CN110240668A - The internal electron donor of Ziegler-Natta catalyst, catalytic component, preparation method and applications - Google Patents
The internal electron donor of Ziegler-Natta catalyst, catalytic component, preparation method and applications Download PDFInfo
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- CN110240668A CN110240668A CN201910547870.3A CN201910547870A CN110240668A CN 110240668 A CN110240668 A CN 110240668A CN 201910547870 A CN201910547870 A CN 201910547870A CN 110240668 A CN110240668 A CN 110240668A
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Abstract
The present invention relates to a kind of internal electron donors, catalytic component, preparation method and applications for vinyl polymerization Ziegler-Natta catalyst.Wherein for the internal electron donor structure such as shown in (I), catalytic component includes a kind of magnesium complex, a kind of titanium compound, a kind of internal electron donor as described in leading to formula (I).The catalyst is used to show higher catalytic activity, preferable hydrogen response and preferable copolymerization performance when vinyl polymerization or combined polymerization, is particularly suitable for ethylene slurry polymerization and ethene gas-phase polymerization to produce high-bulk-density, narrow size distribution, the polymer that fine particle content is few, wax content is low and molecular weight distribution is wide.
Description
Technical field
The invention belongs to ethylene rolymerization catalyst fields, are related to a kind of Ziegler-Natta catalyst, especially a kind of use
In the electron donor of the Ziegler-Natta catalyst of vinyl polymerization, catalytic component and its answering in ethylene polymerization
With.
Technical background
In recent years, the development and application of high-end trade mark polyolefin PP Pipe Compound is always the emphasis in the field, corresponding to be catalyzed
The research and development of agent are also the difficult point in polyolefin resin research field, the knot of the Nomenclature Composition and Structure of Complexes of catalyst to polyolefin resin
Structure and performance have important influence.Titanium system Ziegler-Natta catalyst is still industrial production polyolefin resin at present
Dominant catalyst, develop that high catalytic activity, hydrogen response are good, copolymerization performance is good, obtain polymer particle size and be evenly distributed,
The target that fine powder is few, wax content is low, the steady controllable polyolefin catalyst of production is scientific research personnel and engineers and technicians' pursuit.
There are many titanium system Ziegler-Natta catalysts for preparing magnesium chloride load of many documents and patent report as olefinic polymerization
With the method for copolymerization catalysts.According to the difference of polymerization technique, it is desirable that the performance of corresponding catalyst is also had nothing in common with each other,
Therefore the production method of corresponding catalyst is also slightly different.Such as it is used for the Ziegler- of ethylene gas-phase fluidized bed polymerization process
Natta catalyst, it is desirable that catalyst granules form is good, fine powder is few, and what is generated when being used for ethylene gas fluidised bed polymerisation in this way is poly-
Ethylene fine powder is few, can be to avoid the reactor sheeting because of caused by electrostatic.Catalyst for ethene gas-phase polymerization is usually will
Active component is directly carried on the inert carrier such as silica gel of large surface, since the particle diameter of silica gel is easy to control, and
Particle shape is preferable, therefore evengranular catalyst particle can be obtained.But due to the load capacity of active component on carrier by
Limitation, therefore Ti content is lower in catalyst made from this method, polymerization activity is not high.For example, in patent CN99103280
In, with MgCl2、SiO2For carrier, TiCl4For active component, catalyst the preparation method is as follows: by MgCl2In THF with
TiCl4Reaction forms catalyst mother liquor, then with the carrier S iO that was activated through alkyl aluminum2Mixing removes part tetrahydrofuran
Catalyst precursor component is made afterwards.Be used for vinyl polymerization when, since the Ti content in catalyst is lower, thus polymerization activity compared with
It is low.Therefore, although this catalyst system can be used for the gas-phase fluidized bed polymerization process of ethylene, but due to lower catalytic activity
It is difficult suitable for the slurry polymerization processes of ethylene.
Ziegler-Natta catalyst for ethylene slurry polymerization processes, it is desirable that catalyst activity height, hydrogen response
Can be good, while requiring that polymerizate fine powder is few, wax content is few, it can guarantee the continuous long-term operation of process units in this way.It is right
It is that the dissolution of the magnesium compounds such as magnesium chloride is obtained into homogeneous solution in a solvent in the preparation method of this catalyst, then again should
Solution is mixed with titanium compound and electron donor, obtains the solids containing magnesium, titanium and electron donor by the method for precipitating, and will
The solids obtains catalyst granules after being handled with excessive liquid titanium compound.As Chinese patent CN1099041A,
CN1229092、CN1958620A、CN100513433、CN100532406、CN102344514B、CN102344515B、
CN101274967B、CN102453172A、CN102432726A、CN102344506A、CN102344507、CN102286119A、
CN102286120A etc. discloses the method for preparing this catalyst.The preparation of this catalyst generally by magnesium chloride knot
Partial crystallization goes out the granular size and particle shape of process control catalyst, and the improvement of electron donor compound is added in precipitation process and urges
Agent performance.The electron donor compound of addition had not only influenced the particle shape of catalyst but also had influenced the hydrogen response of catalyst
And copolymerization performance, therefore the selection of electron donor is a key of such catalyst exploitation.Such as Chinese patent CN1958620A
Using tetraethoxysilane is electron donor, CN2010102089331 using a kind of silicone compounds with organo-functional group
It (POSS) is electron donor, but the price of this silicone compounds is very expensive, limits its application in the catalyst.
Summary of the invention
The present invention be directed to the deficiencies of above-mentioned art methods, provide a kind of vinyl polymerization Ziegler-Natta catalysis
The electron donor of agent, the catalytic component comprising the electron donor, the catalyst comprising the catalytic component, and its it is poly- in ethylene
It closes, the application in copolymerization.
A kind of electron donor of Ziegler-Natta catalyst is substituted acetic acid ethyl ester compound, has the following structure:
In formula: R1、R2And R3Can be identical or different, it is respectively selected from hydrogen, methyl, ethyl, the alkyl of C3~C10, cycloalkanes
Base, aromatic radical, halogen, alkyl phosphono, alkoxy and halogenated alkoxy etc.；
Preferably, substituted acetic acid ethyl ester compound are as follows: ethyl chloroacetate, bromoacetate, ethyl iodoacetate, dichloroacetic acid
Ethyl ester, ethyl dibromoacetate, diiodo-acetic acid ethyl ester, ethyl trichloroacetate, ethyl tribromacetate, triiodoacetic acid ethyl ester, trimethyl
Ethyl acetate, cyan-acetic ester, dimethyl phosphine ethylphosphonoacetate, ethyl diacetoacetate, to toluene ethyl acetate, 2-
(chloromethane epoxide) ethyl acetate etc..
A kind of catalytic component comprising the internal electron donor, the catalytic component include:
1. magnesium complex；2. titanium compound；3. substituted acetic acid ethyl ester compound；
Component 1. described in magnesium complex be that magnesium halide is dissolved in institute in the dicyandiamide solution containing organic alcohol compound
Obtained product；The organic alcohol compound be carbon atom number be 1~10 straight chain, the alkylol of branch, carbon atom number 3
The halides for the fragrant and mellow and above-mentioned Organic Alcohol that~10 cyclic alkanol and carbon atom number is 7~20；Above-mentioned alcohol is single one
The mixture of kind or two or more alcohol.
Component 2. described in titanium compound general formula be Ti (OR)aXb, R is the aliphatic group or aryl of C1~C10, X in formula
For halogen, a is 0,1,2 or 3, and b is 1 to 4 integer, a+b=3 or 4.
In terms of every mole of magnesium halide, organic alcohol compound content are as follows: 0.1~10.0 mole, substituted acetic acid ethyl ester compound
Content is 0.05~1.0 mole, and titanium compound content is 1.0~15.0 moles.
There are two types of modes for the addition of substituted acetic acid ethyl ester compound, are respectively as follows:
A kind of preparation method of the catalytic component, steps are as follows:
(1) magnesium halide is dissolved in the dicyandiamide solution containing organic alcohol compound, inert diluent, solution temperature is added
It is 50~125 DEG C, obtains component 1., 3. Xiang Zufen is 1. middle is added component, obtain reaction solution；
(2), at -24 DEG C~10 DEG C, 2. reaction solution and component are subjected to haptoreaction, mixture is to slowly warm up to 80~
125 DEG C, solids is gradually precipitated and is formed particle, after reacting the regular hour, removes unreacted reactant and solvent, and use inertia
Diluent washing, obtains granulated solid titanium catalyst component.
A kind of preparation method of the catalytic component, steps are as follows:
(1) magnesium halide is dissolved in the dicyandiamide solution containing organic alcohol compound, inert diluent, solution temperature is added
It is 50~125 DEG C, obtains component 1.；
(2), at -24 DEG C~10 DEG C, 1. 2. component is first subjected to haptoreaction with component, component is added 3., by mixture
Be to slowly warm up to 80~125 DEG C, solids is gradually precipitated and is formed particle, after reacting the regular hour, remove unreacted reactant and
Solvent, and washed using inert diluent, obtain granulated solid titanium catalyst component.
A kind of catalyst comprising the catalytic component includes:
(1) catalytic component as claimed in claim 3；
(2) general formula is AlRnX3-nOrgano-aluminum compound, the alkyl that R is hydrogen atom or carbon atom number is 1~20 in formula, X
For halogen, 0 < n≤3.
Component (2) in aluminium and component (1) in the molar ratio of titanium be 10~1000.
Application of the electron donor in ethylene polymerization a kind of described in.
The application of catalytic component or catalyst in ethylene polymerization a kind of described in.
Catalyst of the invention is prepared by following steps: (1) being dissolved in halogenated magnesium compound in organic alcohol compound
Prepare homogeneous magnesium solution；(2) make the homogeneous magnesium solution generate magnesium at least one substituted acetic acid ethyl ester compound reaction to combine
Object solution；(3) it reacts the magnesium compositions solution with titanium compound and generates solid titanium catalyst, it can with reacting for titanium compound
It is primary to carry out, it can also carry out repeatedly.The magnesium compound can be halogenated magnesium compound.For magnesium halide of the invention
The type for closing object may include with Types Below: magnesium dihalide compound such as magnesium chloride, magnesium iodide, magnesium fluoride and magnesium bromide；Alkyl halide
Base magnesium compound such as methylmagnesiumhalide, ethyl-magnesium-halide, halogenation propyl magnesium, butyl Grignard reagent, halogenation isobutyl group magnesium, halogenation hexyl
Magnesium and halogenation amyl magnesium；Halogenated alkoxy magnesium compound for example halogenation magnesium methoxide, halogenation magnesium ethylate, halogenation isopropoxy magnesium,
Halogenation butoxy magnesium and halogenation octyloxy magnesium；Halogen aryloxy magnesium such as halogenation phenoxy group magnesium and halogenated methyl phenoxy group magnesium.These
Magnesium compound can be used with single compound or with the form of mixtures of two or more compound.In addition, above-mentioned magnesium compound can
Effectively used in the form of with the complex of other metals.Other magnesium compounds include by can be dependent on magnesium compound preparation
Method and the compound that exists but cannot be indicated with molecular formula, may be generally viewed as the mixture of magnesium compound.For example, can be used to down
Compound is as magnesium compound: by magnesium compound and substituted acetic acid ethyl ester compound, the halogen-containing silane compound of packet, ester,
Or the compound that alcohol reacts；Exist by magnesium metal and alcohol, phenol or ether in halogenated silanes, phosphorus pentachloride or thionyl chloride
It is lower to react obtained compound.The magnesium compound can be magnesium halide, especially magnesium chloride or have the alkane of 1~10 carbon atom
The alkyl magnesium chloride of base；There is the alkoxy magnesium chloride of the alkoxy of 1~10 carbon atom；There is the aryloxy group of 6~20 carbon atoms
Chlorination aryloxy group magnesium.Magnesium solution used can be by keeping the magnesium compound molten presence or absence of hydrocarbon solvent
Solution is made in alcohol and prepares.Type for hydrocarbon solvent of the invention can be aliphatic hydrocarbon such as pentane, hexane, heptane, pungent
Alkane, decane and kerosene；Clicyclic hydrocarbon such as ring benzene, methyl benzene, hexamethylene and hexahydrotoluene；Aromatic hydrocarbon such as benzene, toluene, two
Toluene, ethylo benzene etc.；Halogenated hydrocarbons such as dichloropropane, dichloroethylene, trichloro ethylene, carbon tetrachloride and chlorobenzene etc..By magnesium compound
It prepares magnesium solution and can make solvent of alcohol and carried out in the case where adding or hydrocarbon solvent being not added.The type of alcohol may include containing 1~20
The alcohol of carbon atom such as methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, hexanol, octanol, decyl alcohol, dodecanol, tetradecanol, hexadecane
Alcohol, octadecanol, benzylalcohol, benzyl carbinol, isopropylbenzyl alcohol and cumic alcohol, the alcohol of preferred optional self-contained 1~12 carbon atom of alcohol.
The average particle size and size distribution of gained catalyst may depend on the type of alcohol used, the dosage of alcohol, the type of magnesium compound and
The ratio between magnesium compound and alcohol.During preparing magnesium solution, magnesium compound can be carried out with reacting for alcohol in the presence of hydrocarbon solvent.
Although reaction temperature can change according to the type and dosage of alcohol used, can at least about -25 DEG C, preferably from about -20 to 150 DEG C,
Or more preferably from about -10 to 110 DEG C.Reaction time can be about 15 minutes to 10 hours or preferably from about 30 minutes to 4 hours.
When the magnesium compositions solution is reacted 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 the magnesium compound solution and titanium compound, take
Generation solid substance composition is reacted at temperatures sufficiently low for the mixture of ethyl acetate compound.The substituted acetic acid
Ethyl ester compound can contact preceding addition system with titanium compound in magnesium compound solution, can also be in magnesium compound solution and titanizing
System is added after closing object contact.The reaction temperature can be about -70 to 70 DEG C, more preferably from about -50 to 50 DEG C.The haptoreaction
Later, increase the reaction temperature slowly with the abundant reaction at about 50 to 150 DEG C for about 0.5~5 hour.It can make as above
The obtained solid catalyst particle is reacted with additional titanium compound again.Titanium compound used can be halogenated titanium or halogenation
Alkoxytitanium, wherein alkoxy-functional has 1~20 carbon atom.The mixture of these compounds can also be used when appropriate.This
In a little compounds, the halogenated alkoxy titanium that halogenated titanium or in which alkoxy-functional have 1~8 carbon atom be it is suitable, it is more excellent
The compound of choosing is titanium tetrahalide.It can be used for the polymerization and combined polymerization of ethylene by catalyst prepared by the method for the invention.It is special
, the catalyst not can be used for the homopolymerization of ethylene, it can also be used to ethylene with have 3 or more carbon atoms alpha-olefin such as propylene,
The copolymerization of 1- butylene, 1- amylene, 4-methyl-1-pentene or 1- hexene.It is available using the polymerization reaction of catalyst of the present invention
Catalyst system carries out, and the catalyst system includes: (1) solid titanium described herein including magnesium, titanium and Donor compound
Complex compound catalyst；(2) alkyl metal cpd or alumina metal compound.The organo-metallic compound is to have 1~6
The trialkylaluminium of the alkyl of carbon atom, as triethyl aluminum and triisobutyl aluminium, or mixtures thereof.Where appropriate, can also be used one
Or the organo-aluminum compound of multiple halogens or hydrogen radical group, such as ethylaluminium dichloride, diethylaluminum chloride, sesquialter tonsilon
Aluminium or diisobutylaluminium hydride.Before polymerization reaction, solid titanium complex catalyst component described herein and ethylene can be made
Or alpha-olefin pre-polymerization.The pre-polymerization can in the presence of hydrocarbon solvent such as hexane, at temperatures sufficiently low, in ethylene or α-alkene
It is carried out under the pressure of hydrocarbon and in the presence of above-mentioned catalytic component and organo-aluminum compound such as triethyl aluminum.In polymerization reaction system
The molar ratio of titanium is 1~1000, preferably 20~200 in organo-aluminum compound and solid titanium complex catalyst.It is high poly- to ensure
Reaction rate is closed, the polymerization reaction need to carry out at sufficiently high temperature, generally, suitable temperature is about 20 to 200 DEG C,
More preferably from about 60 to 95 DEG C.The monomer pressure being suitble in polymerization process is 0.1~10.0MPa, more preferably from about 0.2~5.0MPa.
The advantages and positive effects of the present invention
1, it is a discovery of the invention that substituted acetic acid ethyl ester compound is used to be added to the titanium system of magnesium chloride load for electron donor
In Ziegler-Natta catalyst, the catalyst granules form that can make is regular, is in granulated, and particle diameter distribution is good, polymerize
Product powder is few, bulk density is high, while obtained catalyst has preferable hydrogen response energy and copolymerization performance.
2, contain the electronegativity such as halogen, phosphine, cyano in the molecular structure of the substituted acetic acid ethyl ester compound used in the present invention
Biggish group or atom, these electron rich groups participate in the coordination between magnesium, titanium, influence the chemical environment in titanium activated centre,
Therefore achieve the purpose that regulate and control catalyst hydrogen response and copolymerization performance.
3, the substituted acetic acid ethyl ester compound used in the present invention belongs to common chemicals, and lower production costs may be used on
Catalyst it is industrially prepared in.
Specific embodiment
Below by specific embodiment, the invention will be further described, and it is not limit that following embodiment, which is descriptive,
Qualitatively, this does not limit the scope of protection of the present invention.
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, obtain the solution of homogeneous phase transparent within isothermal reaction 3 hours.The tri-methyl ethyl acetate of 15mmol is added into the solution and 50
2 hours are stirred at DEG C so that tri-methyl ethyl acetate is dissolved in the solution.Homogeneous phase solution obtained above is cooled to room temperature, so
It is added dropwise to the 150mL TiCl that temperature remains -10 DEG C while stirring in 1 hour afterwards4In.Make mixture temperature after dripping off
Degree is kept 1 hour at -10 DEG C, and then temperature is being mentioned to 120 DEG C according to certain heating rate under stiring, and this is warm
Degree is kept for 2 hours.After reaction, heat filtering separation is carried out to the solid of generation.Respectively with decane and hexane to solid catalysis
Agent is sufficiently washed, until inspection does not measure the titanium of precipitation in cleaning solution, obtains a kind of solid titanium catalyst group after drying
Point.
Vinyl polymerization
The stainless steel polymerization reaction kettle of 2L is added hexane 1.0L and concentration is 1.0M's after high pure nitrogen is sufficiently displaced from
The catalyst of the above-mentioned preparation of precise is added with syringe, is warming up to 75 DEG C, being passed through hydrogen makes in kettle by triethyl aluminum 1.0mL
Pressure reaches 0.28MPa, then being passed through ethylene makes stagnation pressure in kettle reach 0.73MPa (gauge pressure), polymerize 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.Add the ethyl chloroacetate of 15mmol into the solution and is stirred at 50 DEG C
It mixes 2 hours so that ethyl chloroacetate is dissolved in the solution.All homogeneous phase solutions obtained above are cooled to room temperature, then 1
It is added dropwise to the 200mL TiCl that temperature remains -15 DEG C while stirring in hour4In.Make after dripping off mixture temperature-
It is kept for 1 hour at 15 DEG C, then temperature is mentioned to 120 DEG C in 4 hours under stiring, and this temperature is kept for 2 hours.When 2
Hour carries out heat filtering separation after reaction, to the solid of generation.Solid catalyst is filled with decane and hexane respectively
Divide washing, until inspection does not measure the titanium compound of precipitation in cleaning solution, obtains a kind of solid titanium catalyst component after drying.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, and after high pure nitrogen is sufficiently displaced from, three second of hexane 1L and concentration 1M are added
The catalyst of the above-mentioned preparation of precise is added with syringe, is warming up to 75 DEG C, being passed through hydrogen makes pressure in kettle by base aluminium 1.0mL
Reach 0.28MPa, then being passed through ethylene makes stagnation pressure in kettle reach 0.73MPa (gauge pressure), polymerize 2 hours under the conditions of 80 DEG C, polymerize
It 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.Add the ethyl trichloroacetate of 15mmol into the solution and at 50 DEG C
Stirring 2 hours so that ethyl trichloroacetate is dissolved in the solution.All homogeneous phase solutions obtained above are cooled to room temperature, then
It is added dropwise to the 150mL TiCl that temperature remains 0 DEG C while stirring in 1 hour4In.Make mixture temperature 0 after dripping off
It is kept for 1 hour at DEG C, then temperature is mentioned to 120 DEG C in 2 hours under stiring, and this temperature is kept for 2 hours.When 2 small
When after reaction, heat filtering separation is carried out to the solid of generation.Solid catalyst is carried out sufficiently with decane and hexane respectively
Washing obtains a kind of solid titanium catalyst component until inspection does not measure the titanium compound of precipitation in cleaning solution after drying.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, and after high pure nitrogen is sufficiently displaced from, three second of hexane 1L and concentration 1M are added
The catalyst of the above-mentioned preparation of precise is added with syringe, is warming up to 75 DEG C, being passed through hydrogen makes pressure in kettle by base aluminium 1.0mL
Reach 0.28MPa, then being passed through ethylene makes stagnation pressure in kettle reach 0.73MPa (gauge pressure), polymerize 2 hours under the conditions of 80 DEG C, polymerize
It 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 dimethyl phosphine ethylphosphonoacetate of 15mmol is added into the solution
And 2 hours are stirred at 50 DEG C so that dimethyl phosphine ethylphosphonoacetate is dissolved in the solution.It will be obtained above all homogeneous
Solution is cooled to room temperature, and is then added dropwise to the 150mL TiCl that temperature remains 0 DEG C while stirring in 1 hour4In.Drop
Keep mixture temperature at 0 DEG C 1 hour, then temperature mentioned to 120 DEG C in 2 hours under stiring, and by this
Temperature is kept for 2 hours.After reaction when 2 is small, heat filtering separation is carried out to the solid of generation.Decane and hexane pair are used respectively
Solid catalyst is sufficiently washed, until inspection does not measure the titanium compound of precipitation in cleaning solution, obtains one kind after drying
Solid titanium catalyst component.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, hexane 1L is added and concentration is the three of 1M
The catalyst of the above-mentioned preparation of precise is added with syringe, is warming up to 75 DEG C, being passed through hydrogen makes kettle internal pressure by aluminium ethide 1.0mL
Power reaches 0.28MPa, then being passed through ethylene makes stagnation pressure in kettle reach 0.73MPa (gauge pressure), polymerize 2 hours under the conditions of 80 DEG C, gathers
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 ethyl diacetoacetate of 15mmol is added into the solution and 50
2 hours are stirred at DEG C so that ethyl diacetoacetate is dissolved in the solution.All homogeneous phase solutions obtained above are cooled to room
Then temperature is added dropwise to the 150mL TiCl that temperature remains -10 DEG C while stirring in 1 hour4In.Make to mix after dripping off
Object temperature is kept 1 hour at -10 DEG C, and then temperature is mentioned to 120 DEG C in 2 hours under stiring, and this temperature is kept 2
Hour.After reaction when 2 is small, heat filtering separation is carried out to the solid of generation.Respectively with decane and hexane to solid catalysis
Agent is sufficiently washed, until inspection does not measure the titanium compound of precipitation in cleaning solution, is obtained a kind of solid titanium after drying and is urged
Agent component.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, hexane 1L is added and concentration is the three of 1M
The catalyst of the above-mentioned preparation of precise is added with syringe, is warming up to 75 DEG C, being passed through hydrogen makes kettle internal pressure by aluminium ethide 1.0mL
Power reaches 0.28MPa, then being passed through ethylene makes stagnation pressure in kettle reach 0.73MPa (gauge pressure), polymerize 2 hours under the conditions of 80 DEG C, gathers
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.2- (chloromethane epoxide) ethyl acetate of 15mmol is added into the solution
And it is stirred 2 hours at 50 DEG C so that 2- (chloromethane epoxide) ethyl acetate is dissolved in the solution.It will be obtained above all homogeneous
Solution is cooled to room temperature, and is then added dropwise to the 150mL TiCl that temperature remains -10 DEG C while stirring in 1 hour4In.
It keeps mixture temperature at -10 DEG C 1 hour, then temperature is mentioned to 120 DEG C in 2 hours under stiring, and
This temperature is kept for 2 hours.After reaction when 2 is small, heat filtering separation is carried out to the solid of generation.Respectively with decane and oneself
Alkane sufficiently washs solid catalyst, until inspection does not measure the titanium compound of precipitation in cleaning solution, 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, hexane 1L is added and concentration is the three of 1M
The catalyst of the above-mentioned preparation of precise is added with syringe, is warming up to 75 DEG C, being passed through hydrogen makes kettle internal pressure by aluminium ethide 1.0mL
Power reaches 0.28MPa, then being passed through ethylene makes stagnation pressure in kettle reach 0.73MPa (gauge pressure), polymerize 2 hours under the conditions of 80 DEG C, gathers
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.All homogeneous phase solutions obtained above are cooled to room temperature, then 1
It is added dropwise to the 150mL TiCl that temperature remains -10 DEG C while stirring in hour4In.Then it is added into the solution
The ethyl trichloroacetate of 15mmol.Keep mixture temperature at -10 DEG C 1 hour, then under stiring at 2 hours
It is interior that temperature is mentioned to 120 DEG C, and this temperature is kept for 2 hours.After reaction when 2 is small, hot mistake is carried out to the solid of generation
Filter separation.Solid catalyst is sufficiently washed with decane and hexane respectively, until inspection does not measure precipitation in cleaning solution
Titanium compound 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, hexane 1L is added and concentration is the three of 1M
The catalyst of the above-mentioned preparation of precise is added with syringe, is warming up to 75 DEG C, being passed through hydrogen makes kettle internal pressure by aluminium ethide 1.0mL
Power reaches 0.28MPa, then being passed through ethylene makes stagnation pressure in kettle reach 0.73MPa (gauge pressure), polymerize 2 hours under the conditions of 80 DEG C, gathers
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.All homogeneous phase solutions obtained above are cooled to room temperature, then 1
It is added dropwise to the 150mL TiCl that temperature remains -10 DEG C while stirring in hour4In.Then it is added into the solution
The cyan-acetic ester of 15mmol.Keep mixture temperature at -10 DEG C 1 hour, then under stiring at 2 hours
It is interior that temperature is mentioned to 120 DEG C, and this temperature is kept for 2 hours.After reaction when 2 is small, hot mistake is carried out to the solid of generation
Filter separation.Solid catalyst is sufficiently washed with decane and hexane respectively, until inspection does not measure precipitation in cleaning solution
Titanium compound obtains a kind of solid titanium catalyst component after drying.
Vinyl polymerization
Volume is the stainless steel cauldron of 2L, and after high pure nitrogen is sufficiently displaced from, hexane 1L, the triethyl group of concentration 1M is added
The catalyst of the above-mentioned preparation of precise is added with syringe, is warming up to 75 DEG C, being passed through hydrogen reaches pressure in kettle by aluminium 1.0mL
To 0.28MPa, then being passed through ethylene makes stagnation pressure in kettle reach 0.73MPa (gauge pressure), polymerize 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 into the solution and at 50 DEG C
Lower stirring 2 hours so that tetraethoxysilane is dissolved in the solution.All homogeneous phase solutions obtained above are cooled to -10 DEG C,
Then it will stay in that -10 DEG C of 150mLTiCl while stirring in 1 hour4It is added drop-wise in above-mentioned homogeneous phase solution.Make to mix after dripping off
It closes object temperature to keep at 0 DEG C 1 hour, then temperature is mentioned to 120 DEG C in 2 hours under stiring, and this temperature is kept 2
Hour.After reaction when 2 is small, heat filtering separation is carried out to the solid of generation.Respectively with decane and hexane to solid catalysis
Agent is sufficiently washed, until inspection does not measure the titanium compound of precipitation in cleaning solution, is obtained a kind of solid titanium after drying and is urged
Agent component.
For vinyl polymerization with embodiment 1, polymerization result is shown in Table 1.
What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art
For, under the premise of not departing from inventive concept, various modifications and improvements can be made, these belong to protection of the invention
Range.
Comparative example 2
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 ethyl acetate of 15mmol is added into the solution and is stirred at 50 DEG C
It mixes 2 hours so that ethyl acetate is dissolved in the solution.All homogeneous phase solutions obtained above are cooled to -10 DEG C, it is then small 1
When the interior 150mLTiCl that will stay in that -10 DEG C while stirring4It is added drop-wise in above-mentioned homogeneous phase solution.Make mixture temperature after dripping off
It is kept for 1 hour at 0 DEG C, then temperature is mentioned to 120 DEG C in 2 hours under stiring, and this temperature is kept for 2 hours.When 2
Hour carries out heat filtering separation after reaction, to the solid of generation.Solid catalyst is filled with decane and hexane respectively
Divide washing, until inspection does not measure the titanium compound of precipitation in cleaning solution, obtains a kind of solid titanium catalyst component after drying.
For vinyl polymerization with embodiment 1, polymerization result is shown in Table 1.
1 polymerization experiment result of table
What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art
For, under the premise of not departing from inventive concept, various modifications and improvements can be made, these belong to protection of the invention
Range.
Claims (10)
1. a kind of internal electron donor of vinyl polymerization Ziegler-Natta catalyst, it is characterised in that: ethyl esterified for substituted acetic acid
Object is closed, there is the structure as described in leading to formula (I):
In formula: R1、R2And R3It is identical or different, be respectively selected from hydrogen, methyl, ethyl, the alkyl of C3~C10, naphthenic base, aromatic radical,
Halogen, alkyl phosphono, alkoxy or halogenated alkoxy.
2. the internal electron donor of vinyl polymerization Ziegler-Natta catalyst according to claim 1, it is characterised in that:
The substituted acetic acid ethyl ester compound is ethyl chloroacetate, bromoacetate, ethyl iodoacetate, ethyl dichloroacetate, dibromo second
Acetoacetic ester, diiodo-acetic acid ethyl ester, ethyl trichloroacetate, ethyl tribromacetate, triiodoacetic acid ethyl ester, tri-methyl ethyl acetate, cyanogen
Ethyl, dimethyl phosphine ethylphosphonoacetate, ethyl diacetoacetate, to toluene ethyl acetate, 2- (chloromethane epoxide) second
Acetoacetic ester.
3. a kind of catalytic component comprising internal electron donor of any of claims 1 or 2, it is characterised in that: the catalyst group
Divide and includes:
1. magnesium complex；2. titanium compound；3. substituted acetic acid ethyl ester compound；
Component 1. described in magnesium complex be magnesium halide is dissolved in the dicyandiamide solution containing organic alcohol compound obtained by
Product；The organic alcohol compound be carbon atom number be 1~10 straight chain, the alkylol of branch, carbon atom number be 3~10
Cyclic alkanol and carbon atom number be 7~20 fragrant and mellow and above-mentioned Organic Alcohol halides；Above-mentioned alcohol is single one kind, or
The mixture of two or more alcohol；
Component 2. described in titanium compound general formula be Ti (OR)aXb, R is C in formula1~C10Aliphatic group or aryl, X is halogen
Element, a are 0,1,2 or 3, and b is 1 to 4 integer, a+b=3 or 4.
4. catalytic component according to claim 3, it is characterised in that: in terms of every mole of magnesium halide, organic alcohol compound
Content are as follows: 0.1~10.0 mole, substituted acetic acid ethyl ester compound content is 0.05~1.0 mole, and titanium compound content is 1.0
~15.0 moles.
5. a kind of preparation method of catalytic component as claimed in claim 3, steps are as follows:
(1) magnesium halide is dissolved in the dicyandiamide solution containing organic alcohol compound, inert diluent, solution temperature 50 is added
~125 DEG C, obtain component 1., 3. Xiang Zufen is 1. middle to be added component, obtain reaction solution；
(2), at -24 DEG C~10 DEG C, 2. reaction solution and component are subjected to haptoreaction, mixture is to slowly warm up to 80~125 DEG C,
Solids is gradually precipitated and is formed particle, after reacting the regular hour, removes unreacted reactant and solvent, and use inert diluent
Washing, obtains granulated solid titanium catalyst component.
6. a kind of preparation method of catalytic component as claimed in claim 3, steps are as follows:
(1) magnesium halide is dissolved in the dicyandiamide solution containing organic alcohol compound, inert diluent, solution temperature 50 is added
~125 DEG C, obtain component 1.；
(2), at -24 DEG C~10 DEG C, 1. 2. component is first subjected to haptoreaction with component, adds component 3., mixture is slow
80~125 DEG C are warming up to, solids is gradually precipitated and is formed particle, after reacting the regular hour, unreacted reactant and solvent are removed,
And washed using inert diluent, obtain granulated solid titanium catalyst component.
7. a kind of catalyst comprising catalytic component described in claim 3, includes:
(1) catalytic component as claimed in claim 3；
(2) general formula is AlRnX3-nOrgano-aluminum compound, R is hydrogen in formula or carbon atom number is the alkyl of l~20, and X is halogen, 0 < n
≤3。
8. catalyst according to claim 7, it is characterised in that: component (2) in aluminium and component (1) in the molar ratio of titanium be 10
~1000.
9. a kind of application of electron donor of any of claims 1 or 2 in vinyl polymerization or copolymerization.
10. a kind of catalytic component as claimed in claim 3 or catalyst as claimed in claim 7 are in vinyl polymerization or combined polymerization
Application in reaction.
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