthalate anhydride, continues to react one hour, is cooled to -28 DEG C, 0.51 mole of titanium tetrachloride is added dropwise, 85 DEG C are gradually heating to, 80 DEG C of additions, 8.0 mMs of n-butyl phthalates, 85 DEG C are arrived constant temperature 1 hour after temperature, mother liquor are filtered off, with 0.95 mole of first Benzene is washed twice, and 0.57 mole of toluene is added after filtering, and 0.36 mole of titanium tetrachloride, 110 DEG C of constant temperature 2 hours is weighed again after filtering Multiple processing once, and after 5 washings of hexane is dried, and obtains solid constituent B1.

Preparation example 4

In the reactor of displacement is repeated by High Purity Nitrogen, 52.5mmol anhydrous magnesium chlorides, 328mmol first are sequentially added Benzene, 140mmol2- ethyl hexanols, under conditions of speed of agitator 450rpm, temperature is 110 DEG C, react 3.0 hours, obtain steady Fixed uniform alcohol adduct solution；Add 3,5- heptandiol dibenzoate 0.8mmol, diisobutyl phthalate 5.6mmol, butyl titanate 2.2mmol, stir 60 minutes, are cooled to room temperature.

By above-mentioned added with 3,5- heptandiols dibenzoate 0.8mmol, diisobutyl phthalate 5.6mmol, metatitanic acid Four butyl ester 2.2mmol alcohol adduct homogeneous solution be added to be sufficiently displaced from through nitrogen, equipped with -20 DEG C of 1.0mol titanium tetrachlorides and In the reactor of 190mmol toluene, them is fully contacted at -20 DEG C by stirring, after 5 hours, be warming up to 110 DEG C, Solid precipitation is separated out in temperature-rise period, n-butyl phthalate 5.6mmol is added, reacted 1 hour, after reaction terminates, mistake Liquid is filtered out, then again contacts solid 1 hour, after filtering at 110 DEG C with 680mmol toluene and 437mmol titanium tetrachlorides Repeat and reacted once with the Solids At Low Temperatures at 110 DEG C with 680mmol toluene and 437mmol titanium tetrachlorides.By consolidating for obtaining Body thing is washed 5 times with 919mmol hexanes, is then dried, and obtains solid constituent B2.

Preparation example 5

In the reactor of displacement is repeated by High Purity Nitrogen, 52.5mmol anhydrous magnesium chlorides, 328mmol first are sequentially added Benzene, 140mmol2- ethyl hexanols, under conditions of speed of agitator 450rpm, temperature is 110 DEG C, react 3.0 hours, obtain steady Fixed uniform alcohol adduct solution；Add 3,5- heptandiol dibenzoate 0.8mmol, 2- isopropyls -2-（3- methyl butyls）- 1,3- dimethoxy propane 0.6mmol, diisobutyl phthalate 5.6mmol, butyl titanate 2.2mmol, stir 60 points Clock, is cooled to room temperature.

By above-mentioned added with 3,5 heptandiol dibenzoate 0.8mmol, 2- isopropyl -2-（3- methyl butyls）- 1,3- diformazans Epoxide propane 0.6mmol, diisobutyl phthalate 5.6mmol, butyl titanate 2.2mmol alcohol adduct homogeneous solution add Enter to being sufficiently displaced from through nitrogen, in the reactor equipped with -20 DEG C of 1.0mol titanium tetrachlorides and 190mmol toluene, pass through stirring Them is fully contacted at -20 DEG C, after 5 hours, be warming up to 110 DEG C, solid precipitation temperature-rise period is separated out in temperature-rise period Middle precipitation solid precipitation, adds n-butyl phthalate 5.6mmol, after reacting 1 hour, filters out liquid, then will be solid Body is contacted 1 hour with 680mmol toluene and 437mmol titanium tetrachlorides at 110 DEG C, is repeated after filtering and is used 680mmol toluene And 437mmol titanium tetrachlorides react once at 110 DEG C with the Solids At Low Temperatures.Obtained solids is washed with 919mmol hexanes Wash 5 times, then dry, obtain solid constituent B3.

Embodiment 1

The present embodiment is used for the method for illustrating the olefinic polymerization of the present invention.

（1）Pre- complexing.3.5 liters of autoclave gas phases third of catalyst feeder, propylene and hydrogen feed line will be connected with Alkene is sufficiently displaced from.The hexane solution of 5mL triethyl aluminums is added into catalyst feeder at room temperature（The concentration of triethyl aluminum is 0.5mol/L）, 1mL dicyclopentyl dimethoxyl silanes（DCPMS）Hexane solution（DCPMS concentration is 0.1mol/L）、 The solid constituent A1 of 10mL anhydrous hexanes and 12mg containing magnesium and titanium, mixes 2 minutes, obtains catalyst Cat-1.

（2）Prepolymerization.Catalyst Cat-1 is added to autoclave.Autoclave is closed, 1 standard is introduced and rises hydrogen and 2.4L Liquid propene；Stirring reaction 10 minutes at 15 DEG C；Multiplying power through calculating low-temp reaction is 200g polymer/g catalyst.

（3）Polymerization.It is warming up to 95 DEG C and carries out polymerisation after 1 hour, stops stirring, remove unpolymerized propylene monomer, receive Collection obtains polymer.

Determine polymerization activity, the melt index of polymer of polymerisation（MI）, isotacticity（II）, molecular weight distributing index （MWD）.As a result it is as shown in table 1.

Embodiment 2

According to the method for embodiment 1, unlike：

（2）In, with " stirring reaction 15 minutes at 10 DEG C " replacement " stirring reaction 10 minutes at 15 DEG C "；It is low through calculating The multiplying power of temperature reaction is 150g polymer/g catalyst；

（3）In, with " being warming up to 110 DEG C " replacement " being warming up to 95 DEG C ".

Polymerization, collects obtained polymer.Determine polymerization activity, the melt index of obtained polymer of polymerisation （MI）, isotacticity（II）, molecular weight distributing index（MWD）.As a result it is as shown in table 1.

Embodiment 3

According to the method for embodiment 1, unlike：

（1）In, with " 1mL tetraethoxysilanes（TEOS）Hexane solution（TEOS concentration is 0.1mol/L）" substitute " 1mL dicyclopentyl dimethoxyl silanes（DCPMS）Hexane solution（DCPMS concentration is 0.1mol/L）”；

（2）In, with " stirring reaction 5 minutes at 30 DEG C " replacement " stirring reaction 10 minutes at 15 DEG C "；It is low through calculating The multiplying power of temperature reaction is 500g polymer/g catalyst.

Embodiment 4

According to the method for embodiment 1, unlike：

（1）In, with " 1mL Cyclohexylmethyldimethoxysilanes（CHMMS）Hexane solution（CHMMS concentration is 0.1mol/L）" replacement " 1mL dicyclopentyl dimethoxyl silanes（DCPMS）Hexane solution（DCPMS concentration is 0.1mol/ L）”.

Comparative example 1

（1）Pre- complexing.Nothing.

（2）Prepolymerization.3.5 liters of autoclave gas phases third of catalyst feeder, propylene and hydrogen feed line will be connected with Alkene is sufficiently displaced from.The hexane solution of 5mL triethyl aluminums is added by catalyst feeder at room temperature（The concentration of triethyl aluminum is 0.5mol/L）, 1mL dicyclopentyl dimethoxyl silanes（DCPMS）Hexane solution（DCPMS concentration is 0.1mol/L）To height Press kettle；1 standard is introduced into autoclave and rises hydrogen and 2.4L liquid propene；Added again from catalyst feeder into autoclave 10mL anhydrous hexanes and 12mg solid constituents A1.Close autoclave, stirring reaction 10 minutes at 15 DEG C；Through calculating low-temp reaction Multiplying power be 180g polymer/g catalyst.

Comparative example 2

（1）Pre- complexing.3.5 liters of autoclave gas phases third of catalyst feeder, propylene and hydrogen feed line will be connected with Alkene is sufficiently displaced from.The hexane solution of 5mL triethyl aluminums is added into catalyst feeder at room temperature（The concentration of triethyl aluminum is 0.5mol/L）, 1mL dicyclopentyl dimethoxyl silanes（DCPMS）Hexane solution（DCPMS concentration is 0.1mol/L）、 10mL anhydrous hexanes and 12mg solid constituent A1, are mixed 2 minutes（Pre- complexing）；Obtain catalyst Cat-1.

（2）Prepolymerization.Nothing.

（3）Polymerization.Catalyst Cat-1 is added to autoclave.Closing autoclave, 1 standard of introducing liter hydrogen and 2.4L's Liquid propene；Temperature is risen into 95 DEG C in 20 minutes under agitation to carry out after polymerisation 1 hour, stops stirring, is removed unpolymerized Propylene monomer, collection obtain polymer.

Comparative example 3

According to the method for embodiment 1, unlike：

（3）In, with " being warming up to 70 DEG C " replacement " being warming up to 95 DEG C ".

Comparative example 4

According to the method for embodiment 3, unlike：

Embodiment 5

According to the method for embodiment 1, unlike：

（1）In, with " the solid constituent A2 " containing magnesium and titanium substitutes " the solid constituent A1 " containing magnesium and titanium.

Embodiment 6

According to the method for embodiment 2, unlike：

Embodiment 7

According to the method for embodiment 3, unlike：

Embodiment 8

According to the method for embodiment 4, unlike：

Comparative example 5

According to the method for comparative example 1, unlike：

Comparative example 6

According to the method for comparative example 2, unlike：

Comparative example 7

According to the method for comparative example 3, unlike：

Comparative example 8

According to the method for comparative example 4, unlike：

Comparative example 9

According to the method for embodiment 4, unlike：

（1）In, with " solid constituent B1 " substitutes " the solid constituent A1 " containing magnesium and titanium.

Comparative example 10

According to the method for comparative example 9, unlike：

（1）In, with " being warming up to 70 DEG C " replacement " being warming up to 95 DEG C ".

Comparative example 11

According to the method for comparative example 9, unlike：

（1）In, with " being warming up to 110 DEG C " replacement " being warming up to 95 DEG C ".

Polymerization, it is zero to determine polymerization activity, i.e., do not react substantially.

Comparative example 12

According to the method for embodiment 1, unlike：

（1）In, with " solid constituent B2 " substitutes " the solid constituent A1 " containing magnesium and titanium.

Comparative example 13

According to the method for embodiment 1, unlike：

（1）In, with " solid constituent B3 " substitutes " the solid constituent A1 " containing magnesium and titanium.

Comparative example 14

According to the method for comparative example 10, unlike：No（1）Pre- complexing.

Comparative example 15

According to the method for comparative example 10, unlike：No（2）Prepolymerization.

As can be seen from Table 1, embodiment 1-8 and comparative example 1-8 is the solid constituent A1 and A2 using the present invention.It is right Than embodiment 1-2,5-6 and comparative example 1-2,5-6, embodiment 1-2 is anti-using solid constituent A1, DCPMS, pre- complexing and low temperature Should, it can be polymerize under 95 DEG C and 110 DEG C of high temperature, and have high polymerization activity（AC）, polymerizate more preferable MI, II and MWD.Comparative example 1-2 use A1 and DCPMS, but without in advance complexing or low-temp reaction, at 95 DEG C polymerisation obtain AC, MI, II and MWD are poor；Embodiment 5-6, can be at 95 DEG C and 110 using solid constituent A2, DCPMS, pre- complexing and low-temp reaction It is polymerize under DEG C high temperature, and has high AC, polymerizate more preferable MI, II and MWD.Comparative example 5-6 uses A2 and DCPMS, But without complexing or low-temp reaction in advance, AC, MI, II and MWD that polymerisation is obtained at 95 DEG C are poor.

Comparative example 1 and comparative example 3, only by solid constituent A1, DCPMS, pre- complexing and low-temp reaction condition and height Temperature reaction is engaged, and could be polymerize and be obtained polymer and have a high MI, also high II and width MWD.Same comparative example 5 and contrast Solid constituent A2, DCPMS, pre- complexing and low-temp reaction condition, are only engaged, could polymerize by example 7 with pyroreaction To polymer have high MI on the premise of, also high II and width MWD.

When specific selection organo-silicon compound C is TEOS in embodiment 3 and embodiment 7, polymerization can be obtained with high MI olefin polymer, and the polymer still has preferable II and MWD.

Comparative example 3 and comparative example 4, are TEOS and solid constituent A1, pre- network in specific selection organo-silicon compound C Under conditions of conjunction and low-temp reaction, the olefin polymer for obtaining and having high MI can be polymerize by being engaged with pyroreaction, and The polymer still has preferable II and MWD.Same comparative example 7 and comparative example 8, specific selection organo-silicon compound C is TEOS, can polymerize the olefin polymer for obtaining high MI, and the polymer still has preferable II and MWD.

The solid constituent B1-B3 that the polymerisation carried out in comparative example 9-13 is obtained using prior art.Comparative example 4 With comparative example 9-11, although using CHMMS, pre- complexing and low-temp reaction, but comparative example 9-11 is existing using solid constituent The B1 that technology is obtained, therefore, polymerization activity is extremely low during progress high temperature polymerization, even without polymerization activity, can only carry out low temperature and gather Close.

In comparative example 12-13, when being used for polymerisation containing B2 and B3 solid constituents in olefin polymerization catalysis, although living Property can reach the requirement of commercial Application, but can not obtain isotactic index under the same conditions>99% polymer.

The method that the present invention is provided can carry out alpha-olefine polymerizing under high temperature, can there is high polymerization activity, the alkene of acquisition Polymer can also have high isotactic and wide molecular weight distributing index when obtaining high fusion index, should with good industry With value.

Claims

1. a kind of method for preparing olefin polymer, this method comprises the following steps：

(1) 'alpha '-olefin monomers and olefin polymerization catalysis are subjected to low-temp reaction, the temperature of the low-temp reaction is more than or equal to 0 DEG C and less than 50 DEG C, the time of the low-temp reaction is 1-60 minutes；

(2) the low-temp reaction product for obtaining step (1) carries out high temperature polymerization reaction, and the temperature of the high temperature polymerization reaction is 80-120℃；

(a) magnesium halide is dissolved in the dicyandiamide solution being made up of organic epoxy compound thing, organic phosphorus compound and inert diluent In, homogeneous solution is formed, internal electron donor compound c is optionally added into；

(b) at -30 DEG C to 60 DEG C, the solution for first obtaining titanium compound and step (a) is mixed, and then adds precipitation additive molten Liquid, forms mixture；Or first precipitation additive solution is added in the solution that step (a) is obtained, then at -30 DEG C to 60 DEG C Under, mixed with titanium compound, form mixture；

(c) mixture obtained in step (b) is warming up to 60-110 DEG C, in temperature-rise period or in being optionally added into after temperature Electron donor compound d, to temperature after stir 0.5-8 hour, elimination mother liquor is obtained after being washed through inert diluent containing magnesium and titanium Solids；

(d) by the solids containing magnesium and titanium obtained in step (c) with containing titanium compound, inert diluent and optionally in Electron compound e mixture is handled 1 time, then is handled 1-2 times with the mixture containing titanium compound and inert diluent, with Inert diluent washes clean is used afterwards, and the solid constituent A containing magnesium and titanium is made；

Wherein precipitation additive solution is the mixed solution containing precipitation additive a and precipitation additive b；In terms of every mole of magnesium halide, have Machine epoxide is 0.2-10 moles, and organic phosphorus compound is 0.1-3 moles, and titanium compound is 0.5-50 moles, helps precipitation Agent a is 0.001-0.3 moles, and precipitation additive b is 0.001-0.5 moles, and internal electron donor compound c is 0-3 moles, interior to electricity Donor compound d and e are respectively 0-5 moles, and c+d+e is 0-5 moles；

The organo-silicon compound C is dicyclopentyl dimethoxyl silane, Cyclohexyl Methyl Dimethoxysilane and tetraethoxy At least one of silane；

The precipitation additive b is selected from logical formula (II) R^Ⅰ _aR^Ⅱ _bSi(OR^Ⅲ)_cOne kind of shown organosilicon alkyl compound, formula (II) Middle R^Ⅰ、R^ⅡAnd R^ⅢIt is identical or different, and it is each independently C_l-C₁₀Alkyl, C₃-C₁₀Cycloalkyl or C₆-C₁₀Aromatic yl group, its Middle a and b are 0-2 integer, and c is 1-4 integer, and (a+b+c)=4；

The one kind of the precipitation additive a in the diol-lipid compound shown in logical formula (I)：

R in formula (I)₁-R₆、R¹-R²ⁿGroup is identical or different, and is each independently hydrogen, halogen or substituted or unsubstituted The C of straight or branched₁-C₂₀Alkyl, C₃-C₂₀Cycloalkyl, C₆-C₂₀Aryl, C₇-C₂₀Alkaryl, C₇-C₂₀Aralkyl, C₂-C₁₀Alkene Base or C₁₀-C₂₀Fused ring aryl；Optional R₃-R₆And R¹-R²ⁿAt least two in group link up cyclization；N is 0-10 integer.

2. according to the method described in claim 1, wherein, the olefin polymerization catalysis also include organo-aluminum compound B；It is described The mol ratio of aluminium element in organo-aluminum compound B and the titanium elements in the solid constituent A containing magnesium and titanium is 5-5000：1, The mol ratio of aluminium element and the organo-silicon compound C in the organo-aluminum compound B is 0.1-500:1.

3. method according to claim 1 or 2, wherein, the multiplying power of the low-temp reaction is 10-500g polymer/g catalysis Agent, the temperature of the low-temp reaction is 10 DEG C -50 DEG C, and the time of the low-temp reaction is 0.5-20 minutes, the low-temp reaction Pressure be 0.1-3MPa.

4. method according to claim 1 or 2, wherein, the temperature of the high temperature polymerization reaction is 85-110 DEG C, the height The time of warm polymerisation is 0.5-4 hours, and the pressure of the high temperature polymerization reaction is 0.5-5MPa.

5. method according to claim 1 or 2, wherein, the weight ratio of the monomer and the olefin polymerization catalysis is 50000-200000：1.

6. method according to claim 1 or 2, wherein, the monomer be ethene, propylene, 1- n-butenes, 1- n-pentenes, At least one of the positive octene of 1- n-hexylenes, 1- and 4-methyl-1-pentene.

7. method according to claim 2, wherein, methods described is additionally included in the olefin polymerization catalysis and the list Body is carried out before low-temp reaction, by the solid constituent A containing magnesium and titanium, the organo-aluminum compound B and the organosilicon compound Thing C carries out complex reaction, and the temperature of the complex reaction is 0 DEG C -50 DEG C, and the time of the complex reaction is 0.1-30 minutes.

8. method according to claim 7, wherein, the temperature of the complex reaction is 10-30 DEG C, the complex reaction Time is 0.1-10 minutes.