CN110467694A - Preparation method, propylene high-temperature polymerization catalyst component and the propylene high-temperature polymerization catalyst of propylene high-temperature polymerization catalyst complex carrier - Google Patents
Preparation method, propylene high-temperature polymerization catalyst component and the propylene high-temperature polymerization catalyst of propylene high-temperature polymerization catalyst complex carrier Download PDFInfo
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- CN110467694A CN110467694A CN201810439501.8A CN201810439501A CN110467694A CN 110467694 A CN110467694 A CN 110467694A CN 201810439501 A CN201810439501 A CN 201810439501A CN 110467694 A CN110467694 A CN 110467694A
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- 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
Abstract
The present invention relates to a kind of preparation method of olefin high-temperature polymerization catalyst complex carrier, propylene high-temperature polymerization catalyst component and propylene high-temperature polymerization catalysts, the complex carrier is prepared with by the processed silica-gel carrier of lewis base through chemical reaction by the chlorination magnesium alcoholate of molten state, makes magnesium halide alcohol adduct melt and processed SiO by mechanical stirring2It carries out compound, it can obtain that spherical morphology is good, complex carrier of even particle distribution, the titanium-containing catalyst prepared by the complex carrier is used to show excellent performance when (>=93 DEG C) polymerizations of olefinic polymerization especially propylene high-temperature together with co-catalyst, catalyst polymerization activity with higher, gained high temperature polymer particle shape is good, and product bulk density is high and stereoregularity is good.
Description
Technical field
The present invention relates to a kind of magnesium chloride complex carrier and its catalyst for polymerization of propylene of preparation, specifically, being by chlorine
The catalyst solid constituent changed magnesium and be compounded to form carrier by the processed silica of lewis base and prepared by the carrier, should
For component for showing excellent performance when (>=93 DEG C) polymerizations of olefinic polymerization especially propylene high-temperature, catalyst is with higher
Catalytic activity, gained high temperature polymer particle shape is good, and product bulk density is high and stereoregularity is good.
Background technique
Currently, efficient carrier type Ziegler-Natta (Z-N) catalyst generally used in olefinic polymerization, being will be active
Component (such as Ti compound) is highly dispersed at carrier surface, while specific surface area of catalyst is significantly increased, significantly improves and urges
The catalytic efficiency of agent.In addition, improving polymerization temperature is also an important means for improving catalyst efficiency: improving alkene
Polymerization temperature is conducive to the cooling in industrial processes and improves production efficiency；Secondly, as new polymerization technique is " overcritical
The appearance of polymerization ", can be such that the efficiency of catalyst greatly improves, the content of ashes in polymer is effectively reduced, obtain cleaner
Polymer；Facilitate to develop novel high-performance polypropylene material simultaneously, can neatly produce the polypropylene of different grades, mention
High product added value.But while olefin high-temperature polymerization activity improves, easily lead to that resulting polymers Particle Breakage is more and shape
State is poor, the product conveying being unfavorable in actual production process, therefore proposes to the granule strength of olefin high-temperature polymerization catalyst
Higher requirement.
In Z-N catalyst, magnesium chloride (MgCl2) and silica gel (SiO2) it is most common two kinds of carriers.MgCl2With with
TiCl4Similar layer structure, and Mg2+With active component Ti4+It is the reason for preparing Z-N catalyst with similar ionic radius
Think carrier, but spherical magnesium chloride support particle mechanical strength is poor, is easy to cause polymer particle for olefinic polymerization after load titanium
It is broken.SiO2Carrier specific surface area is high and spherical morphology and mobility are preferable, and SiO2Surface hydroxyl be unevenly distributed, load
Activated centre after catalyst is excessively concentrated, and is unfavorable for olefinic monomer insertion, is kept polymerization activity relatively low.Therefore, by MgCl2With
SiO2It is compounded to form carrier and prepares composite carried catalyst, in olefin polymerization in addition to MgCl2The height of carried catalyst is living
Except property, high stereoselectivity, SiO has also been taken into account2The good mechanical strength of carried catalyst.
In existing public technology, a variety of preparation MgCl have been mentioned2-SiO2The method of complex carrier.Such as infusion process, by spraying
Method etc..British patent GB2028347 gives a kind of prepare and is supported on porous inorganic oxide supported catalyst component
Method, that is, use magnesium chloride solution impregnation of silica carrier, evaporate solvent later, obtained solid product again with transition metal
Compound especially titanium compound reacts.Chinese patent CN1035186C discloses a kind of efficient using silica supports preparation
The technology of polypropylene catalyst.It is the tetrahydrofuran that the porous silicon dioxide carrier that hydroxyl is contained on surface is scattered in magnesium chloride
In solution, dry above-mentioned suspension obtains MgCl2-SiO2Complex carrier, then should with titanium tetrachloride and the processing of electron donor compound
Carrier, finally obtains catalyst prod, but catalysis prepared by the carrier obtained using above-mentioned magnesium chloride solution dipping method
Agent, when being used for propylene polymerization, polymerization activity is unsatisfactory.Chinese patent CN1510055A prepares MgCl to infusion process2-
SiO2Complex carrier improves, and magnesium chloride is dissolved in tetrahydrofuran first, and the SiO of a certain amount of activation is added2Carrier, and
A small amount of alcohol (such as butanol) is added in reaction process to be activated carrier, the complex carrier of preparation can be direct without dealcoholysis
Load active component, for gained catalyst in ethylene slurry homopolymerization, polymerization activity is up to 3453.2g PE/gCat.
Chinese patent CN 1524886A is prepared for MgCl using spray-on process2-SiO2Complex carrier, the complex carrier be by
The contacts such as magnesium halide such as magnesium chloride and one or more electron donor compounds such as fatty alcohol, tetrahydrofuran form solution, this is molten
Silica gel of the liquid with average grain diameter less than 30 μm mixes, spray-dried obtained spherical particle, and the catalytic component is urged with helping
Agent component is used for olefinic polymerization together, when being especially used for propylene polymerization, it is shown that higher polymerization activity and stereotaxis
Property, but spray-on process prepares carrier, needs to evaporate a large amount of solvents, and energy and material consumption is higher and the alcohol content of resulting vehicle is not easily-controllable
System.
Chinese patent CN1597712A is that composite carried catalyst is prepared in situ out in same dicyandiamide solution, by magnesium chloride
It is first dissolved in the dicyandiamide solution containing organic epoxide and organic phosphorus compound, before loading titanium compound, later or together
When introduce SiO2, it is carried on active component on the complex carrier of magnesium halide and silica gel, prepares the Z-N catalysis of complex carrier
Agent.Improve the particle shape of catalyst by Mg/Si ratio in adjusting magnesium chloride and silica gel, while catalyst granules is solid, polymerization
Shi Buyi is broken, but this composite carried catalyst being prepared in situ, and catalytic activity is relatively low and can not solve the part of catalyst
Caking phenomenon.
Chinese patent CN104177523A discloses a kind of preparation method of spherical solid catalytic component, including (1) carries
The preparation of body: using white oil as medium, magnesium chloride, ethyl alcohol and smoke-like silica gel is added, after heating melting, by above-mentioned melting alcohol adduct
And the slurries of smoke-like silica gel are transferred in the methyl-silicone oil medium being preheated, and are quickly stirred and are transferred them to cold hexane
In medium, complex carrier is prepared, above-mentioned carrier is prepared into Titanium series catalyst with conventional loading processes, which is used for
Higher polymerization activity is shown when propylene polymerization, obtained polymer bulk density is higher, and fine polymer powder is less, but this is specially
When composite carried catalyst disclosed in benefit is used for propylene high-temperature polymerization reaction, the isotacticity of catalytic activity and gained high temperature polymer
It is relatively low.
When carrying out propylene polymerization because of traditional Z-N catalyst, polymerization temperature is generally at 80 DEG C hereinafter, higher polymerization temperature
When being such as higher than 80 DEG C, the isotacticity and molecular weight of polymerization activity and prepared polymer, which can all have, significantly to be declined,
The reason is that the inactivation of catalyst active center is accelerated, and the polymerization activity of system is caused to decline with the raising of polymerization temperature, generate
Oligomer increase, the isotacticity of final resulting polymers is relatively low.
It, can be under the polymerization temperature in 150~300 DEG C as disclosed a kind of catalyst in United States Patent (USP) US5385993
Propylene polymerization is carried out, can be obtained with the polypropylene compared with high isotactic, while gained acrylic polymers is relative to 80 DEG C or lower
The propylene polymerization of temperature has broader molecular weight distribution, but under so high polymerization temperature, and resulting polymers are not
Be it is granular, in actual production can exist be not easy the problems such as conveying, meanwhile, the preparation process of the catalyst is complex,
The activity of catalyst is also unsatisfactory.Chinese patent CN1421468A discloses a kind of propylene and polymerize at high temperature or combined polymerization
Method and catalyst prepolymer suitable for this method, process conditions and pre- during passing through pre-polymerization in the polymerization
The control of poly- multiple finally makes traditional Z-N catalyst be suitable for the polymerization reaction of propylene (> 85 DEG C) at relatively high temperatures, but
The control means of process conditions and pre-polymerization multiple that this method is used are complex, the isotacticity of resulting polymers and 70 DEG C of preparations
Polymer phase ratio it is still relatively low.Chinese patent CN1621421A also discloses a kind of preparation method of catalyst, and the catalyst is logical
It crosses the mixture of introducing aikyiaiurnirsoxan beta and alkyl aluminum in polymerization process and realizes that propylene high-temperature polymerize as co-catalyst, equally exist
Complex process, the problem of new component need to be introduced, and also high temperature polymerization activity and polymer isotacticity all need to be further increased.
When being used for (>=93 DEG C) polymerizations of propylene high-temperature for existing traditional Z-N catalyst, catalyst active center's easy in inactivation,
The problems such as polymer isotacticity of preparation is relatively low, the present invention provides a kind of complex carrier of preparation method simplicity and its catalysis
Agent, the composite carried catalyst have higher catalytic activity, the particle shape of resulting polymers when for propylene high-temperature polymerization
Well, heap density is higher, and solves the problems, such as that the high temperature polymer isotacticity of preparation is relatively low.
Summary of the invention
It is answered the object of the present invention is to provide a kind of preparation method of propylene high-temperature polymerization catalyst complex carrier and using this
The catalytic component of carrier preparation is closed, when which polymerize for olefinic polymerization especially propylene high-temperature, has greater catalytic living
Property, the particle shape of resulting polymers is good, and heap density is higher and stereoregularity is good.
A kind of propylene high-temperature polymerization catalyst complex carrier, preparation step are as follows:
(1) under nitrogen protection, the silica supports after activation are added in organic solvent, under agitation,
Lewis base is added, boils off solvent after reacting a period of time, is dried to obtain solid powder；
(2) under nitrogen protection, frit reaction is occurred into for magnesium chloride and ethyl alcohol in a heated condition and is prepared into magnesium chloride alcohol
Object melt is closed, step (1) pretreated solid powder is added into chlorination magnesium alcoholate melt under agitation and carries out instead
It answers, the inertia dispersing agent for being preheated to same temperature is added later, after being dispersed with stirring, reaction mixture is transferred to inertia cooling medium
In, stirring, is formed by curing spherical complex carrier at cooling.
The silica supports substance generally selects the spherical silica gel carrier of average grain diameter≤50 μm, preferably titanium dioxide
The average grain diameter of silicon is 1~30 μm, 100~350m of specific surface area2/ g, 0.5~3ml/g of pore volume, 5~40nm of average pore size.
The silica-gel carrier can be commercial products and directly use, and act on again with above-mentioned lewis base after can also first passing through roasting.
The lewis base generally selects the one of two ethers or two esters or succinate compound or diol-lipid compound
Kind is a variety of, more preferably uses diether compound, most preferably fluorenes diether.
It is the methyl-silicone oil of 50~600 centipoises and the liquid of 30~50 centipoises that the inertia dispersing agent, which is by (20 DEG C) of viscosity,
The mixture of body paraffin composition.
Toluene, dimethylbenzene, tetrahydrofuran equal solvent can be selected in the organic solvent.
The aromatic hydrocarbons of the preferred alkane of inertia cooling medium, halogenated hydrocarbons or 6-12 carbon atom, such as hexane, heptane,
Dichloroethanes, toluene, dimethylbenzene, ethylbenzene etc., preferably hexane.
Magnesium chloride selects anhydrous magnesium chloride, prepares the various liquid reagents of complex carrier, such as ethyl alcohol, inertia dispersing agent, lazy
Property cooling medium etc. is both needed to be carried out dehydrating before use, makes its water content≤10ppm.
Complex carrier specific in the present invention the preparation method is as follows:
(1) silica supports pre-process
Silica-gel carrier is activated first to remove the absorption water of silica-gel carrier and extra surface hydroxyl, it is more excellent
The condition of choosing can be activated first 1~2 hour using 150 DEG C~300 DEG C, then be activated 3~6 hours at 400 DEG C~600 DEG C；In nitrogen
Under gas shielded, the silica supports after activation are added in organic solvent, the quality of organic solvent and silica supports
Than lewis base being added, wherein silica supports and road under agitation for 2.5:1~20:1, preferably 3:1~15:1
The molar ratio of this easy alkali is 1:1~20:1, preferably 5:1~10:1, after reacting 0.5~3 hour under the conditions of 0 DEG C~40 DEG C of temperature
Solvent is boiled off, solid powder is dried to obtain.
(2) chlorination magnesium alcoholate melt is prepared
Under nitrogen protection, anhydrous magnesium chloride and dehydrated alcohol are added into reaction kettle, wherein ethyl alcohol and magnesium chloride rub
You are than being 2.0:1~4.0:1, preferably 2.5:1~3.5:1.Heating makes magnesium chloride be melt into melt completely, and heating temperature is 100 DEG C
~140 DEG C, preferably 110 DEG C~130 DEG C.
(3) spherical shape MgCl is prepared2-SiO2Complex carrier
It keeps above-mentioned heating temperature constant, adds under nitrogen protection and stirring condition into above-mentioned magnesium chloride alcohol adduct melt
Entering step (1) pretreated silica-gel carrier, the additional amount of silica-gel carrier is 0.1~1.5g/g magnesium chloride, after reacting 5~60min,
Inertia dispersing agent is added into reactor, inertia dispersing agent need to be preheated to temperature identical with chlorination magnesium melt system at this time in advance
Degree, dosage are 0~20ml/g magnesium chloride, and inertia dispersing agent selects the mixture of methyl-silicone oil and atoleine, volume ratio
For 1:1~1:7, preferably methyl-silicone oil, atoleine volume ratio be 1:1~1:3, reaction mixture is at 300~2000 revs/min
Speed mixture is transferred to cooling reactor under nitrogen protection after stirring 2~5min under preferably 600~1200 revs/min of revolving speed
It is interior, wherein inertia cooling medium and the volume ratio of dispersing agent are 5:1~10:1, and cooling temperature is -15~-40 DEG C, preferably -20
It~-30 DEG C, stirs, cool down, solidify, washing, is dried to obtain spherical MgCl2-SiO2Complex carrier.Generally, the complex carrier
Composition are as follows:
Magnesium chloride: 20%~60% (weight)
SiO2: 1%~60% (weight)
Ethyl alcohol: 30%~60% (weight)
Lewis base: 1%~20% (weight)
The present invention also provides a kind of catalytic components for propylene high-temperature polymerization, contain above method preparation
MgCl2-SiO2The reaction product of complex carrier and titanium compound, the titanium compound such as general formula Ti (OR1)4-mXmIt is shown, R in formula1
It is C1~C14Aliphatic group, X chooses from or mixtures thereof F, Cl, Br, the integer that m is 1~4.Titanium compound is to apply
At a temperature of, completely soluble liquefied compound in nonpolar solvent, specifically can be selected titanium tetrachloride, titanium tetrabromide, titanium tetra iodide,
Four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygroup titanium, one ethanolato-titanium of trichlorine, in titanium trichloride
One kind or their mixture, preferred titanium tetrachloride.
It, can also be using at internal electron donor compound before complex carrier is reacted with titanium compound or after reaction
Reason, published a large amount of internal electron donor compound, suitable internal electron donor compound in this field, which can be used, can be used
Polyhydric aliphatic race carboxylate or aromatic carboxylic acid esters.Such as: phthalic acid ester, malonic acid esters, succinate, glutaric acid
Ester, pivalate, carbonic ester, diether, diol ester etc., specifically such as: diethyl phthalate, diisobutyl phthalate,
N-butyl phthalate, diisooctyl phthalate, diethyl malonate, dibutyl malonate, 2,3- diisopropyl
Diethyl succinate, 2,3- diisopropyl di-iso-octyl succinate, 2,3- diisopropyl dibutyl succinate, 2,3- diisopropyl
Base dimethyl succinate, 2,2- dimethyl succinate diisobutyl ester, 2- Ethyl-2-Methyl di-iso-octyl succinate, 2- ethyl -2-
Methyl succinic diethyl phthalate, diethylene adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, suitable butadiene
Diethyl phthalate, maleic acid n-butyl, naphthalene dicarboxylic acids diethylester, naphthalene dicarboxylic acids dibutyl ester, triethyl trimellitate, inclined benzene
Three sour tributyls, benzene-1,2,3-tricarboxylic acid triethyl, benzene-1,2,3-tricarboxylic acid tributyl, pyromellitic acid tetra-ethyl ester, four butyl ester of pyromellitic acid, fluorenes diether
Deng.
Prior art preparation can be used in catalytic component of the present invention.Only enumerate the preparation method of one, specific mistake
Journey includes: (1) by above-mentioned MgCl2-SiO2Spherical complex carrier is added to -50~20 DEG C, preferably -30~0 DEG C of titanium tetrachloride
In liquid, react 10 minutes to 4 hours, preferably 1~3 hour, the molar ratio of magnesium and titanium was 1:5~1:100, preferably 1:10
~1:50；(2) it is warming up to 0~80 DEG C, is added internal electron donor compound, the molar ratio of magnesium and internal electron donor is 2:1~20:
1, preferably 2:1~12:1；(3) 100~130 DEG C are warming up to, is reacted 1~6 hour, preferably 1~4 hour；(4) after filtering again
Be added with the same amount of titanium tetrachloride liquid of the first step, reacted in 110~130 DEG C 1~4 hour, preferably 1~2 hour, then pass through
Ingredient of solid catalyst is obtained after being filtered, washed drying.
In addition, it includes the reaction products of following components the invention further relates to a kind of propylene high-temperature polymerization catalyst:
(1) solid catalyst activity group is divided into above-mentioned catalytic component of the invention；
(2) alkyl aluminum compound, general formula AlRnX(3- n), R is C in formula1~C20Alkyl, aryl or aralkyl, X
For halogen, n is the integer of 0≤n≤3, is chosen in particular from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, a chlorine
The mixing of one or both of diethyl aluminum or a chloro-di-isobutyl aluminum, preferably triethyl aluminum or triisobutyl aluminium；
(a kind of 3 external donor compounds, be selected from single or multiple functional group's carboxylic acid, carboxylic acid anhydrides and carboxylate, ketone, ether, alcohol,
Lactone and organic phosphorus and organo-silicon compound, preferably organo-silicon compound such as Cyclohexyl Methyl Dimethoxysilane, two rings penta
Base dimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, dimethoxydimethylsilane,
The mixing of one or more of di ethoxy di methyl-monosilane or dimethoxydiphenyl silane.
Wherein, the ratio between solid catalyst activity component, alkyl aluminum compound and external donor compound, with
Titanium: aluminium: the molar ratio computing between silicon is 1:5~1000:0~500.
Wherein alkyl aluminum compound and external donor compound can mixture individually or as two kinds of ingredients and work
Property component haptoreaction.
The polymerization of alkene carries out according to known methods, in liquid monomer or monomer in the liquid phase in atent solvent, or
In gas phase, or operated by the polymerization mix technique in liquid phase.Polymerization temperature is generally 0 DEG C~150 DEG C, preferably
60 DEG C~100 DEG C.Polymerization pressure is normal pressure or higher.
Complex carrier of the present invention is the chlorination magnesium alcoholate and the dioxy alkali-treated through Louis by molten state
SiClx carrier is prepared through chemical reaction.Chlorination magnesium alcoholate and processed silica-gel carrier " compound " be mainly shown as with
Lower three kinds of modes, chlorination magnesium alcoholate is filled in the internal void of silica-gel carrier, chlorination magnesium alcoholate is coated on silica-gel carrier
The hydroxyl of surface, chlorination magnesium alcoholate and Silica Surface reacts, and forms Mg-Si key, further increases complex carrier
Intensity.Compared with complex carrier prepared by infusion process (CN1510055A), the present invention makes magnesium halide alcohol adduct by mechanical stirring
Melt and processed SiO2Carry out it is compound, further control reaction mixing speed, the spherical morphology of controllable complex carrier,
It is final to obtain that spherical morphology is good, complex carrier of even particle distribution；Because the hydroxyl of chlorination magnesium alcoholate and Silica Surface is anti-
Mg-Si key should be formed, the granule strength of the complex carrier is made to be increased dramatically.Under the conditions of the reaction according to the invention, after activation
Silica-gel carrier elder generation and lewis base such as fluorenes diether act on, then compound with chlorination magnesium alcoholate.Due to two of fluorenes diether compounds
Oxygen-ether linkage coordination ability is very strong, relatively stable in the preparation process of catalyst, and diether compound can be adsorbed in activity
Near heart Ti atom, non-cubic selection activated centre is transformed into three-dimensional selection activated centre, or select with having had solid
The activated centre effect selected keeps three-dimensional selection activated centre more stable, active higher.Again since ethers is that chemical property is stable
Compound is not easily susceptible to the attack of co-catalyst under the high temperature conditions, and secondary counter does not occur with Ti-C key or Al-C key key etc.
It answers, is capable of the activated centre of rugged catalyst, improve polymerization activity of catalyst under the conditions of high temperature polymerization.Therefore, with fluorenes two
When the composite carried catalyst that ether is prepared after pre-processing to silica-gel carrier is used for propylene high-temperature polymerization together with co-catalyst,
Adaptability of catalyst under the conditions of high temperature polymerization is improved, polymerization activity is largely increased, the granulated of resulting polymers
State is good, and heap density is higher, meanwhile, solve the problems, such as that high temperature polymer isotacticity is relatively low.
Specific embodiment
Following example is used to illustrate the present invention, is not for limiting the scope of the invention.
Embodiment 1
1, the preparation of complex carrier
Silica-gel carrier first activates 1.5 hours at 200 DEG C, then improves activation temperature, activates 4 hours at 500 DEG C；In
Under nitrogen protection, activated silica supports 20.0g is added in 70mL toluene the (mass ratio of toluene and silica
14.0g fluorenes diether (molar ratio of silica and fluorenes diether is 6:1) is added, is reacted at 15 DEG C under agitation for 3:1)
Toluene solvant is boiled off after 1 hour, the silica-gel carrier solid powder that is dried to obtain that treated.Under nitrogen protection, into reaction kettle
25.0g magnesium chloride, 42.9mL ethyl alcohol (molar ratio of ethyl alcohol and magnesium chloride is 2.8:1) is added, reaction kettle is warming up to 125 DEG C extremely
Magnesium chloride melts completely.
5.0g average grain diameter is under nitrogen protection added into reaction kettle it is 20 μm and is carried through fluorenes diether treated silica gel
After precursor reactant 30min, by the mixed dispersant addition reaction of the 200mL atoleine and 200mL methyl-silicone oil that are preheating to 125 DEG C
Reaction mixture is transferred in cooling reactor, in cooling reactor by kettle under nitrogen protection after stirring 4min with 800 revs/min of revolving speed
Cryogen is enough anhydrous hexanes for being cooled to -25 DEG C in advance, and MgCl is made after agitated, cooling, solidification, washing, drying2-SiO2It is multiple
Close carrier 1.The group of analysis gained complex carrier 1 becomes (parts by weight), MgCl2: 39.1%；SiO2: 4.6%；Fluorenes diether:
3.2%；C2H5OH:53.1%.
2, the preparation of catalyst
Under the conditions of anhydrous and oxygen-free, the above-mentioned complex carrier particle of 5.0g is added to -20 DEG C of 140mL titanium tetrachloride liquid
In, after reaction 1 hour, it is warming up to 60 DEG C；It is added 0.63mL diisobutyl phthalate (DIBP), is warming up to 120 DEG C, reaction
2 hours, filtering；Add 140mL titanium tetrachloride, in 120 DEG C react 2 hours after filter, wash, dry after obtain complex carrier
Catalyst 1, the Ti content of catalyst: 2.82%；Ester content: 5.91%；Ether content: 3.14%.
3, (>=93 DEG C) of propylene high-temperature polymerizations
Using composite carried catalyst 1, propylene high-temperature polymerization is carried out.In the vacuum dried processing of 10L and with nitrogen and third
In the high temperature polymerization kettle that alkene gas is sufficiently displaced from, it is firstly added 0.5kg propylene, adds the 5mL triisobutyl aluminium (hexane of 1mol/L
Solution) and 0.1mL Cyclohexyl Methyl Dimethoxysilane (CHMMS), 40mg polypropylene catalyst 1 continuously add 1.5kg third
Alkene, polymeric kettle temperature are quickly raised to 93 DEG C, polymerization reaction 1 hour, are vented no reacted propylene, obtain high temperature polymer,
It polymerize related data and is listed in table 1, the screening result of polymer is listed in table 2.
Embodiment 2
1, the preparation of complex carrier
Silica-gel carrier is pre-processed with embodiment 1；
Under nitrogen protection, 20.0g magnesium chloride, the 36.8mL ethyl alcohol (molar ratio of ethyl alcohol and magnesium chloride are added into reaction kettle
For 3.0:1), reaction kettle is warming up to 120 DEG C and is melted completely to magnesium chloride.
It is 20 μm of treated silica-gel carrier reactions that 5.0g average grain diameter is added into reaction kettle under nitrogen protection
After 30min, it will be preheating to 120 DEG C of 200mL atoleine and the mixed dispersant addition reaction kettle of 200mL methyl-silicone oil, with
After 800 revs/min of revolving speed stirring 4min, reaction mixture is transferred in cooling reactor under nitrogen protection, the cryogen in cooling reactor
For enough anhydrous hexanes for being cooled to -27 DEG C in advance, MgCl is made after agitated, cooling, solidification, washing, drying2-SiO2Compound load
Body 2.The group of analysis gained complex carrier 2 becomes (parts by weight), MgCl2: 37.0%；SiO2: 5.5%；Fluorenes diether: 3.8%；
C2H5OH:53.7%.
2, the preparation of catalyst
It is that composite carried catalyst 2 is made in carrier with complex carrier 2 with the method for preparing catalyst of embodiment 1.It is catalyzed
Agent Ti content: 3.01%；Ester content: 6.08%；Ether content；3.56%.
3, (>=93 DEG C) of propylene high-temperature polymerizations
Using composite carried catalyst 2, propylene high-temperature polymerization is carried out, high temperature polymerization method is the same as embodiment 1.The related number of polymerization
According to table 1 is listed in, the screening result of polymer is listed in table 2.
Embodiment 3
1, the preparation of complex carrier
Silica-gel carrier is pre-processed with embodiment 1；
Under nitrogen protection, 20.0g magnesium chloride, the 33.1mL ethyl alcohol (molar ratio of ethyl alcohol and magnesium chloride are added into reaction kettle
For 2.7:1), reaction kettle is warming up to 115 DEG C and is melted completely to magnesium chloride.
It is 20 μm of treated silica-gel carrier reactions that 10.0g average grain diameter is added into reaction kettle under nitrogen protection
After 30min, it will be preheating to 115 DEG C of 200mL atoleine and the mixed dispersant addition reaction kettle of 200mL methyl-silicone oil, with
After 800 revs/min of revolving speed stirring 4min, reaction mixture is transferred in cooling reactor under nitrogen protection, the cryogen in cooling reactor
For enough anhydrous hexanes for being cooled to -25 DEG C in advance, MgCl is made after agitated, cooling, solidification, washing, drying2-SiO2Compound load
Body 3.The group of analysis gained complex carrier 3 becomes (parts by weight), MgCl2: 35.6%；SiO2: 10.5%；Fluorenes diether: 7.3%；
C2H5OH:46.6%.
2, the preparation of catalyst
It is that composite carried catalyst 3 is made in carrier with complex carrier 3 with the method for preparing catalyst of embodiment 1.It is catalyzed
Agent Ti content: 3.16%；Ester content: 5.84%；Ether content: 3.53%.
3, (>=93 DEG C) of propylene high-temperature polymerizations
Using composite carried catalyst 3, propylene high-temperature polymerization is carried out, high temperature polymerization method is the same as embodiment 1.The related number of polymerization
According to table 1 is listed in, the screening result of polymer is listed in table 2.
Embodiment 4
1, the preparation of complex carrier
The preparation method is the same as that of Example 1 for complex carrier, only changes the additional amount of raw material, magnesium chloride, ethyl alcohol and passes through fluorenes
The additional amount of three kinds of raw materials of silica gel is respectively 10.0g, 17.2mL, 10.0g after diether processing.The group of analysis gained complex carrier 4
As (parts by weight), MgCl2: 29.2%；SiO2: 17.2%；Fluorenes diether: 12.1%；C2H5OH:41.5%.
2, the preparation of catalyst
It is that composite carried catalyst 4 is made in carrier with complex carrier 4 with the method for preparing catalyst of embodiment 1.It is catalyzed
Agent Ti content: 3.12%；Ester content: 6.70%；Ether content: 10.86%.
3, (>=93 DEG C) of propylene high-temperature polymerizations
Using composite carried catalyst 4, propylene high-temperature polymerization is carried out, high temperature polymerization method is the same as embodiment 1.The related number of polymerization
According to table 1 is listed in, the screening result of polymer is listed in table 2.
Embodiment 5
1, the preparation of complex carrier
The preprocess method of silica-gel carrier only distinguishes the additional amount of toluene, silica, fluorenes diether with embodiment 1
It is adjusted to 320mL, 20.0g, 9.4g, wherein in pretreatment, the molar ratio of silica and fluorenes diether is adjusted to silica-gel carrier
9:1；The molar ratio of toluene and silica is adjusted to 14:1.
The preparation method is the same as that of Example 1 for complex carrier, only changes the additional amount of raw material, magnesium chloride, ethyl alcohol and silica gel three
The additional amount of kind raw material is respectively 10.0g, 17.2mL, 10.0g.The group of analysis gained complex carrier 5 becomes (parts by weight),
MgCl2: 29.3%；SiO2: 19.9%；Fluorenes diether: 9.3%；C2H5OH:41.5%.
2, the preparation of catalyst
It is that composite carrier load type catalyst 5 is made in carrier with complex carrier 5 with the method for preparing catalyst of embodiment 1.
Its catalyst Ti content: 3.20%；Ester content: 6.25%；Ether content: 7.82%.
3, (>=93 DEG C) of propylene high-temperature polymerizations
Using composite carried catalyst 5, propylene high-temperature polymerization is carried out, high temperature polymerization method is the same as embodiment 1.The related number of polymerization
According to table 1 is listed in, the screening result of polymer is listed in table 2.
Embodiment 6
1, the preparation of complex carrier
The preprocess method of silica-gel carrier only distinguishes the additional amount of silica, fluorenes diether, toluene with embodiment 1
It is adjusted to 20.0g, 10.5g, 185mL wherein, in pretreatment, the molar ratio of silica and fluorenes diether is adjusted to silica-gel carrier
8:1；The molar ratio of toluene and silica is adjusted to 8:1.
Under nitrogen protection, 10.0g magnesium chloride, 17.2mL ethyl alcohol (mole of ethyl alcohol and magnesium chloride are added into reaction kettle
Than reaction kettle being warming up to 125 DEG C and is melted completely to magnesium chloride for 2.8:1).
The pretreated silica-gel carrier of 15.0g is added into reaction kettle under nitrogen protection, after reacting 60min, will be preheating to
Reaction kettle is added in 125 DEG C of 200mL atoleine and the mixed dispersant of 200mL methyl-silicone oil, is stirred with 800 revs/min of revolving speed
After mixing 5min, reaction mixture is transferred in cooling reactor under nitrogen protection, the cryogen in cooling reactor is cooled to -27 to be enough in advance
DEG C anhydrous hexane, agitated, cooling, solidification, washing, it is dry after MgCl is made2-SiO2Complex carrier 6.Analysis gained is compound
The group of carrier 6 becomes (parts by weight), MgCl2: 25.5%；SiO2: 25.7%；Fluorenes diether: 12.6%；C2H5OH:36.2%.
2, the preparation of catalyst
It is that composite carried catalyst 6 is made in carrier with complex carrier 6 with the method for preparing catalyst of embodiment 1.It is catalyzed
Agent Ti content: 3.81%, ester content: 5.75%；Ether content: 11.33%.
3, (>=93 DEG C) of propylene high-temperature polymerizations
Using composite carried catalyst 6, propylene high-temperature polymerization is carried out, high temperature polymerization method is the same as embodiment 1.The related number of polymerization
According to table 1 is listed in, the screening result of polymer is listed in table 2.
Embodiment 7
1, the preparation of complex carrier
Silica-gel carrier first activates 1 hour under the conditions of 300 DEG C of temperature, activation temperature is then improved, in 450 DEG C of temperature conditions
Lower activation 5 hours；Under nitrogen protection, activated silica supports 20.0g is added in 117mL toluene (toluene with
The mass ratio of silica is 5:1, under agitation, 10.3g diisobutyl phthalate (DIBP) (silica is added
It is 9:1 with the molar ratio of DIBP), toluene solvant is boiled off after reacting 2 hours at 35 DEG C, being dried to obtain that treated, silica-gel carrier is solid
Body powder.
The preparation method of complex carrier is the same as embodiment 3.The group of analysis gained complex carrier 7 becomes (parts by weight),
The group of analysis gained complex carrier 3 becomes (parts by weight), MgCl2: 36.6%；SiO2: 10.1%；O-phthalic
Sour diisobutyl ester: 6.8%；C2H5OH:46.5%.
2, the preparation of catalyst
It is that composite carried catalyst 7 is made in carrier with complex carrier 7 with the method for preparing catalyst of embodiment 1.It is catalyzed
Agent Ti content: 3.16%；Ester content: 9.3%.
3, (>=93 DEG C) of propylene high-temperature polymerizations
Using composite carried catalyst 7, propylene high-temperature polymerization is carried out, high temperature polymerization method is the same as embodiment 1.The related number of polymerization
According to table 1 is listed in, the screening result of polymer is listed in table 2.
Comparative example 1
1, the preparation of carrier
25.0g magnesium chloride, the 42.9mL ethyl alcohol (molar ratio of ethyl alcohol and magnesium chloride is added into reaction kettle under nitrogen protection
For 2.8:1), reaction kettle is warming up to 125 DEG C to magnesium chloride melting.125 DEG C of 200mL atoleine and 200mL will be preheating to
The mixed dispersant of methyl-silicone oil is pressed into reaction kettle, after stirring 4min with 800 revs/min of revolving speed, by reaction mixture in nitrogen
It being transferred in cooling reactor under protection, the cryogen in cooling reactor is the anhydrous hexane for being cooled to -25 DEG C in advance, agitated, cooling, solidification,
Chlorination magnesium alcoholate carrier 8 is made after washing, drying.The group for analyzing resulting vehicle 8 becomes (parts by weight), MgCl2:
42.4%；C2H5OH:57.6%.
2, the preparation of catalyst
Carrier 8 is added in titanium tetrachloride liquid, preparation process obtains loaded catalyst 8 with embodiment 1.It is catalyzed
Agent Ti content: 2.73%, ester content: 6.42%.
3, (>=93 DEG C) of propylene high-temperature polymerizations
Using composite carried catalyst 8, propylene high-temperature polymerization is carried out, high temperature polymerization method is the same as embodiment 1.The related number of polymerization
According to table 1 is listed in, the screening result of polymer is listed in table 2.
Comparative example 2
1, the preparation of complex carrier
Under nitrogen protection, 25.0g magnesium chloride, 42.9mL ethyl alcohol (mole of ethyl alcohol and magnesium chloride are added into reaction kettle
Than reaction kettle being warming up to 125 DEG C and is melted completely to magnesium chloride for 2.8:1).
The silica-gel carrier that 5.0g average grain diameter is 20 μm is added into reaction kettle under nitrogen protection, and (silica-gel carrier first exists
Activate under the conditions of 200 DEG C 2 hours, then activated 4 hours under the conditions of 600 DEG C), after reacting 30min, 125 DEG C will be preheating to
Reaction kettle is added in the mixed dispersant of 200mL atoleine and 200mL methyl-silicone oil, stirs 4min with 800 revs/min of revolving speed
Afterwards, reaction mixture is transferred in cooling reactor under nitrogen protection, the cryogen in cooling reactor is enough nothings for being cooled to -25 DEG C in advance
MgCl is made after agitated, cooling, solidification, washing, drying in water hexane2-SiO2Complex carrier 8.Analysis gained complex carrier 8
Group becomes (parts by weight), MgCl2: 39.1%；SiO2: 7.8%；C2H5OH:53.1%.
2, the preparation of catalyst
Catalyst preparation process obtains loaded catalyst 8 with catalyst preparation process in embodiment 1.Its catalyst Ti contains
Amount: 2.82%, ester content: 5.91%.
3, (>=93 DEG C) of propylene high-temperature polymerizations
Using composite carried catalyst 8, propylene high-temperature polymerization is carried out, high temperature polymerization method is the same as embodiment 1.The related number of polymerization
According to table 1 is listed in, the screening result of polymer is listed in table 2.
Comparative example 3
1, the preparation of complex carrier
Under nitrogen protection, 25.0g magnesium chloride, the 46mL ethyl alcohol (molar ratio of ethyl alcohol and magnesium chloride are added into reaction kettle
For 3.0:1) and 7.8g smoke-like silica gel (Cabot company's T S-610, get rid of through hot nitrogen air-blowing except free water), white oil is added
(viscosity is 30 centipoises at 20 DEG C) 145mL, reaction kettle is warming up to after reacting 2.5 hours at 125 DEG C, by the alcohol adduct after melting
And the slurries of smoke-like silica gel are transferred in 125 DEG C of methyl-silicone oil (viscosity the is 300 centipoises at 20 DEG C) medium being preheated,
The dosage of methyl-silicone oil is that above-mentioned height is stirred the slurries of dispersion through major diameter after stirring 15min with 2500 revs/min of revolving speed by 300mL
It is transferred in the hexane medium for being cooled to -30 DEG C in advance (hexane and slurries than the tubule for 45 with the flow velocity of 300mL/min
Volume ratio is 4:1), after keeping 300 revs/min of revolving speed to continue stirring 15 minutes, solid particle is filtered out, and washed with anhydrous hexane
It washs carrier granular six times and drains.The group of analysis gained spherical complex carrier 9 becomes (parts by weight), MgCl2: 36.2%；
SiO2: 11.3%；C2H5OH:52.5%.
2, the preparation of catalyst
100mL titanium tetrachloride is added in catalyst preparation bottle, is cooled to addition 7g complex carrier 9 at -20 DEG C, reaction 1
It after hour, is to slowly warm up to, 1.4mLDIBP is added in 40 DEG C of whens, continues to be to slowly warm up to 100 DEG C, after maintaining reaction 2 hours while hot
Filtering, adds 100mL titanium tetrachloride, is warming up to 125 DEG C, and isothermal reaction is filtered while hot after 2 hours at this temperature, with oneself
Alkane washs 4 times under the conditions of 50~60 DEG C, washs 2 times at room temperature, dry soccer star's solid catalyst 9.Its catalyst Ti contains
Amount: 3.01%, ester content: 6.23%.
3, (>=93 DEG C) of propylene high-temperature polymerizations
Using composite carried catalyst 9, propylene high-temperature polymerization is carried out, high temperature polymerization method is the same as embodiment 1.The related number of polymerization
According to table 1 is listed in, the screening result of polymer is listed in table 2.
It can be seen that prepared by the method composite carried catalyst by 1 data of table, polymerize for propylene high-temperature
When, there is higher catalytic activity, catalytic activity is up to 52.1KgPP/gCat, and the particle shape of resulting polymers is good, heap
Density reaches 0.46g/mL, meanwhile, with high temperature polymer prepared by the present invention, isotacticity has compared with comparative example significantly to be mentioned
Height solves the problems, such as relatively low with the propylene high-temperature polymer isotacticity of conventional polypropylene catalyst preparation.From 2 high temperature propylene of table
The fine powder rate (>=80 mesh) that the screening result of polymer can be seen that polymer in embodiment is respectively less than 1.0%, in comparative example
The fine powder rate of polymer is compared to less.
The performance of 1 catalyst of table and its high temperature polymer
| Number | 93 DEG C of polymerization activity KgPP/gCat | Heap density g/mL | Isotacticity % |
| Embodiment 1 | 43.2 | 0.40 | 97.5 |
| Embodiment 2 | 45.6 | 0.42 | 97.8 |
| Embodiment 3 | 48.3 | 0.44 | 98.2 |
| Embodiment 4 | 52.1 | 0.46 | 98.5 |
| Embodiment 5 | 47.2 | 0.43 | 98.0 |
| Embodiment 6 | 42.7 | 0.41 | 97.9 |
| Embodiment 7 | 30.1 | 0.39 | 96.5 |
| Comparative example 1 | 10.4 | 0.33 | 87.1 |
| Comparative example 2 | 17.5 | 0.42 | 90.1 |
| Comparative example 3 | 11.3 | 0.40 | 85.5 |
The screening result of 2 high temperature polymer of table compares
| Number | ≤ 20 mesh | 20~40 mesh | 40~60 mesh | 60~80 mesh | 80~100 mesh | >=100 mesh |
| Embodiment 1 | 79.42 | 13.45 | 4.48 | 2.03 | 0.33 | 0.29 |
| Embodiment 2 | 80.90 | 14.90 | 3.10 | 0.58 | 0.22 | 0.30 |
| Embodiment 3 | 83.78 | 11.20 | 3.94 | 0.85 | 0.15 | 0.08 |
| Embodiment 4 | 87.67 | 10.62 | 1.38 | 0.16 | 0.12 | 0.05 |
| Embodiment 5 | 82.30 | 13.45 | 3.37 | 0.55 | 0.25 | 0.08 |
| Embodiment 6 | 76.78 | 18.25 | 3.74 | 0.75 | 0.36 | 0.12 |
| Embodiment 7 | 81.20 | 12.43 | 4.56 | 1.19 | 0.45 | 0.17 |
| Comparative example 1 | 89.01 | 8.05 | 1.12 | 0.32 | 0.62 | 0.88 |
| Comparative example 2 | 80.89 | 12.12 | 5.56 | 0.39 | 0.63 | 0.41 |
| Comparative example 3 | 70.16 | 14.25 | 11.24 | 3.29 | 0.80 | 0.26 |
It can be seen that prepared by the method composite carried catalyst by 1 data of table, polymerize for propylene high-temperature
When, there is higher catalytic activity, catalytic activity is up to 52.1KgPP/gCat, and the particle shape of resulting polymers is good, heap density
Up to 0.46g/mL, the isotacticity of gained high temperature polymer is significantly improved compared with comparative example.It polymerize from 2 propylene high-temperature of table
The fine powder rate (>=80 mesh) that the screening result of object can be seen that polymer in embodiment is respectively less than 1.0%, and polymerize in comparative example
The fine powder rate of object is compared to less.
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 the protection scope of the claims in the present invention.
Claims (10)
1. a kind of preparation method of propylene high-temperature polymerization catalyst complex carrier, which is characterized in that the carrier preparation process is,
(1) under nitrogen protection, the silica supports after activation are added in organic solvent, under agitation, Louis are added
This alkali boils off solvent after reacting a period of time, is dried to obtain solid powder；(2) under nitrogen protection, first by magnesium chloride and ethyl alcohol
Frit reaction occurs in a heated condition and prepares chlorination magnesium alcoholate melt, it is then molten to chlorination magnesium alcoholate under agitation
Step (1) pretreated solid powder is added in liquid to be reacted, the inertia dispersing agent for being preheated to same temperature is added later,
After being dispersed with stirring, reaction mixture is transferred in inertia cooling medium, stirring, is formed by curing spherical complex carrier at cooling.
2. the preparation method of propylene high-temperature polymerization catalyst complex carrier according to claim 1, which is characterized in that described
Silica supports substance is the spherical silica gel carrier of average grain diameter≤50 μm, and preferably the average grain diameter of silica is 1~30 μ
M, 100~300m of specific surface area2/ g, 0.5~3ml/g of pore volume, 5~40nm of average pore size.
3. the preparation method of propylene high-temperature polymerization catalyst complex carrier according to claim 1, which is characterized in that described
Organic solvent is toluene, dimethylbenzene, tetrahydrofuran equal solvent.
4. the preparation method of propylene high-temperature polymerization catalyst complex carrier according to claim 1, which is characterized in that described
Lewis base selects one or more, preferably two ethers of two ethers or two esters or succinate compound or diol-lipid compound
Compound.
5. the preparation method of propylene high-temperature polymerization catalyst complex carrier according to claim 1, which is characterized in that described
Inertia dispersing agent is made of mixed the atoleine of methyl-silicone oil and 30~50 centipoises that viscosity at 20 DEG C is 50~600 centipoises
Close object.
6. the preparation method of propylene high-temperature polymerization catalyst complex carrier according to claim 1, which is characterized in that described
Inertia cooling medium is the aromatic hydrocarbons of alkane, halogenated hydrocarbons or 6-12 carbon atom, preferably hexane, heptane, dichloroethanes, toluene, two
Toluene, ethylbenzene.
7. the preparation method of propylene high-temperature polymerization catalyst complex carrier according to claim 1, which is characterized in that described
The preparation method comprises the following steps:
(1) silica supports pre-process
Silica-gel carrier is activated first to remove the absorption water of silica-gel carrier and extra surface hydroxyl, more preferably
Condition can be activated first 1~2 hour using 150 DEG C~300 DEG C, then be activated 3~6 hours at 400 DEG C~600 DEG C；It is protected in nitrogen
Under shield, the silica supports after activation are added in organic solvent, the mass ratio of organic solvent and silica supports is
Under agitation lewis base is added, wherein silica supports and Louis in 2.5:1~20:1, preferably 3:1~15:1
The molar ratio of alkali is 1:1~20:1, preferably 5:1~10:1, is boiled off after reacting 0.5~3 hour under the conditions of 0 DEG C~40 DEG C of temperature
Solvent is dried to obtain solid powder；
(2) chlorination magnesium alcoholate melt is prepared
Under nitrogen protection, anhydrous magnesium chloride and dehydrated alcohol are added into reaction kettle, wherein the molar ratio of ethyl alcohol and magnesium chloride
For 2.0:1~4.0:1, preferably 2.5:1~3.5:1, heating makes magnesium chloride be melt into liquid completely, and heating temperature is 100 DEG C~140
DEG C, preferably 110 DEG C~130 DEG C；
(3) spherical shape MgCl is prepared2-SiO2Complex carrier
It keeps above-mentioned heating temperature constant, step is added into above-mentioned magnesium chloride alcohol adduct melt under nitrogen protection and stirring condition
Suddenly (1) pretreated silica-gel carrier, the additional amount of silica-gel carrier is 0.1~1.5g/g magnesium chloride, after reacting 5~60min, to anti-
It answers and inertia dispersing agent is added in device, inertia dispersing agent need to be preheated to temperature identical with reaction system at this time, dosage 0 in advance
~20ml/g magnesium chloride, inertia dispersing agent select the mixture of methyl-silicone oil and atoleine, and volume ratio is 1:1~1:7, excellent
Select methyl-silicone oil, atoleine volume ratio be 1:1~1:3, speed of the reaction mixture at 300~2000 revs/min, preferably
After stirring 2~5min under 600~1200 revs/min of revolving speed, mixture is transferred in cooling reactor under nitrogen protection, wherein lazy
Property cooling medium and dispersing agent volume ratio be 5:1~10:1, cooling temperature be -15~-40 DEG C, preferably -20~-30 DEG C, stir
It mixes, cool down, solidify, wash, be dried to obtain spherical complex carrier.
8. a kind of propylene high-temperature polymerization catalyst component, which is characterized in that the catalytic component contains claim 1~7 times
The reaction product of spherical complex carrier and titanium compound prepared by one method, the titanium compound such as general formula Ti (OR1)4-mXmInstitute
Show, R in formula1It is the aliphatic group of C1~C14, X chooses from or mixtures thereof F, Cl, Br, the integer that m is 1~4.
9. propylene high-temperature polymerization catalyst component according to claim 8, which is characterized in that the titanium compound is to answer
At a temperature of, completely soluble liquefied compound in nonpolar solvent, it is selected from titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four fourths
Oxygroup titanium, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygroup titanium, one ethanolato-titanium of trichlorine, one in titanium trichloride
Kind or their mixture, preferably titanium tetrachloride.
10. a kind of propylene high-temperature polymerization catalyst, which is characterized in that the catalyst includes the reaction product of following components:
(1) solid catalyst activity group is divided into any catalytic component described in claim 8~9；
(2) alkyl aluminum compound, general formula AlRnX(3-n), R is C in formula1~C20Alkyl, aryl or aralkyl, X is halogen
Element, n are the integer of 0≤n≤3, are chosen in particular from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, a chlorine diethyl
The mixing of one or more of base aluminium or a chloro-di-isobutyl aluminum, preferably triethyl aluminum or triisobutyl aluminium；
(3) a kind of external donor compound, be selected from single or multiple functional carboxylic acid, carboxylic acid anhydrides and carboxylate, ketone, ether, alcohol, lactone with
And organic phosphorus and organo-silicon compound, preferred organo-silicon compound such as Cyclohexyl Methyl Dimethoxysilane, bicyclopentyl diformazan
Oxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, dimethoxydimethylsilane, diethoxy
The mixing of one or more of base dimethylsilane or dimethoxydiphenyl silane；
Wherein, the ratio between solid catalyst activity component, alkyl aluminum compound and external donor compound, with titanium: aluminium:
Molar ratio computing between silicon is 1:5~1000:0~500.
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