CN108084305A - Solid titanium catalyst component for vinyl polymerization and preparation method thereof and ethane polymerization solid titanium catalyst - Google Patents
Solid titanium catalyst component for vinyl polymerization and preparation method thereof and ethane polymerization solid titanium catalyst Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Abstract
A kind of solid titanium catalyst component for vinyl polymerization and preparation method thereof and ethane polymerization solid titanium catalyst, catalytic component preparation method：(1) magnesium compound is dissolved in alcohols solvent；(2) mixture, organo-silicon compound and titanium compound obtained by (1) are reacted, reaction temperature is 50~120 DEG C, and the molar ratio of magnesium, silicon and titanium is 1:0.2~0.4:1.0~15.0；The general formula of magnesium compound is XnMgR2‑n；R is the alkyl of hydrogen or 1~20 carbon atom；X is halogen；0≤n≤2, and n is integer, when n is 0, two R are identical or different；Organo-silicon compound are 3 glycydoxy triethoxysilanes；Titanium compound general formula is Ti (OR ＇)aX ＇b；R ＇ are C1~C10Aliphatic group or aryl, X ＇ be halogen, a 0,1,2 or 3,1≤b≤4, and b for integer, a+b=3 or 4.The catalyst of granulated is easily precipitated in catalytic component of the present invention when preparing；For vinyl polymerization, hydrogen response is good, and gained polyethylene powder fine powder content is low.
Description
Technical field
The present invention relates to a kind of solid titanium catalyst groups closed for ethylene homo or ethylene is closed with other alpha-olefin copolymers
The ethylene rolymerization catalyst of the preparation method divided and the solid titanium catalyst component and organo-metallic compound composition.
Background technology
The preparation method of the efficient Ziegler-Natta catalyst of vinyl polymerization is well-known, mainly by MgCl2Or
SiO2The halide composition of the titanium of load.The preparation method of vinyl polymerization and copolymerization catalyst as disclosed in JP 4951378
It is：The magnesium dichloride of ground crushing generates MgCl with ethanol synthesis2·6C2H5OH alcohol adduct slurries, then with aluminium diethyl monochloride
Generation esterification, last and TiCl4It carries out carrying titanium reaction, obtains MgCl2Carrier loaded Titanium series catalyst.This catalyst
Preparation method is simple, and reaction condition is mild, very high for catalytic activity during catalyzed ethylene polymerization.But this preparation method, which exists, to be carried
Body magnesium chloride cannot dissolve in mineral oil, and magnesium chloride has the irregular piece generated when grinding in slurry reaction system
Shape particle, the solid catalyst particle form caused is poor, and thickness is uneven, thus polymer morphology is also bad, fine powder
It is more, it is easy to produce static electricity and easily block pipeline.After oligomer of the catalyst in polymerization in solvent is relatively mostly simultaneously
Processing brings larger trouble.
Patent CN1229092 discloses a kind of for vinyl polymerization and the catalyst system of combined polymerization, the catalyst system
Including：(1) ingredient of solid catalyst containing Ti, (2) alkyl aluminum compound, wherein the ingredient of solid catalyst containing Ti is by halogenation
Magnesium is dissolved in organic epoxy compound object and organic phosphorus compound forms homogeneous phase solution, adds in the magnesium halide that Ethanol Treatment has dissolved, so
The solution is mixed with titanium tetrahalide afterwards, and in the presence of precipitating reagent such as organic acid anhydride, organic acid, ether, ketone compound, solid is precipitated
Object obtains solid catalyst.When the catalyst system is used for vinyl polymerization, resulting polymers fine powder content is more, catalyst is lived
Property it is relatively low, hydrogen response is poor, be unsuitable for preparing bimodal polymers, it is difficult to substitute the catalysis of existing high activity ethylene slurry polymerization
Agent.The heap density of polymer is also slightly below the level of existing catalyst simultaneously.
Patent CN1112373 discloses a kind of solid titanium catalyst component and its preparation process, mainly using low-carbon alcohols come
Magnesium halide is dissolved, and adds in alkane diluent and silanes electron donor compound, is then acted on halogenated titanium, solid is precipitated and urges
Agent.Although the catalyst is used to that the ethene polymers with excellent particulates' properties can be made during vinyl polymerization, it is catalyzed
Activity and oligomer are still unsatisfactory.
The content of the invention
The object of the present invention is to provide a kind of solid titanium catalyst component for vinyl polymerization and preparation method thereof and vinyl polymerizations
Solid titanium catalyst, to overcome the poor catalytic activity of ethane polymerization solid titanium catalyst in the prior art, hydrogen response is poor, with
And the defects of gained ethylene polymer particles poor morphology.
The object of the present invention is achieved like this, a kind of preparation method of solid titanium catalyst component for vinyl polymerization, the system
Preparation Method is：
(1) magnesium compound is dissolved in alcohols solvent；And
(2) by the titanium compound hybrid reaction of mixture, organo-silicon compound and liquid obtained by step (1), ethylene is precipitated
Polymerization solid titanium catalyst agent component, wherein, reaction temperature is 50~120 DEG C, and the molar ratio of magnesium, silicon and titanium is 1:0.2~0.4:
1.0~15.0；
Wherein, the general formula of magnesium compound is XnMgR2-n；R is the alkyl of hydrogen or 1~20 carbon atom；X is halogen；0≤n
≤ 2, and n is integer, when n is 0, two R are identical or different；
Wherein, organo-silicon compound are 3- glycydoxy triethoxysilanes, and structure is as follows：
Wherein, titanium compound general formula is Ti (OR ＇)aX ＇b；R ＇ are C1~C10Aliphatic group or aryl, X ＇ are halogen, and a is
0th, 1,2 or 3,1≤b≤4, and b be integer, a+b=3 or 4.
The preparation method of solid titanium catalyst component for vinyl polymerization of the present invention, wherein it is preferred that step (2) is
Mixture obtained by step (1) and organo-silicon compound are cooled to room temperature after mixing, are then added drop-wise to temperature as -5~5 DEG C
Liquid titanium compound in, then be warming up to 50~120 DEG C and reacted.
The preparation method of solid titanium catalyst component for vinyl polymerization of the present invention, wherein it is preferred that step (2) is
Mixture obtained by step (1) is cooled to room temperature, is then added drop-wise in the titanium compound for the liquid that temperature is -5~5 DEG C, is dripping
Organo-silicon compound are added in during adding to be uniformly mixed, and are warming up to 50~120 DEG C and are reacted.
The preparation method of solid titanium catalyst component for vinyl polymerization of the present invention, wherein, step (1) course of dissolution is excellent
It is selected in the presence of diluent and carries out, the diluent is preferably aliphatic hydrocarbon.
The preparation method of solid titanium catalyst component for vinyl polymerization of the present invention, wherein, the alcohols solvent is preferred
For carbon number be 1~10 alkylol, the cyclic alkanol that carbon number is 3~10, the halides of the alkylol, the cycloalkanes
Aralkyl alcohol, the fragrant and mellow halides or the institute that fragrant and mellow, the carbon number that the halides of alcohol, carbon number are 6~20 are 6~20
State the halides of aralkyl alcohol.
The preparation method of solid titanium catalyst component for vinyl polymerization of the present invention, wherein, the alcohols solvent and magnesium
The molar ratio of compound is preferably 0.1~10.0:1.
The preparation method of solid titanium catalyst component for vinyl polymerization of the present invention, wherein, the alcohols solvent and magnesium
The solution temperature of compound is preferably 50~150 DEG C.
The vinyl polymerization prepared the present invention also provides the preparation method of above-mentioned solid titanium catalyst component for vinyl polymerization is consolidated
Body titanium catalyst component.
The present invention also provides a kind of ethane polymerization solid titanium catalyst, which includes：
Above-mentioned solid titanium catalyst component for vinyl polymerization；And
Organo-aluminum compound；
Wherein, the general formula of organo-aluminum compound is AlR 〞mX〞3-m, R 〞 are hydrogen or carbon number is l~20 in formula alkyl,
X 〞 be halogen, 0<m≤3；
Wherein, the molar ratio of organo-aluminum compound and above-mentioned solid titanium catalyst component for vinyl polymerization is 20~200:1.
Beneficial effects of the present invention：
The present invention catalyst due to using 3- glycydoxies triethoxysilane to help analysis agent,
It is easy to that spherical catalyst granules is precipitated during catalyst preparation.And substantial amounts of titanizing need not be used during titanium is carried
Object is closed to promote the precipitation of precipitation, it is not required that titanium compound is used for multiple times to handle precipitation, therefore the addition of titanium compound
Greatly reduce.The addition of organo-silicon compound simultaneously also contributes to the activity of catalyst and changing for the particle shape of catalyst
It is kind, so as to further improve the particle shape of polymer, and make the oligomer wax content in product polyethylene relatively low.The catalysis
When agent is used for vinyl polymerization, preferable hydrogen response is shown.
Specific embodiment
The solid titanium catalyst component for vinyl polymerization of the present invention is by a kind of (a) magnesium compound of liquid, (b) 3- glycidols
Ether oxygen base propyl-triethoxysilicane, a kind of (c) titanium compound composition.The solid titanium catalyst component contains magnesium, titanium, silicon and halogen
Element.Each raw material for being used to prepare solid titanium catalyst component of the present invention is described as follows：
(a) liquid magnesium compound
Magnesium compound is dissolved in solvent by liquid magnesium compound to be obtained.Wherein, the general formula of magnesium compound is
XnMgR2-n；R is the alkyl of hydrogen or 1~20 carbon atom；X is halogen；0≤n≤2, and n is integer, when n is 0, two R phases
It is same or different.Magnesium compound is specifically as follows alkyl magnesium, such as dimethyl magnesium, magnesium ethide, dipropyl magnesium, dibutylmagnesium, two
Amyl magnesium, dihexyl magnesium, didecyl magnesium, octyl group dibutyl magnesium and ethyl-butyl magnesium；Magnesium alkyl halide, such as a chloroethyl magnesium,
One chloropropyl magnesium, a chlorobutyl magnesium, a chlorine amyl magnesium and a chlorine hexyl magnesium；Alkyl magnesium alkyl oxide, such as butyl ethyoxyl
Magnesium, ethyl-butoxy magnesium and octyl group butoxy magnesium；Magnesium halide, such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride；Alkoxyl magnesium
Halide, such as a chlorine magnesium methoxide, a chloroethoxy magnesium, a chlorine isopropoxy magnesium, a neoprene oxygroup magnesium and a chlorine octyloxy
Magnesium；Aryloxy group magnesium halide, such as monochloro-benzene oxygroup magnesium, chloromethyl phenoxy group magnesium；Alkoxyl magnesium, such as magnesium ethylate, isopropyl oxygen
Base magnesium, butoxy magnesium, n-octyloxy magnesium and 2- ethyl hexyl oxy magnesium；Aryloxy group magnesium, such as phenoxy group magnesium, two (methylphenoxies)
Magnesium；The carboxylate of magnesium, such as Magnesium dilaurate and magnesium stearate；Magnesium metal, magnesium hydride and a hydrogen dibutyl magnesium.X is halogen, as F, Cl,
Br and I.In above-claimed cpd, preferably halogen-containing magnesium compound.Wherein be preferably magnesium chloride, a chlorine alkoxyl magnesium and
One chlorine aryloxy group magnesium.
Dissolving the solvent of magnesium compound includes alcohol, carboxylic acid, aldehyde, amine and metal acid esters etc..The example of alcohol includes：Fatty alcohol,
As methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, amylalcohol, hexanol, 2- methyl anyl alcohols, 2- ethyl butanols, enanthol, 2-Ethylhexyl Alcohol,
Octanol, decyl alcohol, dodecanol, tetradecanol, hexadecanol, octadecanol, tip-nip, oleyl alcohol and ethylene glycol；Alicyclic ring alcohol, such as
Cyclohexanol and methyl cyclohexanol；It is fragrant and mellow, such as benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol, a- methylbenzyl alcohols, a, a '-two
Methylbenzyl alcohol, benzyl carbinol, cumic alcohol, phenol, cresols, dimethlbenzene, ethyl -phenol, propylphenol, nonyl phenol and naphthols；Containing alkane
The alcohol of oxygroup, such as ethylene glycol-n-butyl ether, glycol-ether, 1- butoxy -2- propyl alcohol；Halogen-containing alcohol, such as trichlorine methanol, three
Chlorethanol and three Mecorals.Carboxylic acid is preferably the carboxylic acid with seven or more carbon atoms, such as octanoic acid, 2 ethyl hexanoic acid, n-nonanoic acid
And undecenoic acid.Aldehyde is preferably the aldehyde with seven or more carbon atoms, such as octanal, 2- ethyl hexanals, the hendecanal, benzene first
Aldehyde, tolualdehyde and naphthaldehyde.The amine of there are six amine preferably tools or more carbon atom, such as heptyl amice, octylame, 2 ethyl hexylamine, nonyl
Amine, decyl amine, undecylamine and lauryl amine.The example of metal acid esters includes：Purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxide
Titanium, four titanium butoxides, four hexyloxy titaniums, tetrabutyl zirconate and tetraethoxy zirconium.Wherein, preferably alcohol, most preferably has
The alcohol of six or more carbon atoms.If using the alcohol of carbon atom there are six tools or more as the molten of liquid magnesium compound processed
Agent, alcohol/magnesium molar ratio are usually not less than 1, preferably 1~40, and preferably 1.0~10.If it uses there are five tools or less
The alcohol of carbon atom, dosage are usually not less than 1.
When solid-state magnesium compound is contacted with alcohol, a kind of varsol can be used.The example of the varsol includes fat
Fat hydrocarbon, such as pentane, hexane, heptane, octane, decane, dodecane, the tetradecane and kerosene；Alicyclic such as pentamethylene, methyl ring penta
Alkane, hexamethylene, hexahydrotoluene and cyclooctane；Aromatic hydrocarbon such as benzene,toluene,xylene, ethylbenzene, cumene and isopropyl methyl
Benzene；Halogenated hydrocarbons, such as carbon tetrachloride, dichloroethanes, dichloropropane, trichloro ethylene and chlorobenzene.If virtue is used in these solvents
Hydrocarbon, the dosage of alcohol is identical with dosage during above-mentioned situation using six or more carbon atom alcohols, no matter with which kind of carbon number
Alcohol, magnesium compound all can dissolve.When using aliphatic hydrocarbon and/or alicyclic, the dosage of alcohol is according to carbon by above-mentioned
Atomicity and it is different.In the present invention, solid-state magnesium compound is preferably made to be contacted with alcohol in hydrocarbon solvent.In order to make solid-state magnesium
Compound is dissolved in alcohol, and general using solid-state magnesium compound is made to be reacted with alcohol in the case of heating stirring, reaction preferably exists
It carries out in the presence of hydrocarbon solvent, and it is heated as needed.The temperature of usual this contact is 0~300 DEG C, preferably
20~180 DEG C, most preferably 50~150 DEG C, about 15 points of time to 5 it is small when, preferably from about 30 points to 3 it is small when.
(b) organo-silicon compound
The organo-silicon compound of inactive hydrogen atom select 3- glycydoxy triethoxysilanes, structure
It is as follows：
(c) titanium compound of liquid
Liquid titanium compound in the present invention is preferably tetravalent titanium compound.The tetravalent titanium compound can use general formula
It represents：Ti (OR ＇)aX ＇b；R ＇ are C1~C10Aliphatic group or aryl, X ＇ are halogen, a 0,1,2 or 3,1≤b≤4, and b is
Integer, a+b=3 or 4.
Prepare solid titanium catalyst component for vinyl polymerization
1st, the following method preparation can be used in catalytic component of the invention：
(1) magnesium compound is dissolved in alcohols solvent, adds in inert diluent, form homogeneous solution, solution temperature is excellent
Select 50~130 DEG C；3- glycydoxy triethoxysilanes are added in during solution is formed.
(2) above-mentioned solution and titanium compound are subjected to haptoreaction, and mixture is to slowly warm up to 50~120 DEG C, Gu
Body object is gradually precipitated and forms particle, after reacting the regular hour, removes unreacted reactant and solvent, and is washed using inert diluent
It washs, obtains the catalytic component of the present invention.
2nd, the following method preparation also can be used in catalytic component of the invention：
(1) magnesium compound is dissolved in alcohols solvent, adds in inert diluent, form homogeneous solution, solution temperature is excellent
Select 50~130 DEG C；
(2) above-mentioned solution and titanium compound are subjected to haptoreaction, and add in 3- glycydoxies three simultaneously
Ethoxysilane, and mixture is to slowly warm up to 50~120 DEG C, solids is gradually precipitated and forms particle, reacts certain
After time, unreacted reactant and solvent are removed, and is washed using inert diluent, obtains the catalytic component of the present invention.
The present invention also provides a kind of copolymerizations for the homopolymerization reaction of ethylene or ethylene and other alpha-olefins
Catalyst, alpha-olefin therein include propylene, butene-1,4- methylpentenes -1, hexene -1, octene-1, styrene, methylbenzene
Ethylene etc.；The solid titanium catalyst component for vinyl polymerization that the catalyst includes the above-mentioned present invention is AlR 〞 with general formulamX〞3-m's
Organo-aluminum compound, the particularly alkyl that R 〞 are hydrogen or carbon number is l~20 in formula Chinese style, alkyl, aralkyl, aryl；X〞
For halogen, particularly chlorine and bromine；0<m≤3.Particular compound is such as：Trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-octyls
The aluminum alkyl halides such as aluminium, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium, ethyl aluminum dichloride, wherein excellent
Trialkyl aluminium compound is selected, especially preferably triethyl aluminum, triisobutyl aluminium.Wherein the molar ratio of component aluminium and component titanium for 5~
500:1, preferably 20~200:1.
Above-mentioned solid titanium catalyst is used to that liquid phase polymerization to may be employed during vinyl polymerization, can also use gas-phase polymerization.Liquid
Phase-polymerization medium includes：Iso-butane, hexane, heptane, hexamethylene, naphtha, raffinate oil, hydrogasoline, kerosene, benzene, toluene, two
The atent solvents such as the aliphatic saturated hydrocarbons such as toluene or aromatic hydrocarbon.
Intermittent, semi continuous or continous way may be employed in polymerization methods.Polymerization temperature is 0~150 DEG C, with 40~100
DEG C preferably.In order to adjust the molecular weight of final polymer, using hydrogen as molecular weight regulator.
Embodiment 1
(1) preparation of catalytic component：4.76 grams of (50mmol) anhydrous magnesium chlorides, 75 milliliters of decane and 16.3 grams
(125mmol) isooctanol is heated to 130 DEG C, be allowed to be stirred to react 3 it is small when, obtain a kind of homogeneous phase solution.It is added in into the solution
The 3- glycydoxies triethoxysilane of 12.5mmol and when stirring 2 is small at 50 DEG C so that its to be dissolved in this molten
Liquid.All homogeneous phase solutions obtained above are cooled to room temperature, it is then interior when 1 is small to be added dropwise to temperature holding while stirring
For in 0 DEG C of 150mL titanium tetrachlorides.Make after dripping off mixture temperature kept at 0 DEG C 1 it is small when, then under stiring when 2 is small
It is interior that temperature is carried to 120 DEG C, and by this temperature keep 2 it is small when.When 2 is small after reaction, hot mistake is carried out to the solid of generation
Filter separation.Solid catalyst is fully washed with decane and hexane respectively, until inspection does not measure precipitation in cleaning solution
Titanium compound obtains solid titanium catalyst component after drying.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, and after high pure nitrogen is sufficiently displaced from, it is 1mol/L to add in hexane 1L and concentration
Triethyl aluminum 1.0mL, with syringe add in precise above-mentioned catalyst, be warming up to 75 DEG C, being passed through hydrogen makes kettle internal pressure
Power reaches 0.28MPa, then being passed through ethylene makes stagnation pressure in kettle reach 0.73MPa (gauge pressure), when polymerization 2 is small under the conditions of 80 DEG C, gathers
It closes object evaluation result and is shown in Table 1.
Embodiment 2
(1) preparation of catalyst component：4.76 grams of (50mmol) anhydrous magnesium chlorides, 75 milliliters of decane and 16.3 grams
(125mmol) isooctanol is heated to 130 DEG C, be allowed to react 3 it is small when, obtain a kind of homogeneous phase solution.It mixes obtained above
Liquid is cooled to room temperature, and then when 1 is small, the interior temperature that is added dropwise to while stirring is remained in 0 DEG C of 150mL titanium tetrachlorides.Drop
Make after complete mixture temperature kept at 0 DEG C 1 it is small when, into the solution add in 12.5mmol 3- glycydoxies
Triethoxysilane, so that 3- glycydoxy triethoxysilanes are dissolved in the solution system when holding 1 is small.So
It is interior when 2 is small under stiring afterwards that temperature is carried to 120 DEG C, and by this temperature keep 2 it is small when.When 2 is small after reaction, to life
Into solid carry out heat filtering separation.Solid catalyst is fully washed with decane and hexane respectively, until in cleaning solution
It is middle to examine the titanium compound for not measuring precipitation, solid titanium catalyst component is obtained after drying.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, and after high pure nitrogen is sufficiently displaced from, it is 1.0mol/ to add in hexane 1L and concentration
The triethyl aluminum 1.0mL of L adds in the catalyst of the above-mentioned preparation of precise with syringe, is warming up to 75 DEG C, being passed through hydrogen makes
Pressure reaches 0.28MPa in kettle, then being passed through ethylene makes stagnation pressure in kettle reach 0.73MPa (gauge pressure), and it is small that 2 are polymerize under the conditions of 80 DEG C
When, evaluation of polymer the results are shown in Table 1.
Embodiment 3
With embodiment 1, the difference is that the addition of 3- glycydoxy triethoxysilanes is
20mmol.Polymerization result is shown in Table 1.
Embodiment 4
With embodiment 2, the difference is that the addition of 3- glycydoxy triethoxysilanes is
10mmol.Polymerization result is shown in Table 1.
Embodiment 5
With embodiment 1, the difference is that the addition of decane is 50mL.Polymerization result is shown in Table 1.
Embodiment 6
With embodiment 1, the difference is that the addition of decane is 100mL.Polymerization result is shown in Table 1.
Comparative example 1
With embodiment 1.Simply it is not added with 3- glycydoxy triethoxysilanes.It is tired that shaping is precipitated in catalyst
Difficulty, precipitation particles are superfine, it is difficult to settle, when suction filtration is pumped entirely, fails to form catalyst.
Comparative example 2
With embodiment 1.The difference is that precipitation additive is changed to tetraethoxysilane, vinyl polymerization the results are shown in Table 1.
Comparative example 3
The synthesis of catalyst is prepared by 1 the method for CN1229092 embodiments.
In the reactor being sufficiently displaced from through high pure nitrogen, the anhydrous MgCl of 0.042mol are sequentially added2(about 4g), 60ml first
Benzene, 0.032mol epoxychloropropane, 0.022mol tributyl phosphates, 0.017mol ethyl alcohol, are warming up to 80 DEG C, and maintain under stirring
Solid is completely dissolved within 15 minutes, formed homogeneous solution, then add in phthalic anhydride 0.0074mol, then maintain 1 it is small when, will
The solution is cooled to -25 DEG C, then 0.5mol titanium tetrachlorides (about 55ml) are instilled in it, is then to slowly warm up to 80 DEG C, reaction 3
Hour, it is washed 3 times with toluene and hexane respectively after filtering, is dried in vacuo, obtains solid catalyst.
For vinyl polymerization condition with embodiment 1, evaluation of polymer the results are shown in Table 1.
1 evaluation of polymer result of table
As can be seen from Table 1, the polymer particle diameter distribution that prepared by embodiment is relatively concentrated, and is concentrated mainly on 100-140 mesh, secondary
For 80-100 mesh, and comparative example 1 is not plus in the case of 3- glycydoxy triethoxysilanes, catalyst analysis
Go out difficult forming, catalyst can not be obtained at all, although and comparative example 2 and 3 can obtain catalyst, resulting polymers grain
Footpath size is uneven, the polymer of each particle size interval distribution significant proportion in 20-200 mesh, and grain size smaller portions
Polymer ratio is substantially more than embodiment.
Beneficial effects of the present invention：
The present invention catalyst due to using 3- glycydoxies triethoxysilane to help analysis agent,
It is easy to that spherical catalyst granules is precipitated during catalyst preparation.And substantial amounts of titanizing need not be used during titanium is carried
Object is closed to promote the precipitation of precipitation, it is not required that titanium compound is used for multiple times to handle precipitation, therefore the addition of titanium compound
Greatly reduce.The addition of organo-silicon compound simultaneously also contributes to the activity of catalyst and changing for the particle shape of catalyst
It is kind, so as to further improve the particle shape of polymer, and make the oligomer wax content in product polyethylene relatively low.The catalysis
When agent is used for vinyl polymerization, preferable hydrogen response is shown.
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 deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (9)
1. a kind of preparation method of solid titanium catalyst component for vinyl polymerization, which is characterized in that the preparation method is：
(1) magnesium compound is dissolved in alcohols solvent；And
(2) by the titanium compound hybrid reaction of mixture, organo-silicon compound and liquid obtained by step (1), vinyl polymerization is precipitated
Solid titanium catalyst component, wherein, reaction temperature is 50~120 DEG C, and the molar ratio of magnesium, silicon and titanium is 1:0.2~0.4:1.0~
15.0；
Wherein, the general formula of the magnesium compound is XnMgR2-n；R is the alkyl of hydrogen or 1~20 carbon atom；X is halogen；0≤n≤
2, and n is integer, when n is 0, two R are identical or different；
Wherein, the organo-silicon compound are 3- glycydoxy triethoxysilanes, and structure is as follows：
Wherein, the titanium compound general formula is Ti (OR ＇)aX ＇b；R ＇ are C1~C10Aliphatic group or aryl, X ＇ are halogen, and a is
0th, 1,2 or 3,1≤b≤4, and b be integer, a+b=3 or 4.
2. the preparation method of solid titanium catalyst component for vinyl polymerization according to claim 1, which is characterized in that the step
Suddenly (2) are that mixture obtained by step (1) and organo-silicon compound are cooled to room temperature after mixing, are then added drop-wise to temperature
In titanium compound for -5~5 DEG C of liquid, then it is warming up to 50~120 DEG C and is reacted.
3. the preparation method of solid titanium catalyst component for vinyl polymerization according to claim 1, which is characterized in that the step
Suddenly (2) are that mixture obtained by step (1) is cooled to room temperature, are then added drop-wise to the titanium compound for the liquid that temperature is -5~5 DEG C
In, addition organo-silicon compound are uniformly mixed during being added dropwise, and are warming up to 50~120 DEG C and are reacted.
4. according to the preparation method of claim 1-3 any one of them solid titanium catalyst component for vinyl polymerization, feature exists
In step (1) course of dissolution carries out in the presence of diluent, and the diluent is aliphatic hydrocarbon.
5. the preparation method of solid titanium catalyst component for vinyl polymerization according to claim 4, which is characterized in that the alcohol
Class solvent be carbon number be 1~10 alkylol, the cyclic alkanol that carbon number is 3~10, the halides of the alkylol, institute
It states the halides of cyclic alkanol, is the aralkyl alcohol that fragrant and mellow, the carbon number that carbon number is 6~20 are 6~20, described fragrant and mellow halogenated
The halides of object or the aralkyl alcohol.
6. the preparation method of solid titanium catalyst component for vinyl polymerization according to claim 4, which is characterized in that the alcohol
The molar ratio of class solvent and magnesium compound is 0.1~10.0:1.
7. the preparation method of solid titanium catalyst component for vinyl polymerization according to claim 4, which is characterized in that the alcohol
The solution temperature of class solvent and magnesium compound is 50~150 DEG C.
8. vinyl polymerization prepared by the preparation method of claim 1-7 any one of them solid titanium catalyst component for vinyl polymerization
Solid titanium catalyst component.
9. a kind of ethane polymerization solid titanium catalyst, which is characterized in that the catalyst includes：
Solid titanium catalyst component for vinyl polymerization described in claim 8；And
Organo-aluminum compound；
Wherein, the general formula of organo-aluminum compound is AlR 〞mX〞3-m, R 〞 are hydrogen or carbon number is l~20 in formula alkyl, X 〞 are
Halogen, 0<m≤3；
Wherein, the molar ratio of the solid titanium catalyst component for vinyl polymerization described in organo-aluminum compound and claim 8 for 20~
200:1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611053975.6A CN108084305B (en) | 2016-11-22 | 2016-11-22 | Ethylene polymerization solid titanium catalyst component, preparation method thereof and ethylene polymerization solid titanium catalyst |
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| CN115043961A (en) * | 2022-07-25 | 2022-09-13 | 吉化集团吉林市天龙催化剂有限公司 | Ziegler-Natta catalyst, preparation method and catalyst component for ethylene polymerization |
| CN115975080A (en) * | 2021-10-14 | 2023-04-18 | 中国石油化工股份有限公司 | Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method |
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| CN102060945A (en) * | 2009-11-17 | 2011-05-18 | 中国石油天然气股份有限公司 | Preparation and application of solid titanium catalyst component for vinyl polymerization |
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| CN115975080A (en) * | 2021-10-14 | 2023-04-18 | 中国石油化工股份有限公司 | Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method |
| CN115043961A (en) * | 2022-07-25 | 2022-09-13 | 吉化集团吉林市天龙催化剂有限公司 | Ziegler-Natta catalyst, preparation method and catalyst component for ethylene polymerization |
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