CN106008759A - Electron donor of Ziegler-Natta catalyst and application of electron donor in vinyl polymerization - Google Patents

Electron donor of Ziegler-Natta catalyst and application of electron donor in vinyl polymerization Download PDF

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CN106008759A
CN106008759A CN201610466750.7A CN201610466750A CN106008759A CN 106008759 A CN106008759 A CN 106008759A CN 201610466750 A CN201610466750 A CN 201610466750A CN 106008759 A CN106008759 A CN 106008759A
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component
catalyst
sial
ester
electron donor
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CN106008759B (en
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姜涛
高金龙
李健
李明凯
张眉
邵怀启
陈延辉
闫冰
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Tianjin University of Science and Technology
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • C08F4/6465—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 containing silicium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/656—Pretreating with metals or metal-containing compounds with silicon or compounds thereof
    • C08F4/6565—Pretreating with metals or metal-containing compounds with silicon or compounds thereof and magnesium or compounds thereof

Abstract

The invention relates to an electron donor of a Ziegler-Natta catalyst, a catalyst component comprising the electron donor and the catalyst. The electron donor adopts a Si-Al ester compound; the catalyst prepared from the Si-Al ester compound serving as the electron donor shows higher catalytic activity, better hydrogen response and better copolymerization performance when applied to vinyl polymerization and copolymerization, and can be used for catalyzing vinyl homopolymerization or production of high-performance polyolefin materials with high bulk density, narrow particle size distribution and small fine grain content through copolymerization of vinyl and other alpha-olefins.

Description

The electron donor of a kind of Ziegler-Natta catalyst and at ethylene polymerization In application
Technical field
The invention belongs to vinyl polymerization catalytic field, relate to Ziegler-Natta catalyst, especially a kind of Ziegler- The electron donor of Natta catalyst and the application in ethylene polymerization thereof
Technical background
In recent years, the emphasis in the exploitation of high-end trade mark polyolefin PP Pipe Compound always this field, grinding of corresponding catalyst Studying carefully exploitation is also the difficult point in polyolefin research field.Ziegler-Natta Titanium series catalyst remains industrial production at present Polyolefinic dominant catalyst, develops high catalytic activity, hydrogen response is good, copolymerization performance is good, obtain polymer particle size divides Cloth is uniform, fine powder is few, oligomer wax content is low, produce the most controlled polyolefin catalyst is the target that scientific research personnel pursues. A lot of document and patent report many is had to prepare the titanio Ziegler-Natta catalyst of magnesium chloride load as olefinic polymerization Method with copolymerization catalyst.Difference according to polymerization technique, it is desirable to the performance of corresponding catalyst is also had nothing in common with each other, because of The production method of the catalyst of this correspondence is also slightly different.Such as the Ziegler-for ethylene gas-phase fluidized bed polymerization process Natta catalyst, it is desirable to catalyst granules form is good, fine powder is few, so produce when ethylene gas fluidised bed polymerisation is poly- Ethylene fine powder is few, can avoid the reactor sheeting caused because of electrostatic.Catalyst for ethene gas-phase polymerization is usually will Active component is directly carried on the inert carrier such as silica gel on big surface etc., owing to the particle diameter of silica gel is easily controlled, and Particle shape is preferable, therefore can get evengranular catalyst particle.But owing on carrier, the load capacity of active component is subject to Limiting, in the catalyst that the most this method prepares, Ti content is relatively low, and polymerization activity is the highest.Such as, in patent CN99103280 In, with MgCl2、SiO2For carrier, TiCl4For active component, the preparation method of catalyst is as follows: by MgCl2In THF with TiCl4Reaction formed catalyst mother solution, then with carrier S iO processed through alkyl aluminum2Mixing, makes after removing part oxolane Obtain catalyst precursor component.When for vinyl polymerization, owing to the Ti content in catalyst is relatively low, thus polymerization activity is relatively low. Therefore, although this catalyst system can be used for the gas-phase fluidized bed polymerization process of ethylene, but due to relatively low catalysis activity very Difficulty is be applicable to the slurry polymerization processes of ethylene.
Ziegler-Natta catalyst for ethylene slurry polymerization processes, it is desirable to catalyst activity is high, hydrogen response Can be good, require that polymerizate fine powder is few, wax content is few simultaneously, so can ensure that the continuous long-term operation of process units.Right Preparation method in this catalyst is to dissolve magnesium compounds such as magnesium chlorides to obtain homogeneous solution in a solvent, should the most again Solution mixes with titanium compound and electron donor, obtains the solids containing magnesium, titanium and electron donor by the method for precipitation, and will The liquid titanium compound of this solids excess obtains catalyst granules after processing.As Chinese patent CN1099041A, CN1229092、CN1958620A、CN100513433、CN100532406、CN102344514B、CN102344515B、 CN101274967B、CN102453172A、CN102432726A、CN102344506A、CN102344507、CN102286119A、 CN102286120A etc. disclose the method preparing this catalyst.The preparation of this catalyst is generally by the knot of magnesium chloride Partial crystallization goes out granular size and the particle shape of process control catalyst, adds the improvement of electron donor compound and urge in precipitation process Agent performance.The electron donor compound added not only had affected the particle shape of catalyst, but also had affected the hydrogen response of catalyst And copolymerization performance, therefore the selection of electron donor is a key of such catalyst development.Such as Chinese patent CN1958620A Employing tetraethoxysilane is electron donor, a class silicone compounds of CN2010102089331 employing band organo-functional group (POSS) it is electron donor, but the price of this silicone compounds is much more expensive, limit its application in the catalyst.
Summary of the invention
The present invention be directed to the deficiency of above-mentioned art methods, it is provided that giving of a kind of Ziegler-Natta catalyst is electric Daughter, comprise the catalytic component of this electron donor, comprise the catalyst of this catalytic component, and in vinyl polymerization, copolymerization Close the application in reaction.
The electron donor of a kind of Ziegler-Natta catalyst, for sial ester compounds, has a following structure:
In formula: R is selected from C1-C4 alkyl, C1-C4 alkoxyl.
Described sial ester compounds be two tert-butoxy triethoxy sial esters, diisopropoxy triethoxy sial ester, Diethoxy triethoxy sial ester, dimethoxy triethoxy sial ester, di-t-butyl triethoxy sial ester, diisopropyl Triethoxy sial ester, diethyl triethoxy sial ester, dimethyl triethoxy sial ester.
A kind of catalytic component comprising electron donor described in claim 1 or 2, this catalytic component includes
1. magnesium complex；2. titanium compound；3. sial ester compounds；
Component 1. described in magnesium complex be that magnesium halide is dissolved in the dicyandiamide solution containing organic alcohol compound institute The product obtained；Described organic alcohol compound be carbon number be straight chain, the alkylol of side chain, cyclic alkanol or the carbon of 1～10 Atomic number is the fragrant and mellow or aralkyl alcohol of 6～20, or the halides of above-mentioned Organic Alcohol；
Component 2. described in titanium compound formula be Ti (OR) aXb, in formula, R is aliphatic group or the aryl of C1～C10, X is halogen, and a is 0,1,2 or 3, and b is the integer of 1 to 4, a+b=3 or 4.
In terms of every mole of magnesium halide, organic alcohol compound content is: 0.1～10.0 mole, and sial ester compounds content is 0.05～1.0 mole, titanium compound content is 1.0～15.0 moles.
Sial ester compounds there was added two ways, specifically have two ways, be respectively as follows:
A kind of preparation method of described catalytic component, step is as follows:
(1) magnesium halide is dissolved in the dicyandiamide solution containing organic alcohol compound, adds inert diluent, solution temperature It is 50～125 DEG C, obtains component 1., 3., obtain reactant liquor to component 1. middle addition component；
(2), at-24 DEG C～10 DEG C, 2. reactant liquor and component is carried out haptoreaction, mixture is to slowly warm up to 80～ 125 DEG C, solids gradually separates out and is formed granule, after the reaction regular hour, removes unreacted reactant and solvent, and uses inertia Diluent washs, and obtains granulated solid titanium catalyst component.
A kind of preparation method of described catalytic component, step is as follows:
(1) magnesium halide is dissolved in the dicyandiamide solution containing organic alcohol compound, adds inert diluent, solution temperature It is 50～125 DEG C, obtains component 1.；
(2), at-24 DEG C～10 DEG C, 1. component is the most first carried out with component haptoreaction, adds component 3., by mixture Being to slowly warm up to 80～125 DEG C, solids gradually separates out and is formed granule, after the reaction regular hour, remove unreacted reactant and Solvent, and use inert diluent to wash, obtain granulated solid titanium catalyst component.
A kind of catalyst comprising described catalytic component, comprises:
(1) the catalytic component described in claim 3；
(2) formula is the organo-aluminum compound of AlRnX3-n, and in formula, R is hydrogen or alkyl that carbon number is l～20, and X is halogen Element, 0 < n≤3.
The mol ratio of component (2) middle aluminum and component (1) middle titanium is 10～1000.
The application in ethylene polymerization of a kind of described electron donor.
A kind of described catalytic component or catalyst application in ethylene polymerization.
The catalyst of the present invention is prepared by following steps: (1) makes halogenated magnesium compound be dissolved in organic alcohol compound Prepare homogeneous magnesium solution；(2) described homogeneous magnesium solution and at least one sial ester compounds is made to react generation magnesium compositions solution； (3) making described magnesium compositions solution and titanium compound react generation solid titanium catalyst, the reaction with titanium compound can be carried out Once, it is also possible to carry out repeatedly.Described magnesium compound can be halogenated magnesium compound.Halogenated magnesium compound for the present invention Type can include with Types Below: magnesium dihalide compound such as magnesium chloride, magnesium iodide, Afluon (Asta) and magnesium bromide；Alkyl magnesium halide Compound such as methylmagnesiumhalide, ethyl-magnesium-halide, halogenation propyl group magnesium, butyl Grignard reagent, halogenation isobutyl group magnesium, halogenation hexyl magnesium and Halogenation amyl group magnesium；Halogenated alkoxy magnesium compound such as halogenation magnesium methoxide, halogenation magnesium ethylate, halogenation isopropoxy magnesium, halogenation Butoxy magnesium and halogenation octyloxy magnesium；Halogen aryloxy magnesium such as benzene halide epoxide magnesium and halogenated methyl phenoxy group magnesium.These magnesium Compound can the form of mixtures with single compound or with two or more compound use.Additionally, above-mentioned magnesium compound can be effective Ground uses with the coordination compound form with other metal.Other magnesium compound includes by can be dependent on magnesium compound preparation method And exist but the compound that can not represent by molecular formula, may be generally viewed as the mixture of magnesium compound.Such as, may be used to lower chemical combination Thing is as magnesium compound: by magnesium compound and sial ester compounds, wraps halogen-containing silane compound, ester or alcohol and reacts The compound arrived；Reacted in the presence of halogenated silanes, phosphorus pentachloride or thionyl chloride with alcohol, phenol or ether by magnesium metal and obtain Compound.Described magnesium compound can be magnesium halide, especially magnesium chloride or have the kelene of alkyl of 1～10 carbon atom Base magnesium；There is the alkoxy magnesium chloride of the alkoxyl of 1～10 carbon atom；There is the chlorination virtue oxygen of the aryloxy group of 6～20 carbon atoms Base magnesium.Magnesium solution used can be made molten by making described magnesium compound be dissolved in alcohol in the case of presence or absence varsol Liquid and prepare.Type for the varsol of the present invention can be aliphatic hydrocarbon such as pentane, hexane, heptane, octane, decane and coal Oil；Clicyclic hydrocarbon such as ring benzene, methyl benzene, hexamethylene and hexahydrotoluene；Aromatic hydrocarbon such as benzene,toluene,xylene, ethylo benzene Deng；Halogenated hydrocarbons such as dichloropropane, dichloroethylene, trichloro ethylene, carbon tetrachloride and chlorobenzene etc..Being prepared magnesium solution by magnesium compound can Make solvent with alcohol to carry out in the case of adding or being not added with varsol.The type of alcohol can include that the alcohol containing 1～20 carbon atom is such as Methanol, ethanol, propanol, butanol, amylalcohol, hexanol, capryl alcohol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, Benzylalcohol, phenethanol, isopropylbenzyl alcohol and cumic alcohol, preferred alcohol is selected from the alcohol containing 1～12 carbon atom.Gained catalyst Particle mean size and particle size distribution can be depending on the type of alcohol used, the consumption of alcohol, the type of magnesium compound and magnesium compound and alcohol Ratio.During preparing magnesium solution, magnesium compound can be carried out with the reaction of alcohol in the presence of hydrocarbon solvent.Although reaction temperature Can change according to the type of alcohol used and consumption, but-25 DEG C, preferably from about-20 to 150 DEG C or more preferably from about-10 can be at least about To 110 DEG C.Response time can be about 15 minutes to 10 hours or preferably from about 30 minutes to 4 hours.
When described magnesium compositions solution reacts with titanium compound, the shapes and sizes of the solid titanium catalyst component of precipitation Depend primarily on the condition of reaction.In order to control shape of particle, it may be preferred to make described magnesium compound solution and titanium compound, silicon The mixture of aluminum ester compounds reacts generation solid substance composition at temperatures sufficiently low.Described sial ester compounds can With addition system before magnesium compound solution contacts with titanium compound, it is possible to add after magnesium compound solution contacts with titanium compound Enter system.Described reaction temperature can be about-70 to 70 DEG C, more preferably from about-50 to 50 DEG C.After described haptoreaction, make described Reaction temperature slowly raises with the abundant reaction of the most about 0.5～5 hour at about 50 to 150 DEG C.Can make to obtain as mentioned above Solid catalyst particle reacts with additional titanium compound again.Titanium compound used can be halogenated titanium or halogenated alkoxy titanium, Wherein alkoxy-functional has 1～20 carbon atom.The mixture of these compounds it is used as time suitably.These compounds In, halogenated titanium or wherein alkoxy-functional have the halogenated alkoxy titanium of 1～8 carbon atom to be applicable, preferred chemical combination Thing is titanium tetrahalide.The catalyst prepared by the method for the invention can be used for polymerization and the combined polymerization of ethylene.Especially, described Catalyst can be used for the homopolymerization of ethylene it can also be used to ethylene and alpha-olefin such as propylene, 1-butylene, the 1-having 3 or more carbon atoms Amylene, 4-methyl-1-pentene or the copolymerization of 1-hexene.Use the polyreaction useful catalyst system of catalyst of the present invention Carrying out, described catalyst system includes: (1) solid titanium complex catalysis including magnesium, titanium and Donor compound described herein Agent；(2) alkyl metal cpd or alumina metal compound.Described organo-metallic compound is the alkane having 1～6 carbon atom The trialkylaluminium of base, such as triethyl aluminum and triisobutyl aluminium or its mixture.Time suitably, it is possible to use have one or more halogen Or the organo-aluminum compound of hydrogen radical group, such as ethylaluminium dichloride, diethylaluminum chloride, ethylaluminum sesquichloride or hydrogenation two Aluminium isobutyl.Before polyreaction, solid titanium complex catalyst component described herein can be made pre-with ethylene or alpha-olefin Poly-.Described pre-polymerization can in the presence of varsol is such as hexane, at temperatures sufficiently low, under the pressure of ethylene or alpha-olefin and Carry out in the presence of above-mentioned catalytic component and organo-aluminum compound are such as triethyl aluminum.Organo-aluminum compound in polymerization reaction system It is 1～1000 with the mol ratio of titanium in solid titanium complex catalyst, preferably 20～200.For guaranteeing high polymerization rate, institute State polyreaction need to carry out at sufficiently high temperature, usually, be suitable for temperature be about 20 to 200 DEG C, more preferably from about 60 to 95℃.The monomer pressure being suitable in polymerization process is 0.1～10.0MPa, more preferably from about 0.2～5.0MPa.
Advantages of the present invention and good effect
1 it is a discovery of the invention that using sial ester compounds is the titanium system Ziegler-that electron donor joins magnesium chloride load In Natta catalyst so that arrive catalyst granules form rule, in granulated, particle diameter is distributed, polymerizate fine powder Less, bulk density high, the catalyst simultaneously obtained has preferable hydrogen response energy and copolymerization performance.
2, used by the present invention, sial ester compounds belongs to conventional chemicals, and production cost is relatively low, may be used on catalyst In industrially prepared.
Detailed description of the invention
Below by specific embodiment, the invention will be further described, and following example are illustrative, is not limit Qualitatively, it is impossible to limit protection scope of the present invention with this.
Embodiment 1
4.76 grams of (50mmol) anhydrous MgCl2, 75 milliliters of decane and 16.3 grams of (125mmol) isooctanol be heated to 125 DEG C, isothermal reaction obtains the solution of homogeneous phase transparent for 3 hours.The two tert-butoxy triethoxysilicanes of 15mmol are added in this solution Aluminum ester also stirs 2 hours so that two tert-butoxy triethoxy sial esters are dissolved in this solution at 50 DEG C.By obtained above Homogeneous phase solution is cooled to room temperature, was then added dropwise to temperature in 1 hour while stirring and remains the 150mL of-10 DEG C TiCl4In.Mixture temperature is made to keep at-10 DEG C 1 hour, the most under agitation according to certain heating rate after dripping off Temperature is carried to 120 DEG C, and this temperature is kept 2 hours.After reaction terminates when 2 is little, the solid generated is carried out heat filtering Separate.With decane and hexane, solid catalyst is fully washed respectively, until inspection does not measures the titanium of precipitation in cleanout fluid, Obtain a kind of solid titanium catalyst component after drying.
Vinyl polymerization
The rustless steel polymerization reaction kettle of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1.0L and concentration is 1.0M's Triethyl aluminum 1.0mL, adds the catalyst of the above-mentioned preparation of precise, is warming up to 75 DEG C with syringe, is passed through in hydrogen makes still Pressure reaches 0.28MPa, then is passed through stagnation pressure in ethylene makes still and reaches 0.73MPa (gauge pressure), is polymerized 2 hours under the conditions of 80 DEG C, Polymerization result is shown in Table 1.
Embodiment 2
4.76 grams of (50mmol) anhydrous MgCl2, 75 milliliters of decane and 16.3 grams of (125mmol) isooctanol be heated to 125 DEG C, isothermal reaction 3 hours, obtain a kind of homogeneous phase solution.The diisopropoxy triethoxy sial of 15mmol is added in this solution Ester also stirs 2 hours so that diisopropoxy triethoxy sial ester is dissolved in this solution at 50 DEG C.By institute obtained above There is homogeneous phase solution to be cooled to room temperature, in 1 hour, be then added dropwise to temperature while stirring remain the 200mL of-15 DEG C TiCl4In.Make mixture temperature keep 1 hour at-15 DEG C after dripping off, the most under agitation in 4 hours temperature carry to 120 DEG C, and this temperature is kept 2 hours.After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.Use respectively Solid catalyst is fully washed by decane and hexane, until inspection does not measures the titanium compound of precipitation in cleanout fluid, through dry A kind of solid titanium catalyst component is obtained after dry.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1L and three second of concentration 1M Base aluminum 1.0mL, adds the catalyst of the above-mentioned preparation of precise, is warming up to 75 DEG C, is passed through hydrogen and makes pressure in still with syringe Reach 0.28MPa, then be passed through stagnation pressure in ethylene makes still and reach 0.73MPa (gauge pressure), be polymerized 2 hours under the conditions of 80 DEG C, polymerization The results are shown in Table 1.
Embodiment 3
4.76 grams of (50mmol) anhydrous magnesium chlorides, 75 milliliters of decane and 16.3 grams of (125mmol) isooctanol are heated to 125 DEG C, isothermal reaction 3 hours, obtain a kind of homogeneous phase solution.The diethoxy triethoxy sial ester of 15mmol is added in this solution And at 50 DEG C, stir 2 hours so that diethoxy triethoxy sial ester is dissolved in this solution.By obtained above all Phase solution is cooled to room temperature, was then added dropwise to temperature in 1 hour while stirring and remains the 150mL TiCl of 0 DEG C4In. Make mixture temperature keep at 0 DEG C after dripping off 1 hour, the most under agitation in 2 hours, temperature is carried to 120 DEG C, and will This temperature keeps 2 hours.After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.Respectively with decane and hexane Solid catalyst is fully washed, until inspection does not measures the titanium compound of precipitation in cleanout fluid, obtains one after drying Plant solid titanium catalyst component.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1L and three second of concentration 1M Base aluminum 1.0mL, adds the catalyst of the above-mentioned preparation of precise, is warming up to 75 DEG C, is passed through hydrogen and makes pressure in still with syringe Reach 0.28MPa, then be passed through stagnation pressure in ethylene makes still and reach 0.73MPa (gauge pressure), be polymerized 2 hours under the conditions of 80 DEG C, polymerization The results are shown in Table 1.
Embodiment 4
4.76 grams of (50mmol) anhydrous magnesium chlorides, 75 milliliters of decane and 16.3 grams of (125mmol) isooctanol are heated to 125 DEG C, isothermal reaction 3 hours, obtain a kind of homogeneous phase solution.The dimethoxy triethoxy sial of 15mmol is added in this solution Ester also stirs 2 hours so that dimethoxy triethoxy sial ester is dissolved in this solution at 50 DEG C.By obtained above all Homogeneous phase solution is cooled to room temperature, was then added dropwise to temperature in 1 hour while stirring and remains the 150mL TiCl of 0 DEG C4 In.Make mixture temperature keep at 0 DEG C after dripping off 1 hour, the most under agitation in 2 hours, temperature is carried to 120 DEG C, and This temperature is kept 2 hours.After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.Respectively with decane with own Solid catalyst is fully washed by alkane, until inspection does not measures the titanium compound of precipitation in cleanout fluid, obtains after drying A kind of solid titanium catalyst component.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1L and concentration is the three of 1M Aluminium ethide 1.0mL, adds the catalyst of the above-mentioned preparation of precise, is warming up to 75 DEG C, is passed through hydrogen and makes still intrinsic pressure with syringe Power reaches 0.28MPa, then is passed through stagnation pressure in ethylene makes still and reaches 0.73MPa (gauge pressure), is polymerized 2 hours under the conditions of 80 DEG C, poly- Conjunction the results are shown in Table 1.
Embodiment 5
4.76 grams of (50mmol) anhydrous magnesium chlorides, 75 milliliters of decane and 16.3 grams of (125mmol) isooctanol are heated to 125 DEG C, isothermal reaction 3 hours, obtain a kind of homogeneous phase solution.The di-t-butyl triethoxy sial of 15mmol is added in this solution Ester also stirs 2 hours so that di-t-butyl triethoxy sial ester is dissolved in this solution at 50 DEG C.By obtained above all Homogeneous phase solution is cooled to room temperature, was then added dropwise to temperature in 1 hour while stirring and remains the 150mL of-10 DEG C TiCl4In.Make mixture temperature keep 1 hour at-10 DEG C after dripping off, the most under agitation in 2 hours temperature carry to 120 DEG C, and this temperature is kept 2 hours.After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.Use respectively Solid catalyst is fully washed by decane and hexane, until inspection does not measures the titanium compound of precipitation in cleanout fluid, through dry A kind of solid titanium catalyst component is obtained after dry.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1L and concentration is the three of 1M Aluminium ethide 1.0mL, adds the catalyst of the above-mentioned preparation of precise, is warming up to 75 DEG C, is passed through hydrogen and makes still intrinsic pressure with syringe Power reaches 0.28MPa, then is passed through stagnation pressure in ethylene makes still and reaches 0.73MPa (gauge pressure), is polymerized 2 hours under the conditions of 80 DEG C, poly- Conjunction the results are shown in Table 1.
Embodiment 6
4.76 grams of (50mmol) anhydrous magnesium chlorides, 75 milliliters of decane and 16.3 grams of (125mmol) isooctanol are heated to 125 DEG C, isothermal reaction 3 hours, obtain a kind of homogeneous phase solution.The diisopropyl triethoxy sial of 15mmol is added in this solution Ester also stirs 2 hours so that diisopropyl triethoxy sial ester is dissolved in this solution at 50 DEG C.By obtained above all Homogeneous phase solution is cooled to room temperature, was then added dropwise to temperature in 1 hour while stirring and remains the 150mL of-10 DEG C TiCl4In.Make mixture temperature keep 1 hour at-10 DEG C after dripping off, the most under agitation in 2 hours temperature carry to 120 DEG C, and this temperature is kept 2 hours.After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.Use respectively Solid catalyst is fully washed by decane and hexane, until inspection does not measures the titanium compound of precipitation in cleanout fluid, through dry A kind of solid titanium catalyst component is obtained after dry.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1L and concentration is the three of 1M Aluminium ethide 1.0mL, adds the catalyst of the above-mentioned preparation of precise, is warming up to 75 DEG C, is passed through hydrogen and makes still intrinsic pressure with syringe Power reaches 0.28MPa, then is passed through stagnation pressure in ethylene makes still and reaches 0.73MPa (gauge pressure), is polymerized 2 hours under the conditions of 80 DEG C, poly- Conjunction the results are shown in Table 1.
Embodiment 7
4.76 grams of (50mmol) anhydrous magnesium chlorides, 75 milliliters of decane and 16.3 grams of (125mmol) isooctanol are heated to 125 DEG C, isothermal reaction 3 hours, obtain a kind of homogeneous phase solution.The diethyl triethoxy sial ester of 15mmol is added in this solution And at 50 DEG C, stir 2 hours so that diethyl triethoxy sial ester is dissolved in this solution.By obtained above all homogeneously Solution is cooled to room temperature, was then added dropwise to temperature in 1 hour while stirring and remains the 150mL TiCl of-10 DEG C4In. Make mixture temperature keep at-10 DEG C after dripping off 1 hour, the most under agitation in 2 hours, temperature is carried to 120 DEG C, and This temperature is kept 2 hours.After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.Respectively with decane with own Solid catalyst is fully washed by alkane, until inspection does not measures the titanium compound of precipitation in cleanout fluid, obtains after drying A kind of solid titanium catalyst component.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1L and concentration is the three of 1M Aluminium ethide 1.0mL, adds the catalyst of the above-mentioned preparation of precise, is warming up to 75 DEG C, is passed through hydrogen and makes still intrinsic pressure with syringe Power reaches 0.28MPa, then is passed through stagnation pressure in ethylene makes still and reaches 0.73MPa (gauge pressure), is polymerized 2 hours under the conditions of 80 DEG C, poly- Conjunction the results are shown in Table 1.
Embodiment 8
4.76 grams of (50mmol) anhydrous magnesium chlorides, 75 milliliters of decane and 16.3 grams of (125mmol) isooctanol are heated to 125 DEG C, isothermal reaction 3 hours, obtain a kind of homogeneous phase solution.The dimethyl triethoxy sial of 15 mMs is added in this solution Ester also stirs 2 hours so that dimethyl triethoxy sial ester is dissolved in this solution at 50 DEG C.By obtained above all Phase solution is cooled to room temperature, was then added dropwise to temperature in 1 hour while stirring and remains the 150mL TiCl of-10 DEG C4 In.Make mixture temperature keep at-10 DEG C after dripping off 1 hour, the most under agitation in 2 hours, temperature carried to 120 DEG C, And this temperature is kept 2 hours.After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.Respectively with decane and Solid catalyst is fully washed by hexane, until inspection does not measures the titanium compound of precipitation in cleanout fluid, obtains after drying To a kind of solid titanium catalyst component.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1L, the triethyl group of concentration 1M Aluminum 1.0mL, adds the catalyst of the above-mentioned preparation of precise, is warming up to 75 DEG C, is passed through pressure in hydrogen makes still and reaches with syringe To 0.28MPa, then it is passed through stagnation pressure in ethylene makes still and reaches 0.73MPa (gauge pressure), be polymerized 2 hours under the conditions of 80 DEG C, polymerization knot Fruit is shown in Table 1.
Comparative example 1
4.76 grams of (50mmol) anhydrous magnesium chlorides, 75 milliliters of decane and 16.3 grams of (125mmol) isooctanol are heated to 125 DEG C, isothermal reaction 3 hours, obtain a kind of homogeneous phase solution.The tetraethoxysilane of 15mmol is added and at 50 DEG C in this solution Lower stirring 2 hours is so that tetraethoxysilane is dissolved in this solution.All homogeneous phase solutions obtained above are cooled to-10 DEG C, Then in 1 hour, will stay in that the 150mL TiCl of-10 DEG C while stirring4It is added drop-wise in above-mentioned homogeneous phase solution.Make after dripping off Mixture temperature keeps 1 hour at 0 DEG C, the most under agitation in 2 hours, temperature is carried to 120 DEG C, and this temperature is protected Hold 2 hours.After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.With decane and hexane, solid is urged respectively Agent is fully washed, until inspection does not measures the titanium compound of precipitation in cleanout fluid, obtains a kind of solid titanium after drying Catalytic component.
Vinyl polymerization is with embodiment 1, and polymerization result is shown in Table 1.
Table 1 polymerization experiment result
Above-described is only the preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art For, on the premise of without departing from inventive concept, it is also possible to make some deformation and improvement, these broadly fall into the protection of the present invention Scope.

Claims (10)

1. an electron donor for Ziegler-Natta catalyst, for sial ester compounds, has a following structure:
In formula: R is selected from C1-C4 alkyl, C1-C4 alkoxyl.
Electron donor the most according to claim 1, it is characterised in that: described sial ester compounds is two tert-butoxy three second Epoxide sial ester, diisopropoxy triethoxy sial ester, diethoxy triethoxy sial ester, dimethoxy triethoxysilicane Aluminum ester, di-t-butyl triethoxy sial ester, diisopropyl triethoxy sial ester, diethyl triethoxy sial ester, diformazan Ethyl triethoxy silicane aluminum ester.
3. the catalytic component comprising electron donor described in claim 1 or 2, it is characterised in that: this catalytic component bag Include 1. magnesium complex；2. titanium compound；3. sial ester compounds；
Component 1. described in magnesium complex be magnesium halide is dissolved in the dicyandiamide solution containing organic alcohol compound obtained by Product；Described organic alcohol compound be carbon number be straight chain, the alkylol of side chain, cyclic alkanol or the carbon atom of 1～10 Number is the fragrant and mellow or aralkyl alcohol of 6～20, or the halides of above-mentioned Organic Alcohol；
Component 2. described in titanium compound formula be Ti (OR)aXb, in formula, R is C1～C10Aliphatic group or aryl, X is halogen Element, a is 0,1,2 or 3, and b is the integer of 1 to 4, a+b=3 or 4.
Catalytic component the most according to claim 3, it is characterised in that: in terms of every mole of magnesium halide, organic alcohol compound Content is: 0.1～10.0 mole, and sial ester compounds content is 0.05～1.0 mole, and titanium compound content is 1.0～15.0 Mole.
5. a preparation method for the catalytic component described in claim 3, step is as follows:
(1) being dissolved in the dicyandiamide solution containing organic alcohol compound by magnesium halide, add inert diluent, solution temperature is 50 ～125 DEG C, obtain component 1., 3., obtain reactant liquor to component 1. middle addition component；
(2), at-24 DEG C～10 DEG C, 2. reactant liquor and component are carried out haptoreaction, mixture are to slowly warm up to 80～125 DEG C, Solids gradually separates out and is formed granule, after the reaction regular hour, removes unreacted reactant and solvent, and uses inert diluent Washing, obtains granulated solid titanium catalyst component.
6. a preparation method for the catalytic component described in claim 3, step is as follows:
(1) being dissolved in the dicyandiamide solution containing organic alcohol compound by magnesium halide, add inert diluent, solution temperature is 50 ～125 DEG C, obtain component 1.；
(2), at-24 DEG C～10 DEG C, 1. component is the most first carried out with component haptoreaction, adds component 3., mixture is slow Being warming up to 80～125 DEG C, solids gradually separates out and is formed granule, after the reaction regular hour, removes unreacted reactant and solvent, And use inert diluent to wash, obtain granulated solid titanium catalyst component.
7. the catalyst comprising catalytic component described in claim 3, it is characterised in that: comprise:
(1) the catalytic component described in claim 3；
(2) formula is AlRnX3-nOrgano-aluminum compound, in formula, R is hydrogen or alkyl that carbon number is l～20, and X is halogen, 0 < n ≤3。
Catalyst the most according to claim 7, it is characterised in that: the mol ratio of component (2) middle aluminum and component (1) middle titanium is 10 ～1000.
9. the application in vinyl polymerization, copolymerization of the electron donor described in a claim 1 or 2.
10. the catalytic component described in a claim 3 or the catalyst described in claim 7 are in vinyl polymerization, combined polymerization Application in reaction.
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