CN109293805A - Olefin polymerization solid catalytic component, component preparation method and catalyst system thereof - Google Patents

Olefin polymerization solid catalytic component, component preparation method and catalyst system thereof Download PDF

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CN109293805A
CN109293805A CN201710613258.2A CN201710613258A CN109293805A CN 109293805 A CN109293805 A CN 109293805A CN 201710613258 A CN201710613258 A CN 201710613258A CN 109293805 A CN109293805 A CN 109293805A
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bis
phosphoryl
compound
benzene
catalytic component
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CN109293805B (en
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徐人威
朱博超
王雄
韩晓昱
韩振刚
任峰
剡军
李德旭
陈兴锋
陈龙
王
王一
陈陆军
张平生
穆蕊娟
张鹏
王海
许云波
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Petrochina Co Ltd
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Petrochina Co Ltd
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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
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

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

Abstract

The invention discloses an olefin polymerization solid catalystThe catalytic component has better catalytic activity when used for propylene polymerization, higher isotacticity of the polymer and better comprehensive performance, thereby having good application prospect. The invention further discloses a preparation method of the solid catalytic component and a catalyst system containing the catalytic component.

Description

Olefin polymerization solid catalyst component, method for preparing ingredients thereof and its catalyst system
Technical field
The present invention relates to a kind of olefin polymerization solid catalyst component, method for preparing ingredients thereof and its catalyst systems, specifically relate to And high isotatic polypropylene solid catalytic component, method for preparing ingredients thereof and its catalyst system.
Background technique
Since Ziegler-Natta catalyst come out since, polypropylene realizes large-scale production, nowadays polypropylene at For most fast one of the kind of demand growth rate in thermoplastic resin.Although being changed by means such as blending, copolymerization, filling and enhancings Property each field such as high-performance polypropylene can be obtained, and be widely used in packaging, household electrical appliances, automobile, chemical industry, building, but promote The key developed into polypropylene industrial is still the improvement of catalyst.Currently, the most commonly used catalyst of industrial application is Ziegler-Natta catalyst, conventional Ziegler-Natta catalyst be by magnesium compound, titanium compound, halide and to electricity Donor compound contacts to be formed.The study found that the electron donor introduced in catalyst plays key to the improvement of catalyst performance Effect, electron donor can not only improve the activity and capacity of orientation of catalyst, it is often more important that can change the molecule knot of polymer Structure improves polyacrylic quality.So far, the research main attention of polypropylene Z-N catalyst is started to have gone to searching comprehensive Energy is more preferably or the electron donor compound for the energy that has specific characteristics, the variation of electron donor compound also become promotion catalyst updating and change The principal element in generation.
Currently, largely disclosing a variety of Donor compounds, such as polybasic carboxylic acid, monocarboxylic esters or multi-carboxylate Or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and its derivative, wherein more the most commonly used is the fragrance of binary Carboxylic acid esters, such as n-butyl phthalate or diisobutyl phthalate etc. are (referring to Chinese patent CN85100997A), it also industrially obtains widely application.In recent years the study found that phthalate chemical combination Object, which has human health, to be endangered, and the area such as European Union of the U.S. has begun the use of limitation phthalic acid ester in the plastic.Cause This, finds the novel internal electron donor of one kind to replace phthalate internal electron donor extremely urgent.In addition, people couple Containing heteroatomic internal electron donor compound research and few.Wherein, Dow Global Technologies Inc. is in diester Introducing hetero-atoms on the main chain of class compound structure have synthesized a kind of compound containing silyl ester (referring to CN 102282181) catalyst activity, but when being used as electron donor prepared is not high.Continually develop the internal electron donor of new construction Closing object still has positive meaning and good technical prospect.
Summary of the invention
The present invention provides a kind of olefin polymerization solid catalyst component, includes specific double dialkoxy phosphoryls in catalyst component The Donor compound of benzene structure can assign product higher stereoregularity, especially suitable for propylene polymerization.The present invention The preparation method of solid catalytic component, and the catalyst system comprising solid catalytic component are also provided.
Technical solution of the present invention is accomplished in that
A kind of olefin polymerization solid catalyst component includes (1) magnesium halide；(2) titanium compound；(3) at least one meeting formula (I) double dialkoxy phosphoryl benzene-like compounds of structure:
In formula, R1、R2、R3、R4It is identical or different, it is each independently selected from the alkyl, naphthenic base, aryl of 1-8 carbon atom Or heteroaryl；
R5、R6、R7、R8It is identical or different, respectively alkyl, naphthenic base or aralkyl selected from hydrogen, 1-8 carbon atom by oneself Base；
By weight percentage, the content of titanium compound is 0.5-15%, preferably 2%-12% to each component；To electricity Donor compound content is 3-30%, preferably 3-15%；Halogenation content of magnesium is 60%-90%, preferably 60%-85%.
According to the present invention, meet in double dialkoxy phosphoryl benzene-like compounds of formula (I) structure, preferably R1、R2、R3、R4 It is each independently selected from the alkyl or cycloalkyl of 1-6 carbon atom, specifically includes methyl, ethyl, n-propyl, isopropyl, positive fourth Base, isobutyl group, n-pentyl, isopentyl, n-hexyl or cyclohexyl；More preferable R1、R2、R3、R4It is each independently selected from 3-6 carbon The alkyl or cycloalkyl of atom specifically includes isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, n-hexyl or cyclohexyl.
, according to the invention it is preferred to R5、R6、R7、R8It is the alkyl or cycloalkyl of hydrogen, 1-6 carbon atom, specifically includes hydrogen, first Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, n-hexyl or cyclohexyl；More preferable R5、R6、 R7、R8It is the alkyl of hydrogen or 1-3 carbon atom, specifically includes hydrogen, methyl, ethyl, n-propyl, isopropyl.
According to the present invention, the compound for meeting formula (I) structure includes but is not limited to: 1,2- bis- (dimethoxyphosphoryls) Bis- (diethoxy phosphoryl) benzene of benzene, 1,2-, bis- (positive propoxy phosphoryl) benzene of 1,2-, 1,2- bis- (isopropoxy phosphoryls) Bis- (n-butoxy phosphoryl) benzene of benzene, 1,2-, bis- (isobutoxy phosphoryl) benzene of 1,2-, 1,2- bis- (n-pentyloxy phosphoryls) Bis- (isoamoxy phosphoryl) benzene of benzene, 1,2-, bis- (positive hexyloxy phosphoryl) benzene of 1,2-, 1,2- bis- (dissident's oxygroup phosphoryls) Bis- (diethoxy the phosphoryl) -3,6- methylbenzenes of bis- (the dimethoxyphosphoryl) -3,6- methylbenzenes of benzene, 1,2-, 1,2-, 1,2- are bis- Bis- (isopropoxy the phosphoryl) -3,6- methylbenzenes of (positive propoxy phosphoryl) -3,6- methylbenzene, 1,2-, the bis- (n-butoxies of 1,2- Phosphoryl) -3,6- methylbenzene, bis- (isobutoxy the phosphoryl) -3,6- methylbenzenes of 1,2-, 1,2- bis- (n-pentyloxy phosphoryls) - Bis- (isoamoxy the phosphoryl) -3,6- methylbenzenes of 3,6- methylbenzene, 1,2-, bis- (positive hexyloxy the phosphoryl) -3,6- methyl of 1,2- Bis- (dissident's oxygroup phosphoryl) -3,6- methylbenzenes of benzene, 1,2-, bis- (the dimethoxyphosphoryl) -3,6- ethylo benzenes of 1,2-, 1,2- are bis- (diethoxy phosphoryl) -- 3,6- ethylo benzene, 1,2- bis- (positive propoxy phosphoryls) -- bis- (isopropyl oxygen of 3,6- ethylo benzene, 1,2- Base phosphoryl) -3,6- ethylo benzene, bis- (n-butoxy the phosphoryl) -3,6- ethylo benzenes of 1,2-, bis- (the isobutoxy phosphinylidynes of 1,2- Base) -3,6- ethylo benzene, bis- (n-pentyloxy the phosphoryl) -3,6- ethylo benzenes of 1,2-, bis- (isoamoxy the phosphoryl) -3,6- of 1,2- Bis- (positive hexyloxy the phosphoryl) -3,6- ethylo benzenes of ethylo benzene, 1,2-, 1,2- bis- (dissident's oxygroup phosphoryl) -3,6- ethylo benzenes, 1, Bis- (diethoxy the phosphoryl) -3,6- n-propylbenzenes of bis- (the dimethoxyphosphoryl) -3,6- n-propylbenzenes of 2-, 1,2-, 1,2- are bis- Bis- (isopropoxy the phosphoryl) -3,6- n-propylbenzenes of (positive propoxy phosphoryl) -3,6- n-propylbenzene, 1,2-, bis- (the positive fourths of 1,2- Oxygroup phosphoryl) -3,6- n-propylbenzene, bis- (isobutoxy the phosphoryl) -3,6- n-propylbenzenes of 1,2-, the bis- (n-pentyloxies of 1,2- Phosphoryl) -3,6- n-propylbenzene, bis- (isoamoxy the phosphoryl) -3,6- n-propylbenzenes of 1,2-, bis- (the positive hexyloxy phosphinylidynes of 1,2- Base) -3,6- n-propylbenzene, bis- (dissident's oxygroup phosphoryl) -3,6- n-propylbenzenes of 1,2-, 1,2- bis- (dimethoxyphosphoryls) - Bis- (diethoxy the phosphoryl) -3,4,5,6- methylbenzenes of 3,4,5,6- methylbenzene, 1,2-, 1,2- bis- (positive propoxy phosphoryls) - Bis- (isopropoxy the phosphoryl) -3,4,5,6- methylbenzenes of 3,4,5,6- methylbenzene, 1,2-, 1,2- bis- (n-butoxy phosphoryls) - Bis- (isobutoxy the phosphoryl) -3,4,5,6- methylbenzenes of 3,4,5,6- methylbenzene, 1,2-, 1,2- bis- (n-pentyloxy phosphoryls) - Bis- (isoamoxy the phosphoryl) -3,4,5,6- methylbenzenes of 3,4,5,6- methylbenzene, 1,2-, 1,2- bis- (positive hexyloxy phosphoryls) - Bis- (dissident's oxygroup phosphoryl) -3,4,5,6- methylbenzenes of 3,4,5,6- methylbenzene, 1,2-, 1,2- bis- (dimethoxyphosphoryls) - Bis- (diethoxy the phosphoryl) -3,4,5,6- ethylo benzenes of 3,4,5,6- ethylo benzene, 1,2-, 1,2- bis- (positive propoxy phosphoryls) - Bis- (isopropoxy the phosphoryl) -3,4,5,6- ethylo benzenes of 3,4,5,6- ethylo benzene, 1,2-, 1,2- bis- (n-butoxy phosphoryls) - Bis- (isobutoxy the phosphoryl) -3,4,5,6- ethylo benzenes of 3,4,5,6- ethylo benzene, 1,2-, 1,2- bis- (n-pentyloxy phosphoryls) - Bis- (isoamoxy the phosphoryl) -3,4,5,6- ethylo benzenes of 3,4,5,6- ethylo benzene, 1,2-, 1,2- bis- (positive hexyloxy phosphoryls) - Bis- (dissident's oxygroup phosphoryl) -3,4,5,6- ethylo benzenes of 3,4,5,6- ethylo benzene, 1,2-, 1,2- bis- (dimethoxyphosphoryls) - Bis- (diethoxy the phosphoryl) -3,4,5,6- n-propylbenzenes of 3,4,5,6- n-propylbenzene, 1,2-, bis- (the positive propoxy phosphinylidynes of 1,2- Base) -3,4,5,6- n-propylbenzene, bis- (isopropoxy the phosphoryl) -3,4,5,6- n-propylbenzenes of 1,2-, the bis- (n-butoxies of 1,2- Phosphoryl) -3,4,5,6- n-propylbenzene, bis- (isobutoxy the phosphoryl) -3,4,5,6- n-propylbenzenes of 1,2-, 1,2- bis- (positive penta Oxygroup phosphoryl) -3,4,5,6- n-propylbenzene, bis- (isoamoxy the phosphoryl) -3,4,5,6- n-propylbenzenes of 1,2-, 1,2- be bis- (positive hexyloxy phosphoryl) -3,4,5,6- n-propylbenzene or bis- (dissident's oxygroup phosphoryl) -3,4,5,6- n-propylbenzenes of 1,2-.
Double dialkoxy phosphoryl benzene-like compounds can be using the 1,2- halogeno-benzene of formula (a) and the Asia of formula (b) Alkyl acid phosphate ester compounds hybrid reaction synthesizes to obtain.
R in formula (a) 1,2- halogeno-benzene5、R6、R7、R8It is identical as formula (I) institute's definition；X is identical or different, be Cl, Br or I, It is preferred that Cl；
R in formula (b) alkyl ester compounds1’、R2’、R3' identical or different, alkyl selected from 1-8 carbon atom, Naphthenic base or aralkyl preferably are selected from the alkyl or cycloalkyl of 1-8 carbon atom, the more preferably alkyl or ring from 1-6 carbon atom Alkyl.
The preparation of compound is as shown in formula -1,30-100 DEG C of reaction temperature, preferably 50-80 DEG C, and most preferably 60 DEG C.
According to the present invention, magnesium halide described in solid catalytic component is selected from magnesium chloride, magnesium bromide or magnesium iodide, preferably chlorine Change magnesium.
According to the present invention, titanium compound described in solid catalytic component is the compound for meeting formula (II):
TiX1 p(OR1)4-p (II)
Wherein X1For halogen atom, preferably chlorine or bromine, more preferable chlorine；P is the integer of 0-4.
R1For the alkyl containing 1-10 carbon atom, the alkyl is saturations or undersaturated straight chain, branch or cyclic hydrocarbon Base or the alkyl further contain hetero atom, such as S, N, O, Si；The alkyl is preferably alkyl, alkenyl, alkynyl, ring Alkyl, aryl, aralkyl.R1The alkyl of more preferable linear chain or branched chain.
As R1Example include but is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding Base, n-pentyl, n-hexyl, n-heptyl, n-octyl, positive decyl, allyl, cyclobutenyl, cyclopenta, cyclohexyl, cyclohexenyl group, benzene Base, benzyl, tolyl, phenethyl.
The example of the titanium compound includes but is not limited to: tetraalkoxy titanium, such as titanium tetramethoxide, purity titanium tetraethoxide, four Positive propoxy titanium, tetraisopropoxy titanium, four titanium n-butoxides, four isobutoxy titaniums, four cyclohexyloxy titaniums, four phenoxide titaniums；Or It is titanium tetrahalide, such as titanium tetrachloride, titanium tetrabromide, titanium tetra iodide；Or three halogenated titanium of alkoxy, such as methoxytitanium trichloride, Ethyoxyl titanium trichloride, positive propoxy titanium trichloride, nbutoxytitanium trichloride, ethyoxyl titanium tribromide；Or dialkoxy Dihalide titanium, such as dimethoxy titanium chloride, diethoxy titanium chloride, diisopropoxy titanium chloride, dipropoxy dichloro Change titanium, diethoxy dibrominated titanium；Or tri-alkoxy list halogenated titanium, such as trimethoxy titanium chloride, triethoxy titanium chloride, three Isopropoxy titanium chloride, three positive propoxy titanium chlorides, three n-Butoxyl titanium-chlorides.The preferred high halogen-containing titanizing of the present invention is closed Object, especially titanium tetrachloride.
Present invention further propose that the preparation method of the olefin polymerization solid catalyst component.
In this case, proposition of the present invention prepares two kinds of preferred method of solid catalytic component, but does not show to prepare institute of the present invention The solid catalytic component stated is only limitted to following two method.
According to the first preparation method, preparation process includes:
(1) magnesium halide alcohol adduct solution is prepared
Under nitrogen atmosphere, anhydrous magnesium halide, alcohol compound are stirred in alkane solvent to being uniformly dispersed, metatitanic acid is added Ester and the compound for meeting formula (I) structure continue to stir at the same temperature, obtain the magnesium halide alcohol adduct solution of stable and uniform And be cooled to room temperature for use,
In formula, R1、R2、R3、R4It is identical or different, it is each independently selected from the alkyl, naphthenic base, aryl of 1-8 carbon atom Or heteroaryl；R5、R6、R7、R8It is identical or different, respectively alkyl, naphthenic base or aralkyl selected from hydrogen, 1-8 carbon atom by oneself Base；
Wherein, the molar ratio of alcohol compound and magnesium halide is 1-10:1；The molar ratio of formula (I) compound and magnesium halide is 0.01-0.2:1；The molar ratio 0.9-1.1:1 of titanate esters and magnesium halide；It is 1-6h in 40-200 DEG C of reaction total time；
(2) solid catalytic component is prepared
At a temperature of nitrogen atmosphere and -25-40 DEG C, titanium compound is mixed with the magnesium halide alcohol adduct solution of step (1), is stirred It mixes and is gradually warming up to 80-135 DEG C, add the chemical combination for meeting formula (I) structure for being 0.01-0.2:1 with magnesium halide molar ratio Object reacts 1-4 hours, equivalent titanium compound is added again, the reaction was continued at a temperature of 80-135 DEG C 1-4 hours, is filtered, is washed It washs, be dried to obtain solid catalytic component, it is 1- that total amount and the volume ratio of magnesium halide alcohol adduct solution, which is added, in the titanium compound 4:1.
According to the first preparation method, the titanium compound has the general formula as shown in formula (II):
TiX1 p(OR1)4-p... (II), each substituent group are defined as described above.
The compound for meeting formula (I) structure is selected from the compound of single kind or multiple compounds are used in compounding.
The total amount and magnesium halide molar ratio for the compound for meeting formula (I) structure being added twice in step (1) and step (2) For 0.05-0.25:1.
The magnesium halide is magnesium chloride, magnesium bromide or magnesium iodide, preferably magnesium chloride.
The alcohol compound be selected from 1-10 carbon atom monohydric alcohol, preferred alcohol, propyl alcohol, butanol, 2- ethyl-oneself Alcohol.The molar ratio of alcohol compound and magnesium halide preferred 2-8:1, more preferable 3-6:1；
The titanate esters are that general formula is Ti (OR)4Compound, wherein R is the alkyl or cycloalkyl of 1-8 carbon, preferably titanium Sour four butyl esters.
The preferred C of alkane solvent8-C12Alkane solvent, the amount ratio of alkane solvent and magnesium halide is 0.5-20mL/g, It is preferred that 1-15mL/g, more preferable 3-10mL/g；
In step (1), reaction temperature is 40-200 DEG C, preferably 60-180 DEG C, more preferable 80-150 DEG C.
Second of method for preparing the ingredient of solid catalyst is proposed according to the present invention.Its preparation process includes:
S1 is under nitrogen atmosphere, abundant with spherical magnesium halide alcohol polymer particle form and -25-40 DEG C of titanium compounds by magnesium halide Contact is warming up to 40-80 DEG C and the compound for meeting formula (I) structure is added, and meets the compound and magnesium halide mole of formula (I) structure Than for 0.01-0.2:1；
When S2 is warming up to 80-135 DEG C again, continuously adds and meet formula (I) knot with magnesium halide molar ratio for 0.01-0.2:1 The compound of structure simultaneously reacts 1-4 hours；
S3 filters out liquid, and adding titanium compound, the reaction was continued at a temperature of 80-135 DEG C 1-4 hours, titanium compound and halogen The mass ratio for changing magnesium alcoholate particle is 10-30:1, using filter, washing, dry obtained solid catalysis component.
According to second method, wherein the mass ratio of titanium compound and magnesium halide alcohol adduct particle is preferably 1-6:1, more excellent Select 1-4:1.
The total amount for meeting the compound of formula (I) structure is added in step S1 and step S2 twice and magnesium halide molar ratio is 0.05-0.25:1.
The spheric granules that the preferred anhydrous magnesium chloride of magnesium halide alcohol adduct particle/ethyl alcohol compound is formed, and suggest referring in The method that state patent CN94103454.2 is provided prepares.
Further, the present invention proposes a kind of olefin polymerization catalyst system including aforesaid solid catalyst component, can be wide It is general to be used for olefinic polymerization.
Optimal technical scheme according to the present invention, catalyst system include following component:
(1) solid catalytic component above-mentioned；
(2) alkyl aluminum compound；
(3) at least one silane compound.
It is not particularly limited for alkyl aluminum compound of the invention, trialkylaluminium is selected from, such as trimethyl aluminium, triethyl group Aluminium, triisopropylaluminiuand, triisobutyl aluminium or trioctylaluminum；It is further selected from the monochlorinated aluminium of dialkyl group, such as the monochlorinated aluminium of diethyl, two different The monochlorinated aluminium of propyl, the monochlorinated aluminium of diisobutyl or the monochlorinated aluminium of dioctyl；It is further selected from dialkyl group sesquialter aluminium, such as ethyl sesquialter chlorine Change aluminium；It is further selected from alkylaluminoxane, such as methylaluminoxane.
The trialkylaluminium of low alkyl group specifically preferred according to the invention with 1-5 carbon atom, including trimethyl aluminium, triethyl group The mixture of aluminium, tri-propyl aluminum and triisobutyl aluminium, most preferably triethyl aluminum, triisobutyl aluminium or both.
There is following general formula for silane compound of the invention:
R2 nSi(OR3)4-n (III)
Wherein R2And R3It is saturations or undersaturated straight chain, branch or cyclic group or R2And R3It is further preferably miscellaneous Atom, such as containing halogen, S, N, O group；When there are two or more R2When, they are identical or different.It is preferred that R2It is 1-10 Alkyl, alkenyl, naphthenic base, aryl, the aralkyl of carbon atom, optimizing alkyl or aryl.As R3Example have methyl, ethyl, N-propyl, isopropyl.N be 0-4 integer, preferably 1 or 2.
The example of above-mentioned silane compound includes but is not limited to: dimethoxydiphenylsilane, Bicvclopentyl dimethoxy Silane, Cyclohexyl Methyl Dimethoxysilane, double isopropyl dimethoxysilanes, double isobutyl group dimethoxysilanes, n-propyl Trimethoxy silane, tetraethoxy disilane, n-propyl triethoxysilane.These silane compounds can be used alone, can also It is used in mixed way with two or more.
By weight percentage, in catalyst system, the dosage of solid catalytic component is 0.01-6%, preferably 0.01%-2%；The dosage of alkyl aluminum compound is 85%-95%, preferably 88%-92%；The dosage of silane compound are as follows: 0.01-10%, preferably 0.01%-5%.
The alkene of optimal technical scheme according to the present invention, the catalyst system catalysis can be selected from ethylene, propylene, fourth The alpha-olefins such as alkene, 1- hexene.
The polymerization reaction of another optimal technical scheme according to the present invention, the catalyst system catalysis includes homopolymerization or is total to Polymerization.
Specific embodiment
The present invention is described further with reference to embodiments, it should be noted that following embodiments cannot function as pair The limitation of the scope of the present invention, any improvement made on the basis of the present invention is all within protection scope of the present invention.
Test condition:
Polypropylene isotacticity (II.) test method: 6h is extracted using boiling heptane, insoluble matter is measured after dry and accounts for total weight Percentage composition.
Embodiment 1
(1) after being sufficiently displaced from side-neck flask with nitrogen, 4.94g anhydrous magnesium chloride, 18.9g isooctanol, 30mL is added Decane, warming while stirring react 2 hours at this temperature to 130 DEG C, obtain uniform mixture.In advance by 2.65g metatitanic acid Four butyl esters and bis- (dimethoxyphosphoryl) benzene compounds of 1.8g 1,2- are added in 5ml toluene, and reaction 0.5h is stirred at room temperature and obtains It to mixed solution, transfers them in aforementioned mixture, at 130 DEG C, the reaction was continued 1 hour.Reaction terminates, and is cooled to room temperature Form the alcohol adduct solution of stable and uniform.
(2) it by the homogeneous solution of above-mentioned preparation, is added drop-wise to and is sufficiently displaced from through nitrogen and equipped with -20 DEG C of 250ml tetra- in 1h It in the reactor of titanium chloride, is added dropwise, is warming up to 110 DEG C by 3.5h, addition contains 2g1, the bis- (dimethoxyphosphoryls of 2- Base) benzene-like compounds toluene solution, react 2h at this temperature.Liquid is filtered out after reaction, rejoins 250ml tetra- Titanium chloride, in 110 DEG C of reaction 2h.Reaction solution is filtered out after reaction, is washed 6 times with dried hexane, after vacuum drying To ingredient of solid catalyst.
Catalyst composition analysis result:
Titanium compound content: 10.1% (wt)
Content of magnesium chloride: 81.7% (wt)
Electron donor compounds content: 8.2% (wt)
(3) polymerization reaction.1.2kg purification is added after nitrogen is sufficiently displaced from 5 liters of stainless steel cauldrons equipped with blender Propylene and 2.7ml triethyl aluminum (concentration 1moL/L) and 0.08ml Bicvclopentyl dimethoxysilane dimethoxysilane, add Enter the catalyst solid constituent 15mg of above-mentioned preparation, 2g hydrogen is added, then heats to 70 DEG C, at this temperature polymerization reaction 1h.Unreacting gas is discharged after reaction, obtains white polypropylene.
Polymerization result: catalytic activity 19,500gPP/gCat, polymer apparent density 0.45g/cm3, isotacticity is 98.6%.
Embodiment 2
(1) after being sufficiently displaced from side-neck flask with nitrogen, 4.94g anhydrous magnesium chloride, 18.9g isooctanol, 30mL is added Decane, warming while stirring react 2 hours at this temperature to 130 DEG C, obtain uniform mixture.In advance by 2.65g metatitanic acid Four butyl esters and 1.8g contain bis- (dimethoxyphosphoryl) benzene of 1,2- and bis- (the dimethoxyphosphoryl) -3,6- methylbenzenes of 1,2- The mixture of (molar ratio 1:1) is added in 5ml toluene, and reaction 0.5h is stirred at room temperature and obtains mixed solution, transfers them to In aforementioned mixture, at 130 DEG C, the reaction was continued 1 hour.Reaction terminates, be cooled to room temperature to be formed stable and uniform alcohol adduct it is molten Liquid.
(2) it by the homogeneous solution of above-mentioned preparation, is added drop-wise to and is sufficiently displaced from through nitrogen and equipped with -20 DEG C of 250ml tetra- in 1h It in the reactor of titanium chloride, is added dropwise, is warming up to 110 DEG C by 3.5h, is added and contains bis- (the dimethoxy phosphorus of 1,2- containing 2g Acyl group) benzene and 1, the toluene solution of the mixture of bis- (dimethoxyphosphoryl) -3,6- methylbenzenes (molar ratio 1:1) of 2-, herein At a temperature of react 2h.Liquid is filtered out after reaction, rejoins 250ml titanium tetrachloride, in 110 DEG C of reaction 2h.Reaction knot Reaction solution is filtered out after beam, is washed 6 times with dried hexane, ingredient of solid catalyst is obtained after vacuum drying.
Catalyst composition analysis result:
Titanium compound content: 7.1% (wt)
Content of magnesium chloride: 82.5% (wt)
Electron donor compounds content: 10.4% (wt)
(3) polymerization reaction.1.2kg purification is added after nitrogen is sufficiently displaced from 5 liters of stainless steel cauldrons equipped with blender Propylene and 2.7ml triethyl aluminum (concentration 1moL/L) and 0.08ml Bicvclopentyl dimethoxysilane dimethoxysilane, add Enter the catalyst solid constituent 15mg of above-mentioned preparation, 2g hydrogen is added, then heats to 70 DEG C, at this temperature polymerization reaction 1h.Unreacting gas is discharged after reaction, obtains white polypropylene.
Polymerization result: catalytic activity 20,500gPP/gCat, polymer apparent density 0.43g/cm3, isotacticity is 98.7%.
Embodiment 3
It is sufficiently displaced from band branch pipe reaction flask addition with nitrogen, titanium tetrachloride is added and is cooled to -20 DEG C, then in 1 plus 1h Spheric granules (the molecular formula MgX of chlorination magnesium alcoholate is added in time2.2.8ROH, 20 μm of partial size, by CN94103454.2 institute State method preparation), it stirs and is started to warm up after coming into full contact with, be added when temperature rises to 60 DEG C and with magnesium halide molar ratio be Bis- (dimethoxyphosphoryl) benzene compounds of 1, the 2- of 0.125:1, continue to heat up, when temperature rises to 110 DEG C, continuously add with Magnesium chloride molar ratio is bis- (dimethoxyphosphoryl) benzene compounds of 1,2- of 0.125:1, and reacts 2h at such a temperature, reacts After, filter out liquid, add titanium tetrachloride, the reaction was continued at a temperature of 110 DEG C 2 hours, filter out liquid, with it is dry oneself Solid titanium catalyst component is made in alkane washing, vacuum drying, and wherein titanium chloride and alcohol adduct molar ratio are 2.8:1.It is added twice The total amount and magnesium chloride molar ratio of bis- (dimethoxyphosphoryl) benzene compounds of compound 1,2- are 0.25:1.Polymerizing condition is the same as real Apply example 1.Catalyst composition analysis result:
Titanium compound content: 11.1% (wt)
Content of magnesium chloride: 79.7% (wt)
Electron donor compounds content: 9.2% (wt)
Polymerization result: catalytic activity 23,600gPP/gCat, polymer apparent density 0.46g/cm3, isotacticity is 98.5%.
Embodiment 4
It is sufficiently displaced from band branch pipe reaction flask addition with nitrogen, titanium tetrachloride is added and is cooled to -20 DEG C, then in 1 plus 1h Spheric granules (the molecular formula MgX of chlorination magnesium alcoholate is added in time2.2.8ROH, 20 μm of partial size), it stirs after coming into full contact with It starts to warm up, is added when temperature rises to 60 DEG C and contains the bis- (dimethoxyphosphoryls of 1,2- with magnesium halide molar ratio for 0.125:1 Base) benzene and 1, the mixture of bis- (dimethoxyphosphoryl) -3,6- methylbenzenes (molar ratio 1:1) of 2- continues to heat up, when temperature liter When to 110 DEG C, continuously adding with magnesium chloride molar ratio is that 0.125:1 contains bis- (dimethoxyphosphoryl) benzene of 1,2- and 1,2- The mixture of bis- (dimethoxyphosphoryl) -3,6- methylbenzenes (molar ratio 1:1), and 2h is reacted at such a temperature, reaction terminates Afterwards, liquid is filtered out, titanium tetrachloride is added, the reaction was continued at a temperature of 110 DEG C 2 hours, filters out liquid, is washed with dry hexane It washs, is dried in vacuo, solid titanium catalyst component is made, wherein titanium chloride and alcohol adduct molar ratio are 2.8:1.It is added and contains twice The mixing of bis- (dimethoxyphosphoryl) benzene of 1,2- and bis- (the dimethoxyphosphoryl) -3,6- methylbenzenes (molar ratio 1:1) of 1,2- The total amount and magnesium chloride molar ratio of object are 0.25:1.Polymerizing condition is the same as embodiment 1.Catalyst composition analysis result:
Titanium compound content: 9.0% (wt)
Content of magnesium chloride: 82.7% (wt)
Electron donor compounds content: 8.3% (wt)
Polymerization result: catalytic activity 24,600gPP/gCat, polymer apparent density 0.44g/cm3, isotacticity is 98.9%.
Embodiment 5
Bis- (dimethoxyphosphoryl) benzene compounds of 1,2- are changed to bis- (the dimethoxyphosphoryl) -3,6- methyl of 1,2- Benzene, content is respectively 1.9g and 2.1g the other the same as in Example 1 twice.Catalyst composition analysis result:
Titanium compound content: 6.1% (wt)
Content of magnesium chloride: 83.7% (wt)
Electron donor compounds content: 10.2% (wt)
Polymerization result: catalytic activity 27,000gPP/gCat, polymer apparent density 0.43g/cm3, isotacticity is 98.7%.
Embodiment 6
Bis- (dimethoxyphosphoryl) benzene of 1,2- are changed to bis- (dimethoxyphosphoryl) -3,6- methylbenzenes of 1,2-, twice Additional amount it is identical, it is 0.27:1, the other the same as in Example 3 that total amount and magnesium chloride molar ratio, which is added,.Catalyst composition analysis result:
Titanium compound content: 9.7% (wt)
Content of magnesium chloride: 82.5% (wt)
Electron donor compounds content: 7.8% (wt)
Polymerization result: catalytic activity 25,050gPP/gCat, polymer apparent density 0.45g/cm3, isotacticity is 98.6%.
Embodiment 7
Bis- (dimethoxyphosphoryl) benzene of 1,2- are changed to bis- (dimethoxyphosphoryl) -3,6- ethylo benzenes of 1,2-, twice Additional amount is respectively 1.9g and 2.1g, the other the same as in Example 1.Catalyst composition analysis result:
Titanium compound content: 8.1% (wt)
Content of magnesium chloride: 79.3% (wt)
Electron donor compounds content: 12.6% (wt)
Polymerization result: catalytic activity 26.100gPP/gCat, polymer apparent density 0.43g/cm3, isotacticity is 98.8%.
Embodiment 8
Bis- (dimethoxyphosphoryl) benzene of 1,2- are changed to bis- (dimethoxyphosphoryl) -3,6- ethylo benzenes of 1,2-, twice Additional amount is identical, and total amount is added and magnesium chloride molar ratio is 0.23:1, the other the same as in Example 3.Catalyst composition analysis result:
Titanium compound content: 9.2% (wt)
Content of magnesium chloride: 81.7% (wt)
Electron donor compounds content: 9.1% (wt)
Polymerization result: catalytic activity 28.000gPP/gCat, polymer apparent density 0.44g/cm3, isotacticity is 98.8%.
Embodiment 9
Bis- (dimethoxyphosphoryl) benzene of 1,2- are changed to bis- (diethoxy phosphoryl) -3, the 6- ethylo benzenes of 1,2-, twice Additional amount is respectively 1.5g and 1.8g, the other the same as in Example 1.Catalyst composition analysis result:
Titanium compound content: 10.1% (wt)
Content of magnesium chloride: 83.7% (wt)
Electron donor compounds content: 6.2% (wt)
Polymerization result: catalytic activity 31,500gPP/gCat, polymer apparent density 0.43g/cm3, isotacticity is 98.9%.
Embodiment 10
Bis- (dimethoxyphosphoryl) benzene of 1,2- are changed to bis- (diethoxy phosphoryl) -3, the 6- ethylo benzenes of 1,2-, twice Additional amount is identical, and total amount is added and magnesium chloride molar ratio is 0.25:1, the other the same as in Example 3.Catalyst composition analysis result:
Titanium compound content: 8.1% (wt)
Content of magnesium chloride: 82.9% (wt)
Electron donor compounds content: 9.0% (wt)
Polymerization result: catalytic activity 30,800gPP/gCat, polymer apparent density 0.43g/cm3, isotacticity is 99.0%.
Embodiment 11
By bis- (dimethoxyphosphoryl) benzene of 1,2- and bis- (the dimethoxyphosphoryl) -3,6- methylbenzene (molar ratios of 1,2- Mixture 1:1) changes bis- (the dimethoxyphosphoryl) -3,6- methylbenzenes of 1,2- and bis- (diethoxy the phosphoryl) -3,6- of 1,2- The mixture (molar ratio 1:1) of ethylo benzene, additional amount is respectively 1.9g and 2.1g the other the same as in Example 2 twice.Catalyst composition Analyze result:
Titanium compound content: 9.5% (wt)
Content of magnesium chloride: 80.7% (wt)
Electron donor compounds content: 9.8% (wt)
Polymerization result: catalytic activity 30,000gPP/gCat, polymer apparent density 0.43g/cm3, isotacticity is 99.0%.
Embodiment 12
By bis- (dimethoxyphosphoryl) benzene of 1,2- and bis- (the dimethoxyphosphoryl) -3,6- methylbenzene (molar ratios of 1,2- Mixture 1:1) changes bis- (the dimethoxyphosphoryl) -3,6- methylbenzenes of 1,2- and bis- (diethoxy the phosphoryl) -3,6- of 1,2- The mixture (molar ratio 1:1) of ethylo benzene, additional amount is respectively 1.9g and 2.1g the other the same as in Example 4 twice.Catalyst composition Analyze result:
Titanium compound content: 9.8% (wt)
Content of magnesium chloride: 80.7% (wt)
Electron donor compounds content: 9.5% (wt)
Polymerization result: catalytic activity 32,000gPP/gCat, polymer apparent density 0.43g/cm3, isotacticity is 99.3%.
Comparative example 1
Using same procedure, internal electron donor is changed to DIBP used in tradition (diisobutyl phthalate), it is other It operates same as Example 1.Catalytic component analyzes result:
Titanium compound content: 9.5% (wt)
Content of magnesium chloride: 81.9% (wt)
Electron donor compounds content: 8.6% (wt)
Polymerization result: catalytic activity 19,500gPP/gCat, polymer apparent density 0.44g/cm3, isotacticity are 97.7%.
Comparative example 2
Internal electron donor is changed to DIBP used in tradition (diisobutyl phthalate), the other the same as in Example 3. Catalyst composition analysis result:
Titanium compound content: 9.2% (wt)
Content of magnesium chloride: 80.7% (wt)
Electron donor compounds content: 10.1% (wt)
Polymerization result: catalytic activity 20,700gPP/gCat, polymer apparent density 0.44g/cm3, isotacticity are 96.5%.
By comparing as it can be seen that the internal electron donor containing structure of the present invention prepares the catalytic activity and polypropylene of catalyst Isotacticity be superior to traditional diisobutyl phthalate, the comprehensive performance of catalyst is more excellent.When two kinds of electron donors compound In use, the catalytic activity of catalyst and polyacrylic isotacticity further increase.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art It all should belong to protection scope of the present invention.

Claims (35)

1. a kind of olefin polymerization solid catalyst component, it is characterised in that include (1) magnesium halide；(2) titanium compound；(3) at least one Kind meets double dialkoxy phosphoryl benzene-like compounds of formula (I) structure as electron donor compound:
In formula, R1、R2、R3、R4It is identical or different, it is each independently selected from the alkyl, naphthenic base, aryl or miscellaneous of 1-8 carbon atom Aryl；
R5、R6、R7、R8It is identical or different, respectively alkyl, naphthenic base or aralkyl selected from hydrogen, 1-8 carbon atom by oneself；
By weight percentage, titanium compound content is 0.5-15% to each component, and electron donor compounds content is 3- 30%, halogenation content of magnesium is 60%-90%.
2. solid catalytic component according to claim 1, it is characterised in that the double dialkoxies for meeting formula (I) structure In phosphoryl benzene-like compounds, R1、R2、R3、R4It is each independently selected from the alkyl or cycloalkyl of 1-6 carbon atom；R5、R6、R7、 R8The respectively alkyl or cycloalkyl selected from hydrogen, 1-6 carbon atom by oneself.
3. solid catalytic component according to claim 2, it is characterised in that it is characterized in that the formula (I) structure of meeting In double dialkoxy phosphoryl benzene-like compounds, R1、R2、R3、R4It is each independently selected from the alkyl or cycloalkanes of 3-6 carbon atom Base；R5、R6、R7、R8It is respectively selected from the alkyl of hydrogen or 1-3 carbon atom by oneself.
4. solid catalytic component according to claim 1, it is characterised in that the compound packet for meeting formula (I) structure It includes: bis- (diethoxy phosphoryl) benzene of bis- (dimethoxyphosphoryl) benzene of 1,2-, 1,2-, 1,2- bis- (positive propoxy phosphoryls) Bis- (isopropoxy phosphoryl) benzene of benzene, 1,2-, bis- (n-butoxy phosphoryl) benzene of 1,2-, 1,2- bis- (isobutoxy phosphoryls) Bis- (n-pentyloxy phosphoryl) benzene of benzene, 1,2-, bis- (isoamoxy phosphoryl) benzene of 1,2-, 1,2- bis- (positive hexyloxy phosphoryls) Bis- (the dissident's oxygroup phosphoryl) benzene of benzene, 1,2-, bis- (the dimethoxyphosphoryl) -3,6- methylbenzenes of 1,2-, the bis- (diethoxies of 1,2- Phosphoryl) -3,6- methylbenzene, bis- (positive propoxy the phosphoryl) -3,6- methylbenzenes of 1,2-, 1,2- bis- (isopropoxy phosphoryls) - Bis- (n-butoxy the phosphoryl) -3,6- methylbenzenes of 3,6- methylbenzene, 1,2-, bis- (isobutoxy the phosphoryl) -3,6- methyl of 1,2- Bis- (n-pentyloxy the phosphoryl) -3,6- methylbenzenes of benzene, 1,2-, bis- (isoamoxy the phosphoryl) -3,6- methylbenzenes of 1,2-, 1,2- are bis- Bis- (dissident's oxygroup phosphoryl) -3,6- methylbenzenes of (positive hexyloxy phosphoryl) -3,6- methylbenzene, 1,2-, the bis- (dimethoxys of 1,2- Phosphoryl) -3,6- ethylo benzene, 1,2- bis- (diethoxy phosphoryls) -- bis- (the positive propoxy phosphinylidynes of 3,6- ethylo benzene, 1,2- Base) -- bis- (isopropoxy the phosphoryl) -3,6- ethylo benzenes of 3,6- ethylo benzene, 1,2-, bis- (n-butoxy the phosphoryl) -3,6- of 1,2- Bis- (isobutoxy the phosphoryl) -3,6- ethylo benzenes of ethylo benzene, 1,2-, 1,2- bis- (n-pentyloxy phosphoryl) -3,6- ethylo benzenes, 1, Bis- (isoamoxy the phosphoryl) -3,6- ethylo benzenes of 2-, bis- (positive hexyloxy the phosphoryl) -3,6- ethylo benzenes of 1,2-, the bis- (dissidents of 1,2- Oxygroup phosphoryl) -3,6- ethylo benzene, bis- (the dimethoxyphosphoryl) -3,6- n-propylbenzenes of 1,2-, bis- (the diethoxy phosphorus of 1,2- Acyl group) -3,6- n-propylbenzene, bis- (positive propoxy the phosphoryl) -3,6- n-propylbenzenes of 1,2-, bis- (the isopropoxy phosphinylidynes of 1,2- Base) -3,6- n-propylbenzene, bis- (n-butoxy the phosphoryl) -3,6- n-propylbenzenes of 1,2-, 1,2- bis- (isobutoxy phosphoryls) - Bis- (n-pentyloxy the phosphoryl) -3,6- n-propylbenzenes of 3,6- n-propylbenzene, 1,2-, bis- (isoamoxy the phosphoryl) -3,6- of 1,2- Bis- (dissident's oxygroup phosphoryl) -3,6- positive third of bis- (positive hexyloxy the phosphoryl) -3,6- n-propylbenzenes of n-propylbenzene, 1,2-, 1,2- Bis- (diethoxy the phosphoryl) -3,4,5,6- first of bis- (the dimethoxyphosphoryl) -3,4,5,6- methylbenzenes of base benzene, 1,2-, 1,2- Bis- (positive propoxy the phosphoryl) -3,4,5,6- methylbenzenes of base benzene, 1,2-, bis- (isopropoxy the phosphoryl) -3,4,5,6- first of 1,2- Bis- (n-butoxy the phosphoryl) -3,4,5,6- methylbenzenes of base benzene, 1,2-, bis- (isobutoxy the phosphoryl) -3,4,5,6- first of 1,2- Bis- (n-pentyloxy the phosphoryl) -3,4,5,6- methylbenzenes of base benzene, 1,2-, bis- (isoamoxy the phosphoryl) -3,4,5,6- first of 1,2- Bis- (dissident's oxygroup phosphoryl) -3,4,5,6- first of bis- (positive hexyloxy the phosphoryl) -3,4,5,6- methylbenzenes of base benzene, 1,2-, 1,2- Bis- (diethoxy the phosphoryl) -3,4,5,6- second of bis- (the dimethoxyphosphoryl) -3,4,5,6- ethylo benzenes of base benzene, 1,2-, 1,2- Bis- (positive propoxy the phosphoryl) -3,4,5,6- ethylo benzenes of base benzene, 1,2-, bis- (isopropoxy the phosphoryl) -3,4,5,6- second of 1,2- Bis- (n-butoxy the phosphoryl) -3,4,5,6- ethylo benzenes of base benzene, 1,2-, bis- (isobutoxy the phosphoryl) -3,4,5,6- second of 1,2- Bis- (n-pentyloxy the phosphoryl) -3,4,5,6- ethylo benzenes of base benzene, 1,2-, bis- (isoamoxy the phosphoryl) -3,4,5,6- second of 1,2- Bis- (dissident's oxygroup phosphoryl) -3,4,5,6- second of bis- (positive hexyloxy the phosphoryl) -3,4,5,6- ethylo benzenes of base benzene, 1,2-, 1,2- Bis- (diethoxy the phosphoryl) -3,4,5,6- of bis- (the dimethoxyphosphoryl) -3,4,5,6- n-propylbenzenes of base benzene, 1,2-, 1,2- Bis- (positive propoxy the phosphoryl) -3,4,5,6- n-propylbenzenes of n-propylbenzene, 1,2-, bis- (the isopropoxy phosphoryls) -3,4 of 1,2-, Bis- (n-butoxy the phosphoryl) -3,4,5,6- n-propylbenzenes of 5,6- n-propylbenzene, 1,2-, 1,2- bis- (isobutoxy phosphoryls) - Bis- (n-pentyloxy the phosphoryl) -3,4,5,6- n-propylbenzenes of 3,4,5,6- n-propylbenzene, 1,2-, bis- (the isoamoxy phosphinylidynes of 1,2- Base) -3,4,5,6- n-propylbenzene, bis- (positive hexyloxy the phosphoryl) -3,4,5,6- n-propylbenzenes of 1,2- or bis- (the dissident's oxygroups of 1,2- Phosphoryl) -3,4,5,6- n-propylbenzene.
5. solid catalytic component according to claim 1, it is characterised in that the magnesium halide be selected from magnesium chloride, magnesium bromide and At least one of magnesium iodide.
6. solid catalytic component according to claim 5, it is characterised in that the magnesium halide is magnesium chloride.
7. solid catalytic component according to claim 1, it is characterised in that the titanium compound is the change for meeting formula (II) Close object:
TiX1 p(OR1)4-p (II)
Wherein X1For halogen atom；P is the integer of 0-4；R1For the alkyl containing 1-10 carbon atom, the alkyl is for saturation or not Straight chain, branch or the cyclic hydrocarbon group of saturation or the alkyl further contain hetero atom.
8. solid catalytic component according to claim 7, it is characterised in that X in the formula (II) of the titanium compound1For chlorine or Bromine atom, R1For alkyl, alkenyl, alkynyl, naphthenic base, aryl or aralkyl.
9. solid catalytic component according to claim 8, it is characterised in that X in the formula (II) of the titanium compound1For chlorine original Son, R1For the alkyl of linear chain or branched chain.
10. solid catalytic component according to claim 9, it is characterised in that the titanium compound is titanium tetrachloride.
11. the solid catalytic component according to any of claims 1 to 10, it is characterised in that each component is by weight percentage Meter, titanium compound content are 2%-12%, and electron donor compounds content is 3-15%, and halogenation content of magnesium is 60%-85%.
12. a kind of preparation method of olefin polymerization solid catalyst component described in claim 1, it is characterised in that process includes:
(1) preparation of magnesium halide alcohol adduct solution
Under nitrogen atmosphere, anhydrous magnesium halide, alcohol compound are stirred in alkane solvent to being uniformly dispersed, be added titanate esters and The compound for meeting formula (I) structure continues to stir at the same temperature, obtains the magnesium halide alcohol adduct solution of stable and uniform, cooling It is stand-by to room temperature,
In formula, R1、R2、R3、R4It is identical or different, it is each independently selected from the alkyl, naphthenic base, aryl or miscellaneous of 1-8 carbon atom Aryl；R5、R6、R7、R8It is identical or different, respectively alkyl, naphthenic base or aralkyl selected from hydrogen, 1-8 carbon atom by oneself；
Wherein, the molar ratio of alcohol compound and magnesium halide is 1-10:1；Meet the compound of formula (I) structure and rubbing for magnesium halide You are than being 0.01-0.2:1；Titanate esters and the molar ratio of magnesium halide are 0.9-1.1:1；It is 1- that total time is reacted at 40-200 DEG C 6h；
(2) preparation of solid catalytic component
Under nitrogen atmosphere, titanium compound is mixed with the magnesium halide alcohol adduct solution of step (1) at -25-40 DEG C, stir and by Step is warming up to 80-135 DEG C, adds compound reaction 1-4 hours for meeting formula (I) structure, meets the compound of formula (I) structure It is 0.01-0.2:1 with the molar ratio of magnesium halide, equivalent titanium compound and the reaction was continued at a temperature of 80-135 DEG C 1- is added again It 4 hours, is filtered, washed, is dried to obtain solid catalytic component,
It is 1-4:1, the titanium compound meeting formula that total amount and the volume ratio of magnesium halide alcohol adduct solution, which is added, in the titanium compound (II)
TiX1 p(OR1)4-p (II)
Wherein X1For halogen atom；P is the integer of 0-4；R1For the alkyl containing 1-10 carbon atom, the alkyl is for saturation or not Straight chain, branch or the cyclic hydrocarbon group of saturation or the alkyl further contain hetero atom.
13. the preparation method of solid catalytic component according to claim 12, it is characterised in that the alcohol compound choosing From the monohydric alcohol of 1-10 carbon atom.
14. the preparation method of solid catalytic component according to claim 13, it is characterised in that the alcohol compound is Ethyl alcohol, propyl alcohol, butanol or 2- ethyl-hexanol.
15. the preparation method of solid catalytic component according to claim 12, it is characterised in that the alcohol compound with The molar ratio of magnesium halide is 2-8:1.
16. the preparation method of solid catalytic component according to claim 15, it is characterised in that the alcohol compound with The molar ratio of magnesium halide is 3-6:1.
17. the preparation method of solid catalytic component according to claim 12, it is characterised in that the titanate esters are general formulas For Ti (OR)4Compound, wherein R be 1-8 carbon alkyl or cycloalkyl.
18. the preparation method of solid catalytic component according to claim 17, it is characterised in that the titanate esters are metatitanic acids Four butyl esters.
19. the preparation method of solid catalytic component according to claim 12, it is characterised in that the alkane solvent is C8- C12Alkane solvent, the amount ratio of alkane solvent and magnesium halide is 0.5-20mL/g.
20. the preparation method of solid catalytic component according to claim 19, it is characterised in that the alkane solvent and halogen The amount ratio for changing magnesium is 1-15mL/g.
21. the preparation method of solid catalytic component according to claim 20, it is characterised in that the alkane solvent and halogen The amount ratio for changing magnesium is 3-10mL/g.
22. the preparation method of solid catalytic component according to claim 12, it is characterised in that step (1) and step (2) In the total amount of the compound for meeting formula (I) structure that is added twice and magnesium halide molar ratio be 0.05-0.25:1.
23. the preparation method of 2 to 22 described in any item solid catalytic components according to claim 1, it is characterised in that step (1) In, reaction temperature is 60-180 DEG C.
24. the preparation method of solid catalytic component according to claim 23, it is characterised in that in step (1), reaction temperature Degree is 80-150 DEG C.
25. a kind of preparation method of olefin polymerization solid catalyst component described in claim 1, it is characterised in that process includes:
S1 is in nitrogen atmosphere and at a temperature of -25-40 DEG C, by magnesium halide in the form of spherical magnesium halide alcohol polymer particle and titanium compound It comes into full contact with, is warming up to 40-80 DEG C and the compound for meeting formula (I) structure is added, meet the compound and magnesium halide of formula (I) structure Molar ratio is 0.01-0.2:1；
In formula, R1、R2、R3、R4It is identical or different, it is each independently selected from the alkyl, naphthenic base, aryl or miscellaneous of 1-8 carbon atom Aryl；R5、R6、R7、R8It is identical or different, respectively alkyl, naphthenic base or aralkyl selected from hydrogen, 1-8 carbon atom by oneself；
S2 is warming up to 80-135 DEG C and continuously adds the compound for meeting formula (I) structure and react 1-4 hours, meets formula (I) structure Compound and magnesium halide molar ratio be 0.01-0.2:1；
S3 filters out liquid, and adding titanium compound, the reaction was continued at a temperature of 80-135 DEG C 1-4 hours, titanium compound and magnesium halide The mass ratio of alcohol adduct particle is 10-30:1, using filter, washing, dry obtained solid catalysis component.
26. the preparation method of solid catalytic component according to claim 25, it is characterised in that titanium compound and magnesium halide The mass ratio of alcohol adduct particle is 1-6:1.
27. the preparation method of solid catalytic component according to claim 26, it is characterised in that titanium compound and magnesium halide The mass ratio of alcohol adduct particle is 1-4:1.
28. the preparation method of solid catalytic component according to claim 25, it is characterised in that in step S1 and step S2 The total amount for meeting the compound of formula (I) structure is added twice and magnesium halide molar ratio is 0.05-0.25:1.
29. the preparation method of solid catalytic component according to claim 25, it is characterised in that magnesium halide alcohol adduct particle It is the spheric granules that anhydrous magnesium chloride/ethyl alcohol compound is formed.
30. a kind of olefin polymerization catalyst system, it is characterised in that including following component:
(1) solid catalytic component described in claim 1；
(2) alkyl aluminum compound；
(3) at least one silane compound；
By weight percentage, solid catalytic component dosage is 0.01-6%, and alkyl aluminum compound dosage is 85%-95%, silicon Hydride compounds dosage are as follows: 0.01-10%.
31. olefin polymerization catalyst system according to claim 30, it is characterised in that alkyl aluminum compound is with 1-5 The trialkylaluminium of the low alkyl group of a carbon atom.
32. olefin polymerization catalyst system according to claim 30, it is characterised in that silane compound is meeting formula (III)R2 nSi(OR3)4-nCompound, wherein R2And R3It is saturations or undersaturated straight chain, branch or cyclic group or R2With R3Further contain hetero atom；N is the integer of 0-4.
33. according to the described in any item olefin polymerization catalyst systems of claim 30 to 32, it is characterised in that percentage by weight Than meter, solid catalytic component dosage is 0.01%-2% in component；Alkyl aluminum compound dosage is 88%-92%；Silane chemical combination Object dosage is 0.01%-5%.
34. olefin polymerization catalyst system according to claim 31, it is characterised in that the catalyst system catalysis Alkene is ethylene, propylene, butylene or 1- hexene.
35. olefin polymerization catalyst system according to claim 31, it is characterised in that the catalyst system catalysis Polymerization reaction includes homopolymerization or combined polymerization.
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