CN105859927A - Ethylene polymerization Ziegler-Natta catalyst electron donor, catalyst component, and catalyst - Google Patents
Ethylene polymerization Ziegler-Natta catalyst electron donor, catalyst component, and catalyst Download PDFInfo
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- CN105859927A CN105859927A CN201610475374.8A CN201610475374A CN105859927A CN 105859927 A CN105859927 A CN 105859927A CN 201610475374 A CN201610475374 A CN 201610475374A CN 105859927 A CN105859927 A CN 105859927A
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- 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
The invention relates to Ziegler-Natta catalyst electron donor, comprising a catalyst component of the electron donor and a catalyst of the electron donor. The electron donor is acetoxylsilane compound, the catalyst prepared with the acetoxylsilane compound as an electron donor shows high catalytic activity, good hydrogen modulation sensitivity and good copolymerizing performance when used in ethylene polymerization and copolymerization and can be used in homopolymerization of catalytic ethylene or copolymerization of ethylene with other Alpha-olefins to produce high-performance polyolefin material with high bulk density, narrow particle size distribution and low fine particle content.
Description
Technical field
The invention belongs to vinyl polymerization catalytic field, relate to Ziegler-Natta catalyst, especially a kind of vinyl polymerization
Ziegler-Natta catalyst electron donor, catalytic component, catalyst.
Technical background
In recent years, the emphasis in the exploitation of high-end trade mark polyolefin PP Pipe Compound always this field, the research and development of corresponding catalyst
Also it is the difficult point in polyolefin research field.It is polyolefinic mainly that Ziegler-Natta Titanium series catalyst remains industrial production at present
Catalyst, develops high catalytic activity, hydrogen response is good, copolymerization performance is good, obtain polymer particle size is evenly distributed, fine powder
Less, oligomer wax content is low, produce the most controlled polyolefin catalyst is the target that scientific research personnel pursues.Have a lot of document and
Patent report is many prepares the titanio Ziegler-Natta catalyst of magnesium chloride load as olefinic polymerization and copolymerization catalyst
Method.Difference according to polymerization technique, it is desirable to the performance of corresponding catalyst is also had nothing in common with each other, therefore corresponding catalyst
Production method is also slightly different.Such as the Ziegler-Natta catalyst for ethylene gas-phase fluidized bed polymerization process, it is desirable to catalyst particles
Form is good, fine powder is few for grain, and the polyethylene fine powder so produced when ethylene gas fluidised bed polymerisation is few, can avoid because of electrostatic
And the reactor sheeting caused.Catalyst for ethene gas-phase polymerization is usually and active component is directly carried on the lazy of big surface
Property carrier such as silica gel etc. on, owing to the particle diameter of silica gel is easily controlled, and particle shape is preferable, therefore can get granule equal
Even catalyst particle.But owing on carrier, the load capacity of active component is restricted, 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, with MgCl2、SiO2For carrier, TiCl4For
Active component, the preparation method of catalyst is as follows: by MgCl2With TiCl in THF4Reaction formed catalyst mother solution, then with warp
Carrier S iO that alkyl aluminum processed2Mixing, prepares catalyst precursor component after removing part oxolane.For vinyl polymerization
Time, 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 second
The gas-phase fluidized bed polymerization process of alkene, but owing to relatively low catalysis activity is difficult to 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, with
Shi Yaoqiu polymerizate fine powder is few, wax content is few, so can ensure that the continuous long-term operation of process units.Urge for this
The preparation method of agent is to dissolve magnesium compounds such as magnesium chlorides to obtain homogeneous solution in a solvent, the most again by this solution and titanizing
Compound and electron donor mixing, obtain the solids containing magnesium, titanium and electron donor by the method for precipitation, and used by this solids
The liquid titanium compound of 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 crystallization of magnesium chloride
Precipitation process controls granular size and the particle shape of catalyst, adds electron donor compound and improve catalyst in precipitation process
Performance.The electron donor compound added not only had affected the particle shape of catalyst, but also had affected hydrogen response and the copolymerization of catalyst
Performance, therefore the selection of electron donor is a key of such catalyst development.As Chinese patent CN1958620A uses tetrem
TMOS be electron donor, CN2010102089331 use band organo-functional group a class silicone compounds (POSS) for giving
Electron, but the price of this silicone compounds is much more expensive, limits 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 the electron donor of a kind of Ziegler-Natta catalyst, comprise
The catalytic component of this electron donor, comprises the catalyst of this catalytic component, and in vinyl polymerization, copolymerization
Application.
The electron donor of a kind of Ziegler-Natta catalyst, for acetoxylsilane compound, has a following structure:
In formula: R1, R2, R3 are selected from identical or different C1-C4 alkyl, C2-C4 acyl group.
Described acetoxylsilane compound is acetoxyl group trimethoxy silane, acetoxyl group triethoxysilane, acetyl oxygen
Base tripropoxy silane, acetoxyl group three butoxy silane, diacetoxy dimethoxysilane, diacetoxy diethoxy
Silane, diacetoxy dipropoxy silane, diacetoxy dibutoxy silane, triacetoxyl group methoxy silane, three second
Oyloxyethoxy silane.
A kind of catalytic component comprising described electron donor, this catalytic component includes
1. magnesium complex；2. titanium compound；3. acetoxylsilane compound；
Component 1. described in magnesium complex be magnesium halide is dissolved in the dicyandiamide solution containing organic alcohol compound obtained by product
Thing；Described organic alcohol compound be carbon number be straight chain, the alkylol of side chain, cyclic alkanol or the carbon number of 1～10 be 6～20
Fragrant and mellow or aralkyl alcohol, 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, and 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.
In terms of every mole of magnesium halide, organic alcohol compound content is: 0.1～10.0 mole, and acetoxylsilane compounds content is
0.05～1.0 mole, titanium compound content is 1.0～15.0 moles.
Acetoxylsilane compound 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) 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 is to slowly warm up to 80～125 DEG C, Gu
Body thing gradually separates out and is formed granule, after the reaction regular hour, removes unreacted reactant and solvent, and uses inert diluent to wash
Wash, obtain granulated solid titanium catalyst component.
A kind of preparation method of described catalytic component, 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 slowly risen
Temperature is to 80～125 DEG C, and solids gradually separates out and formed granule, after the reaction regular hour, removes unreacted reactant and solvent, and
Employing inert diluent washs, and obtains 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, 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: it is homogeneous that (1) makes halogenated magnesium compound be dissolved in organic alcohol compound preparation
Magnesium solution；(2) described homogeneous magnesium solution and at least one acetoxylsilane compound 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,
Can also carry out repeatedly.Described magnesium compound can be halogenated magnesium compound.Type for the halogenated magnesium compound of the present invention can
Including with Types Below: magnesium dihalide compound such as magnesium chloride, magnesium iodide, Afluon (Asta) and magnesium bromide；Halogenated alkyl magnesium compound
Such as methylmagnesiumhalide, ethyl-magnesium-halide, halogenation propyl group magnesium, butyl Grignard reagent, halogenation isobutyl group magnesium, halogenation hexyl magnesium and halogen
Change amyl group magnesium；Halogenated alkoxy magnesium compound such as halogenation magnesium methoxide, halogenation magnesium ethylate, halogenation isopropoxy magnesium, halogenation fourth
Epoxide magnesium and halogenation octyloxy magnesium；Halogen aryloxy magnesium such as benzene halide epoxide magnesium and halogenated methyl phenoxy group magnesium.These magnesium compounds
Can the form of mixtures with single compound or with two or more compound use.Additionally, above-mentioned magnesium compound can effectively with
The coordination compound form of other metal uses.Other magnesium compound include being existed by can be dependent on magnesium compound preparation method 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 compound as magnesium
Compound: by magnesium compound and acetoxylsilane compound, wrap halogen-containing silane compound, ester or alcohol and react and obtain
Compound；Reacted in the presence of halogenated silanes, phosphorus pentachloride or thionyl chloride by magnesium metal and alcohol, phenol or ether and to obtain
Compound.Described magnesium compound can be magnesium halide, especially magnesium chloride or have the alkyl magnesium chloride of alkyl of 1～10 carbon atom；
There is the alkoxy magnesium chloride of the alkoxyl of 1～10 carbon atom；There is the chlorination aryloxy group magnesium of the aryloxy group of 6～20 carbon atoms.Institute
Solution can be made and prepare by making described magnesium compound be dissolved in alcohol in the case of presence or absence varsol with magnesium solution.
Type for the varsol of the present invention can be aliphatic hydrocarbon such as pentane, hexane, heptane, octane, decane and kerosene；Alicyclic ring
Race's hydrocarbon such as ring benzene, methyl benzene, hexamethylene and hexahydrotoluene；Aromatic hydrocarbon such as benzene,toluene,xylene, ethylo benzene etc.；
Halogenated hydrocarbons such as dichloropropane, dichloroethylene, trichloro ethylene, carbon tetrachloride and chlorobenzene etc..Prepared magnesium solution by magnesium compound can use
Alcohol makees solvent to be carried out in the case of adding or being not added with varsol.The type of alcohol can include the such as methanol of the alcohol containing 1～20 carbon atom,
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 it
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
Type according to alcohol used and consumption change, but can be at least about-25 DEG C, preferably from about-20 to 150 DEG C or more preferably from about-10 to
110℃.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 mainly take
Certainly in the condition of reaction.In order to control shape of particle, it may be preferred to make described magnesium compound solution and titanium compound, acetoxyl group
The mixture of silane compound reacts generation solid substance composition at temperatures sufficiently low.Described acetoxylsilane chemical combination
Thing can before magnesium compound solution contacts with titanium compound addition system, it is possible to after magnesium compound solution contacts with titanium compound
Addition 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 institute
State reaction temperature and slowly raise the abundant reaction with 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, its
Middle alkoxy-functional has 1～20 carbon atom.The mixture of these compounds it is used as time suitably.In these compounds, halogen
Change titanium or wherein alkoxy-functional have the halogenated alkoxy titanium of 1～8 carbon atom to be applicable, and preferred compound is four halogenations
Titanium.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
In ethylene homopolymerization it can also be used to ethylene with have the alpha-olefin such as propylene, 1-butylene of 3 or more carbon atoms, 1-amylene, 4-methyl
-1-amylene or the copolymerization of 1-hexene.The polyreaction useful catalyst system using catalyst of the present invention is carried out, described catalysis
Agent system includes: (1) solid titanium complex catalyst including magnesium, titanium and Donor compound described herein；(2) metal alkyl
Compound or alumina metal compound.Described organo-metallic compound is the trialkylaluminium of the alkyl having 1～6 carbon atom, such as three second
Base aluminum and triisobutyl aluminium or its mixture.Time suitably, it is possible to use have organic calorize of one or more halogen or hydrogen radical group
Compound, such as ethylaluminium dichloride, diethylaluminum chloride, ethylaluminum sesquichloride or diisobutylaluminium hydride.Anti-for being polymerized
Before should, solid titanium complex catalyst component described herein and ethylene or alpha-olefin pre-polymerization can be made.Described pre-polymerization can be molten at hydro carbons
In the presence of agent such as hexane, at temperatures sufficiently low, under the pressure of ethylene or alpha-olefin and at above-mentioned catalytic component and organic
Carry out in the presence of aluminium compound such as triethyl aluminum.Organo-aluminum compound and titanium in solid titanium complex catalyst in polymerization reaction system
Mol ratio be 1～1000, preferably 20～200.For guaranteeing high polymerization rate, described polyreaction need to be in sufficiently high temperature
Under carry out, usually, be suitable for temperature be about 20 to 200 DEG C, more preferably from about 60 to 95 DEG C.The monomer pressure being suitable in polymerization process
Power 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 acetoxylsilane compound is the titanium system that electron donor joins magnesium chloride load
In Ziegler-Natta catalyst so that arrive catalyst granules form rule, in granulated, particle diameter is distributed, polymerization is produced
Thing fine powder is few, bulk density is high, and the catalyst simultaneously obtained has preferable hydrogen response energy and copolymerization performance.
2, used by the present invention, acetoxylsilane compound 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 determinate,
Protection scope of the present invention can not be limited 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, permanent
Temperature reaction obtains the solution of homogeneous phase transparent for 3 hours.Add in this solution 15mmol acetoxyl group trimethoxy silane and
2 hours are stirred so that acetoxyl group trimethoxy silane is dissolved in this solution at 50 DEG C.Homogeneous phase solution obtained above 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.Mixture is made after dripping off
Temperature keeps 1 hour at-10 DEG C, the most under agitation according to certain heating rate, temperature is being carried to 120 DEG C, and by this temperature
Degree keeps 2 hours.After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.Use decane and hexane to solid respectively
Body catalyst fully washs, until inspection does not measures the titanium of precipitation in cleanout fluid, obtains a kind of solid titanium catalyst after drying
Agent component.
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 the triethyl group of 1.0M
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
0.28MPa, then be passed through stagnation pressure in ethylene makes still and reach 0.73MPa (gauge pressure), it is polymerized 2 hours under the conditions of 80 DEG C, polymerization result
It 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, permanent
Temperature reaction 3 hours, obtains a kind of homogeneous phase solution.The acetoxyl group triethoxysilane of 15mmol is added and at 50 DEG C in this solution
Lower stirring 2 hours is so that acetoxyl group triethoxysilane is dissolved in this solution.All homogeneous phase solutions obtained above are cooled to room
Temperature, was then added dropwise to temperature in 1 hour while stirring and remains the 200mL TiCl of-15 DEG C4In.Mixture is made after dripping off
Temperature keeps 1 hour at-15 DEG C, the most under agitation in 4 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.With decane and hexane, solid catalyst is filled respectively
Divide washing, until inspection does not measures the titanium compound of precipitation in cleanout fluid, obtain a kind of solid titanium catalyst component after drying.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1L and the triethyl aluminum of concentration 1M
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
0.28MPa, then be passed through stagnation pressure in ethylene makes still and reach 0.73MPa (gauge pressure), it is polymerized 2 hours under the conditions of 80 DEG C, polymerization result
It is 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, obtains a kind of homogeneous phase solution.The acetoxyl group tripropoxy silane of 15mmol is added and at 50 DEG C in this solution
Lower stirring 2 hours is so that acetoxyl group tripropoxy silane is dissolved in this solution.All homogeneous phase solutions obtained above are cooled to room
Temperature, was then added dropwise to temperature in 1 hour while stirring and remains the 150mL TiCl of 0 DEG C4In.Mixture temperature is made after dripping off
Degree 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 kept 2 hours.When
After reaction in 2 hours terminates, the solid generated is carried out heat filtering separation.With decane and hexane, solid catalyst is carried out fully respectively
Washing, until inspection does not measures the titanium compound of precipitation in cleanout fluid, obtains a kind of solid titanium catalyst component after drying.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1L and the triethyl aluminum of concentration 1M
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
0.28MPa, then be passed through stagnation pressure in ethylene makes still and reach 0.73MPa (gauge pressure), it is polymerized 2 hours under the conditions of 80 DEG C, polymerization result
It is 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, obtains a kind of homogeneous phase solution.Add in this solution 15mmol acetoxyl group three butoxy silane and
2 hours are stirred so that acetoxyl group three butoxy silane is dissolved in this solution at 50 DEG C.All homogeneous phase solutions obtained above are cooled down
To room temperature, in 1 hour, then it is added dropwise to temperature while stirring remains the 150mL TiCl of 0 DEG C4In.Mixing is made after dripping off
Thing 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 kept 2 hours.
After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.With decane and hexane, solid catalyst is filled respectively
Divide washing, until inspection does not measures the titanium compound of precipitation in cleanout fluid, obtain a kind of solid titanium catalyst component after drying.
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 triethyl group of 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
0.28MPa, then be passed through stagnation pressure in ethylene makes still and reach 0.73MPa (gauge pressure), it is polymerized 2 hours under the conditions of 80 DEG C, polymerization result
It is 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, obtains a kind of homogeneous phase solution.The diacetoxy dimethoxysilane of 15mmol is added also in this solution
2 hours are stirred so that diacetoxy dimethoxysilane is dissolved in this solution at 50 DEG C.By all homogeneous phase solutions obtained above
It is cooled to room temperature, in 1 hour, is then added dropwise to temperature while stirring remains the 150mL TiCl of-10 DEG C4In.After dripping off
Make mixture temperature keep at-10 DEG C 1 hour, the most under agitation in 2 hours, temperature is carried to 120 DEG C, and by this temperature
Keep 2 hours.After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.Use decane and hexane to solid respectively
Catalyst fully washs, 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
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1L and concentration is the triethyl group of 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
0.28MPa, then be passed through stagnation pressure in ethylene makes still and reach 0.73MPa (gauge pressure), it is polymerized 2 hours under the conditions of 80 DEG C, polymerization result
It is 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, obtains a kind of homogeneous phase solution.The diacetoxy diethoxy silane of 15mmol is added also in this solution
2 hours are stirred so that diacetoxy diethoxy silane is dissolved in this solution at 50 DEG C.By all homogeneous phase solutions obtained above
It is cooled to room temperature, in 1 hour, is then added dropwise to temperature while stirring remains the 150mL TiCl of-10 DEG C4In.After dripping off
Make mixture temperature keep at-10 DEG C 1 hour, the most under agitation in 2 hours, temperature is carried to 120 DEG C, and by this temperature
Keep 2 hours.After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.Use decane and hexane to solid respectively
Catalyst fully washs, 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
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1L and concentration is the triethyl group of 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
0.28MPa, then be passed through stagnation pressure in ethylene makes still and reach 0.73MPa (gauge pressure), it is polymerized 2 hours under the conditions of 80 DEG C, polymerization result
It is 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, obtains a kind of homogeneous phase solution.The diacetoxy dipropoxy silane of 15mmol is added also in this solution
2 hours are stirred so that diacetoxy dipropoxy silane is dissolved in this solution at 50 DEG C.By all homogeneous phase solutions obtained above
It is cooled to room temperature, in 1 hour, is then added dropwise to temperature while stirring remains the 150mL TiCl of-10 DEG C4In.After dripping off
Make mixture temperature keep at-10 DEG C 1 hour, the most under agitation in 2 hours, temperature is carried to 120 DEG C, and by this temperature
Keep 2 hours.After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.Use decane and hexane to solid respectively
Catalyst fully washs, 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
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1L and concentration is the triethyl group of 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
0.28MPa, then be passed through stagnation pressure in ethylene makes still and reach 0.73MPa (gauge pressure), it is polymerized 2 hours under the conditions of 80 DEG C, polymerization result
It is 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, obtains a kind of homogeneous phase solution.The diacetoxy dibutoxy silane of 15 mMs is added also in this solution
2 hours are stirred so that diacetoxy dibutoxy silane is dissolved in this solution at 50 DEG C.By all homogeneous phase solutions obtained above
It is cooled to room temperature, in 1 hour, is then added dropwise to temperature while stirring remains the 150mL TiCl of-10 DEG C4In.After dripping off
Make mixture temperature keep at-10 DEG C 1 hour, the most under agitation in 2 hours, temperature is carried to 120 DEG C, and by this temperature
Keep 2 hours.After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.Use decane and hexane to solid respectively
Catalyst fully washs, 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
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1L, the triethyl aluminum of concentration 1M
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
0.28MPa, then be passed through stagnation pressure in ethylene makes still and reach 0.73MPa (gauge pressure), it is polymerized 2 hours under the conditions of 80 DEG C, polymerization result
It is shown in Table 1.
Embodiment 9
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, obtains a kind of homogeneous phase solution.In this solution add 15 mMs triacetoxyl group methoxy silane and
2 hours are stirred so that triacetoxyl group methoxy silane is dissolved in this solution at 50 DEG C.All homogeneous phase solutions obtained above are cooled down
To room temperature, in 1 hour, then it is added dropwise to temperature while stirring remains the 150mL TiCl of-10 DEG C4In.Make after dripping off to mix
Compound temperature keeps 1 hour at-10 DEG C, the most under agitation in 2 hours, temperature is carried to 120 DEG C, and this temperature is kept 2
Hour.After reaction terminates when 2 is little, the solid generated is carried out heat filtering separation.Use decane and hexane to solid catalyst respectively
Fully wash, until inspection does not measures the titanium compound of precipitation in cleanout fluid, obtain a kind of solid titanium catalyst after drying
Component.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, adds hexane 1L, the triethyl aluminum of concentration 1M
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
0.28MPa, then be passed through stagnation pressure in ethylene makes still and reach 0.73MPa (gauge pressure), it is polymerized 2 hours under the conditions of 80 DEG C, polymerization result
It is shown in Table 1.
Embodiment 10
The preparation of catalyst is with embodiment 1, and difference is that the acetoxylsilane compound added is triacetoxyl group ethyoxyl
Silane.Vinyl polymerization is with embodiment 1, and polymerization result 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, obtains a kind of homogeneous phase solution.In this solution, add the tetraethoxysilane of 15mmol and stir at 50 DEG C
Mix 2 hours so that tetraethoxysilane is dissolved in this solution.All homogeneous phase solutions obtained above are cooled to-10 DEG C, then 1
The 150mL TiCl of-10 DEG C is will stay in that while stirring in hour4It is added drop-wise in above-mentioned homogeneous phase solution.Mixture temperature is made to exist after dripping off
Keep 1 hour at 0 DEG C, the most under agitation in 2 hours, temperature is carried to 120 DEG C, and this temperature is kept 2 hours.When 2 is little
After Shi Fanying terminates, the solid generated is carried out heat filtering separation.With decane and hexane, solid catalyst is fully washed respectively
Wash, until inspection does not measures the titanium compound of precipitation in cleanout fluid, obtain a kind of solid titanium catalyst component after drying.
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 come for those of ordinary skill in the art
Saying, 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 model of the present invention
Enclose.
Claims (10)
1. an electron donor for Ziegler-Natta catalyst, for acetoxylsilane compound, has a following structure:
In formula: R1, R2, R3Selected from identical or different C1-C4 alkyl, C2-C4 acyl group.
Electron donor the most according to claim 1, it is characterised in that: described acetoxylsilane compound is acetyl oxygen
Base trimethoxy silane, acetoxyl group triethoxysilane, acetoxyl group tripropoxy silane, acetoxyl group three butoxy silane,
Diacetoxy dimethoxysilane, diacetoxy diethoxy silane, diacetoxy dipropoxy silane, diethyl acyl-oxygen
Base dibutoxy silane, triacetoxyl group methoxy silane, triacetoxyl group Ethoxysilane.
3. the catalytic component comprising electron donor described in claim 1 or 2, it is characterised in that: this catalytic component includes
1. magnesium complex；2. titanium compound；3. acetoxylsilane compound；
Component 1. described in magnesium complex be magnesium halide is dissolved in the dicyandiamide solution containing organic alcohol compound obtained by product
Thing；Described organic alcohol compound be carbon number be straight chain, the alkylol of side chain, cyclic alkanol or the carbon number of 1～10 be 6～20
Fragrant and mellow or aralkyl alcohol, 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,
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 acetoxylsilane 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 is to slowly warm up to 80～125 DEG C, Gu
Body thing gradually separates out and is formed granule, after the reaction regular hour, removes unreacted reactant and solvent, and uses inert diluent to wash
Wash, obtain 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 slowly risen
Temperature is to 80～125 DEG C, and solids gradually separates out and formed granule, after the reaction regular hour, removes unreacted reactant and solvent, and
Employing inert diluent washs, and obtains granulated solid titanium catalyst component.
7. comprise a catalyst for catalytic component described in claim 3, 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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