CN106243253B - For the catalytic component and preparation method of vinyl polymerization or combined polymerization, the catalyst comprising the catalytic component, preparation method and application - Google Patents
For the catalytic component and preparation method of vinyl polymerization or combined polymerization, the catalyst comprising the catalytic component, preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of catalytic component and preparation method being used for vinyl polymerization or combined polymerization, the catalyst comprising the catalytic component, preparation method and applications.Magnesium compound is dissolved in the alcohols solvent that carbon atom quantity is 6~20 by the preparation method of the catalytic component, including (1)；(2) alcohol and form renovation agent of the carbon atom number less than or equal to 5 is added, is reacted；(3) at 30 DEG C~10 DEG C, above-mentioned reaction solution is added dropwise in titanium compound and is reacted, then heat to 90 DEG C~120 DEG C, solid is precipitated；(4) inert diluent and titanium compound reaction are added in (3) obtained solid, obtains solid precipitation；(5) it washs precipitation in (4) with inert diluent and obtains the catalytic component.The catalyst of ethylene polymerization includes above-mentioned catalytic component and general formula is AlR1 nX3‑nOrgano-aluminum compound.The catalyst particle size of the present invention is uniform, and particle diameter distribution is narrow, and fine polymer powder content is low, while also having good hydrogen response.
Description
Technical field
The present invention relates to vinyl polymerization or copolymerization catalyst system, more particularly, to one kind for vinyl polymerization or
Catalytic component of copolymerization and preparation method thereof, a kind of catalyst comprising the component, preparation method and the catalyst
Application in vinyl polymerization or copolymerization.
Background technology
It is well known that the single site catalysts such as metallocene and Nonmetallocene are studied as polyolefin catalyst in recent years
It is also gradually increased with the industrial applications of the hot spot of exploitation, single-site catalysts, but Ziegler-Natta catalyst is in polyethylene
Industrialized production in still occupy leading position.Since the eighties in last century, Ziegler-Natta catalyst production both domestic and external
Product emerge one after another, and catalyst stability is also continuously improved with polymerization activity.But presently used catalyst is in the course of the polymerization process
It is easy to generate thinner polymer particle, the presence of this fine powder frequently can lead to the low bulk density of polymer, cause to set
Standby or pipeline blocking, influences the long-term operation of device.
Halogenated magnesium compound is dissolved in organic solvent by patent CN101891849A and patent CN102617760A, is formed
Then uniform solution system is added dropwise transition metal halide and solid catalyst is slowly precipitated.But due to mixing to magnesium halide
Directly it is added dropwise that transition metal halide process reaction is violent, and hydrogen chloride gas largely discharges in liquid so that final obtained solid is urged
Catalyst particles form is poor, particle diameter distribution is uneven, and be easy to cause catalyst wall sticking phenomenon.Patent CN102358761A reports
A kind of olefin polymerization catalysis preparation method, first passes through halogenated silicon compound is added dropwise into the homogeneous organic solvent of magnesium halide
Carrier is obtained, then transition metal halide is added dropwise into the organic solvent for be dispersed with carrier and obtains solid polyolefin hydrocarbon catalyst group
Point.For catalyst obtained by this method although particle shape is good, catalytic activity is also higher, but is catalyzed fine powder in products therefrom polymer
Content is higher, therefore is unfavorable for industrial production.
In addition, commercial plant produce polyethylene during, except require catalyst should have higher catalytic activity and
Outside preferable distribution of particles, in order to produce the Alathon or copolymer with preferable performance, also require catalyst that should have
Preferable hydrogen response easily adjusts the melt index of final polymer by hydrogen partial pressure in polymerization process, with
Obtain the polyvinyl resin of different performance.And the hydrogen response of above-mentioned catalyst system can't be satisfactory.
Invention content
The purpose of the present invention is to provide a kind of catalytic component and preparation method, packets being used for vinyl polymerization or combined polymerization
Catalyst, preparation method containing the catalytic component and application, to overcome catalysis resulting polymers fine powder content height, heap in the prior art
The low density deficiency of product.
The object of the present invention is achieved like this, a kind of preparation side for vinyl polymerization or the catalytic component of combined polymerization
Method, this method comprises the following steps：
(1) magnesium compound is dissolved in the alcohols solvent that carbon atom quantity is 6~20, forms solution, solution temperature is
100~150 DEG C；
(2) alcohol and form renovation agent of the carbon atom number less than or equal to 5 are added in above-mentioned solution, is reacted, instead
It is 30~100 DEG C to answer temperature；
(3) at a temperature of -30 DEG C~10 DEG C, above-mentioned reaction solution is added dropwise in titanium compound and is reacted, is then heated up
To 90 DEG C~120 DEG C, solid is precipitated；
(4) the reaction was continued for the mixture of addition inert diluent and titanium compound in step (3) obtained solid, consolidate
Body precipitates；And
(5) catalytic component is obtained with precipitation in inert diluent washing step (4)；
Wherein, titanium compound general formula is Ti (OR)4-nXn, R is the alkyl that carbon atom number is less than 6 in formula, and X is halogen, n 0
~4 integer；Form renovation agent general formula is R1 xR2 yR3(OR4)Z, wherein R1And R2Respectively alkyl or halogen, R3And R4For alkyl,
2,0 z≤4 ＜ 0≤x ＜ 2,0≤y ＜.
Wherein, the magnesium compound is magnesium dihalide, the hydrate of magnesium dihalide, the alcohol adduct of magnesium dihalide, alkyl
One or more of magnesium halide and the formed group of ohydrocarbyl oxyhalides magnesium；Preferably magnesium dichloride.
Wherein, the alcohol that the carbon atom number is 6~20 is hexanol, 2- methyl anyl alcohols, 2- ethyl butanols, enanthol, 2- second
One or more of base hexanol, octanol, decyl alcohol, dodecanol, tetradecanol and the formed group of octadecanol；Preferably 2-
Ethyl hexanol, 2- methyl anyl alcohols and 2- ethyl butanols.
Wherein, alcohol of the carbon atom number less than or equal to 5 is methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol
One or more of with the formed group of amylalcohol；Preferably methanol, ethyl alcohol and propyl alcohol.
Above-mentioned carbon atom number is played the role of different, carbon original less than or equal to 5 alcohol from carbon atom number by the alcohol of 6-20
Subnumber is the effect that the alcohol of 6-20 primarily serves dissolving magnesium compound, and alcohol of the carbon atom number less than or equal to 5 mainly plays adjusting
The effect of cloud density around magnesium atoms, unexpectedly, present invention discover that carbon atom number is less than or equal to 5 alcohol
Addition can greatly improve the melt index of polymer, that is, the hydrogen response of catalyst is improved, in general, carbon atom is added
After alcohol of the number less than or equal to 5, under same polymerizing condition, the melt index of polymer is original 1.5-5 times.
Wherein, the form renovation agent is diethoxymethane, acton, tetra ethoxy methane, 1,1- bis-
Ethoxyethane, 1,2- diethoxyethane, 1- chloro-2-ethoxies ethane, the chloro- 1,1,1- triethoxy ethanes of 2-, 1,2- bis-
Chloroethoxy ethane, 1- ethoxy propanes, tetra- ethoxy of 2,2- di ethyl propyl ethers, 1,1,1- triethoxies propane and 1,1,3,3-
One or more of formed group of base propane.
Above-mentioned form renovation agent, effect are that the alcohol adduct (i.e. the reaction product of magnesium compound and alcohol) of magnesium and titanizing is made to close
The reaction of object is more mild, and the molding of catalyst granules is promoted to be precipitated, and so that it is tended to spherical and homogenization, to improve catalyst
Particle shape and particle diameter distribution.
Wherein, the titanium compound is titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, three ethoxy of a chlorine
One or more of base titanium, dichlorodiethyl oxygroup titanium and the formed group of one ethanolato-titanium of trichlorine.
Wherein, inert diluent can be added in step (1).
Wherein, the inert diluent forms one kind in group or several by hexane, heptane, octane, nonane and decane
Kind；Preferably hexane and decane；The molar ratio of step (4) inert diluent and magnesium compound be 1~150, preferably 5~
30。
Wherein, the molar ratio for the alcohol and magnesium compound that the carbon atom number is 6~20 is 1~10, preferably 2~6.
Wherein, the molar ratio of alcohol of the carbon atom number less than or equal to 5 and magnesium compound is 0.1~10, preferably 0.2
~5.
Wherein, the molar ratio of the form renovation agent and magnesium compound is 0.01~10, preferably 0.05~2.Wherein, institute
The molar ratio for stating titanium compound and magnesium compound is 1~100, preferably 20~50；Titanium compound and step (4) in step (3)
The molar ratio of middle titanium compound is 0.5~20, preferably 1~10.
The present invention also provides what is prepared by above-mentioned preparation method to be used for vinyl polymerization or the catalytic component of combined polymerization.
The present invention also provides a kind of for vinyl polymerization or the catalyst of combined polymerization, the catalyst include following component：
(1) catalytic component for being used for vinyl polymerization or copolymerization prepared by above-mentioned preparation method；
(2) organo-aluminum compound, general formula AlR1 nX3-n, R in formula1It is halogen, n 1,2 or 3 for alkyl, X.
The proportioning of component (2) and component (1), with aluminium titanium molar ratio computing, aluminium:Titanium is 10~1000, preferably 50~500.
Wherein, the organo-aluminum compound is triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, ethyl aluminum dichloride
One or more of with the formed group of sesquialter ethylmercury chloride aluminium, preferably triethyl aluminum and triisobutyl aluminium.
The present invention also provides the above-mentioned preparation methods for vinyl polymerization or the catalyst of combined polymerization, wherein the catalysis
The preparation method of component (1) includes the following steps in agent：
(1) magnesium compound is dissolved in the alcohols solvent that carbon atom quantity is 6~20, forms solution, solution temperature is
100~150 DEG C；
(2) alcohol and form renovation agent of the carbon atom number less than or equal to 5 are added in above-mentioned solution, is reacted, instead
It is 30~100 DEG C to answer temperature；
(3) at a temperature of -30 DEG C~10 DEG C, above-mentioned reaction solution is added dropwise in titanium compound and is reacted, is then heated up
To 90 DEG C~120 DEG C, solid is precipitated；
(4) the reaction was continued for the mixture of addition inert diluent and titanium compound in step (3) obtained solid, consolidate
Body precipitates；And
(5) catalytic component is obtained with precipitation in inert diluent washing step (4)；
Wherein, titanium compound general formula is Ti (OR)4-nXn, R is the alkyl that carbon atom number is less than 6 in formula, and X is halogen, and n is 0
~4 integer；Form renovation agent general formula is R1 xR2 yR3(OR4)Z, wherein R1And R2Respectively alkyl or halogen, R3And R4For alkyl,
0≤x ＜ 2,0≤y ＜ 2 and 0 z≤4 ＜；
The present invention also provides above-mentioned for vinyl polymerization or the catalyst of combined polymerization in ethylene polymerization or combined polymerization
Application in reaction.
Beneficial effects of the present invention：
Prepared catalyst of the present invention is suitable for the homopolymerization of ethylene and the copolymerization of ethylene and other alpha-olefins,
Slurry process, vapor phase method, solwution method etc. can be used in polymerization methods, wherein being best with slurry process.Propylene, fourth can be used in alpha-olefin
Alkene, amylene, hexene, octene, 4- methyl 1- amylenes etc..The catalyst is compared with existing catalyst, its advantage is that catalyst particles
Grain size distribution is uniform, and particle diameter distribution is narrow, and fine polymer powder content is low, while also having good hydrogen response.
Specific implementation mode
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Magnesium compound：
It in the present invention, to magnesium compound and is not particularly limited, can usually be enumerated as magnesium dihalide, the hydration of magnesium dihalide
Object, the alcohol adduct of magnesium dihalide, one or more of alkyl magnesium halide and the formed group of ohydrocarbyl oxyhalides magnesium, preferably two
Magnesium chloride.
The alcohol that carbon atom number is 6~20：
In the present invention, to carbon atom number be 6~20 alcohol and be not particularly limited, can usually be enumerated as hexanol, 2- methylpents
Alcohol, 2- ethyl butanols, enanthol, 2-Ethylhexyl Alcohol, octanol, decyl alcohol, dodecanol, tetradecanol and the formed group of octadecanol
One or more of, preferably 2-Ethylhexyl Alcohol, 2- methyl anyl alcohols and 2- ethyl butanols；To its addition, usual carbon atom
Number is 1~10 for 6~20 alcohol and the molar ratio of magnesium compound, preferably 2~6.If addition is excessive, the form meeting of catalyst
It is deteriorated, if addition is very few, magnesium chloride can not be completely dissolved.
Carbon atom number is less than or equal to 5 alcohol：
In the present invention, the alcohol to carbon atom number less than or equal to 5 is not particularly limited, and can usually be enumerated as methanol, ethyl alcohol, third
One or more of alcohol, isopropanol, butanol, isobutanol and the formed group of amylalcohol, preferably methanol, ethyl alcohol and propyl alcohol；It is right
Its addition, usually carbon atom number less than or equal to 5 alcohol and magnesium compound molar ratio be 0.1~10, preferably 0.2~
5.If addition is excessive, the form of catalyst can be deteriorated, if addition is very few, not have the effect for improving hydrogen response.
Form renovation agent：
In the present invention, form renovation agent is not particularly limited, can usually be enumerated as diethoxymethane, triethoxy first
Alkane, tetra ethoxy methane, 1,1- diethoxyethane, 1,2- diethoxyethane, 1- chloro-2-ethoxies ethane, 2- chloro- 1,1,
1- triethoxy ethanes, 1,2- dichloros Ethoxyethane, 1- ethoxy propanes, 2,2- di ethyl propyl ethers, tri- ethoxies of 1,1,1-
One or more of base propane and the formed group of 1,1,3,3- tetraethoxypropanes；To its addition, usual form reparation
The molar ratio of agent and magnesium compound is 0.01~10, preferably 0.05~2.If addition is excessive, catalyst activity can reduce,
If addition is very few, the effect for improving catalyst form is not had.
Titanium compound：
In the present invention, titanium compound is not particularly limited, can usually be enumerated as titanium tetrachloride, titanium tetrabromide, tetraiodide
One kind in titanium, four titanium butoxides, a chlorine triethoxy titanium, dichlorodiethyl oxygroup titanium and the formed group of one ethanolato-titanium of trichlorine
Or it is several；To its addition, it is 1~100, preferably 20~50 that usual titanium, which closes object and the molar ratio of magnesium compound, in step (3)
The molar ratio of titanium compound and titanium compound in step (4) is 0.5~20, preferably 1~10.If addition is excessive, cause
Wastage of material, if addition is very few, catalyst activity is relatively low.
Inert diluent：
In the present invention, inert diluent is not particularly limited, can usually be enumerated as hexane, heptane, octane, nonane and the last of the ten Heavenly stems
One or more of formed group of alkane；Preferably hexane and decane；Step (4) inert diluent and magnesium compound
Molar ratio is 1~150, preferably 5~30.
The present invention program is further described with specific embodiment below.
Embodiment 1
(1) preparation of catalytic component：
In the reactor being sufficiently displaced from by nitrogen, addition 5g magnesium dichlorides, 50ml n-decanes, 23ml isooctanol,
Stirring is warming up to 130 DEG C, and isothermal reaction 3h, solid is completely dissolved to form homogeneous and transparent solution.70 DEG C are cooled to, is added
1.2ml ethyl alcohol, isothermal reaction 1 hour are cooled to 50 DEG C, and tetra ethoxy methane 3.2ml is added, and react 2h, obtain uniform solution.
Uniform solution obtained above is cooled to room temperature, the 200mL that temperature remains -20 DEG C is then added dropwise in 1 hour
In titanium tetrachloride.So that mixture temperature is kept at -20 DEG C after dripping off 1 hour, system is then warming up to 110 in 3 hours
DEG C, 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, then to solid
Middle addition 70ml titanium tetrachlorides and 80ml hexanes, reaction carries out heat filtering after 0.5 hour to obtained solid, then with hexane to solid
Body catalyst is fully washed, until inspection does not measure the titanium compound of precipitation in cleaning solution, obtained after dry good fluidity,
Particle diameter distribution uniformly, in spherical solid catalyst.
(2) vinyl polymerization：
2L polymeric kettles are flushed with hydrogen gas and are vacuumized alternately three times, 1.0L hexanes, 5mmol triethyl aluminums and above-mentioned is added
Ingredient of solid catalyst, reaction kettle are warming up to 70 DEG C, and being passed through hydrogen makes pressure in kettle reach 0.28MPa, is then passed through ethylene again
Stagnation pressure in kettle is set to reach 0.73MPa, polymerisation 2 hours at 80 DEG C.Polymerization result is shown in Table 1.
Embodiment 2
Catalytic component is made with method same as Example 1, the difference is that the addition of tetra ethoxy methane is
4.8ml.For polymerization with embodiment 1, polymerization result is shown in Table 1.
Embodiment 3
Catalytic component is made with method same as Example 1, the difference is that the addition of tetra ethoxy methane is
1.6ml.For polymerization with embodiment 1, polymerization result is shown in Table 1.
Embodiment 4
Catalytic component is made with method same as Example 1, the difference is that the addition of ethyl alcohol is 2.4ml.It is poly-
For conjunction method with embodiment 1, polymerization result is shown in Table 1.
Embodiment 5
(1) preparation of catalytic component：With embodiment 1.
(2) vinyl polymerization：
2L polymeric kettles are flushed with hydrogen gas and are vacuumized alternately three times, 1.0L hexanes, 5mmol triethyl aluminums and above-mentioned is added
Ingredient of solid catalyst, reaction kettle are warming up to 70 DEG C, and being passed through hydrogen makes pressure in kettle reach 0.73MPa, is then passed through ethylene again
Stagnation pressure in kettle is set to reach 1.0MPa, polymerisation 2 hours at 80 DEG C.Polymerization result is shown in Table 1.
Embodiment 6
(1) preparation of catalytic component：With embodiment 1.
(2) ethylene copolymerization：
2L polymeric kettles are flushed with hydrogen gas and are vacuumized alternately three times, 1.0L hexanes, 5mmol triethyl aluminums and above-mentioned is added
1- hexene 10ml are added in ingredient of solid catalyst, and reaction kettle is warming up to 70 DEG C, and being passed through hydrogen makes pressure in kettle reach 0.28MPa,
Then being passed through ethylene again makes stagnation pressure in kettle reach 0.73MPa, polymerisation 2 hours at 80 DEG C.Polymerization result is shown in Table 1.
Embodiment 7
(1) preparation of catalytic component：
In the reactor being sufficiently displaced from by nitrogen, 5g tertiary butyl magnesium chlorides, 23ml decyl alcohol is added, stirring is warming up to
150 DEG C, isothermal reaction 3h, solid is completely dissolved to form homogeneous and transparent solution.70 DEG C are cooled to, 1.2ml ethyl alcohol, constant temperature is added
Reaction 1 hour is cooled to 50 DEG C, and tetra ethoxy methane 3.2ml is added, and reacts 2h, obtains uniform solution.It will be obtained above equal
One solution is cooled to room temperature, and is then added dropwise in 1 hour in the 200mL titanium tetrachlorides that temperature remains -30 DEG C.It drips off
After so that mixture temperature is kept at -30 DEG C 1 hour, system is then warming up to 120 DEG C in 3 hours, and this temperature is protected
It holds 2 hours.After reaction when 2 is small, heat filtering separation is carried out to the solid of generation, then tetra- chlorinations of 70ml is added into solid
Titanium and 80ml octanes, reaction carry out heat filtering to obtained solid after 0.5 hour, are then carried out fully to solid catalyst with hexane
Washing, until inspection does not measure the titanium compound of precipitation in cleaning solution, obtained after dry good fluidity, particle diameter distribution uniformly, be in
Spherical solid catalyst.
(2) for polymerization with embodiment 1, polymerization result is shown in Table 1.
Embodiment 8
(1) preparation of catalytic component：
In the reactor being sufficiently displaced from by nitrogen, 5g isopropylmagnesium chlorides are added, 23ml 2- ethyl butanols stir
It mixes and is warming up to 100 DEG C, isothermal reaction 3h, solid is completely dissolved to form homogeneous and transparent solution.50 DEG C are cooled to, 1.2ml is added
Ethyl alcohol, isothermal reaction 1 hour are cooled to 30 DEG C, and 1,2- diethoxyethane 3.2ml are added, and react 2h, obtain uniform solution.
Uniform solution obtained above is cooled to room temperature, the 200mL tetra- that temperature remains 10 DEG C is then added dropwise in 1 hour
In titanium chloride.So that mixture temperature is kept 1 hour at 10 DEG C after dripping off, system is then warming up to 90 DEG C in 3 hours, 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, then is added into solid
70ml titanium tetrachlorides and 80ml decane, reaction carries out heat filtering after 0.5 hour to obtained solid, then with hexane to solid catalysis
Agent is fully washed, until inspection does not measure the titanium compound of precipitation in cleaning solution, good fluidity, grain size point are obtained after dry
Cloth uniformly, in spherical solid catalyst.
(2) for polymerization with embodiment 1, polymerization result is shown in Table 1.
Embodiment 9
(1) preparation of catalytic component：
In the reactor being sufficiently displaced from by nitrogen, addition 5g magnesium dichlorides, 50ml n-decanes, 23ml isooctanol,
Stirring is warming up to 130 DEG C, and isothermal reaction 3h, solid is completely dissolved to form homogeneous and transparent solution.70 DEG C are cooled to, is added
1.2ml methanol, isothermal reaction 1 hour are cooled to 50 DEG C, and acton 3.2ml is added, and react 2h, obtain uniform solution.
Uniform solution obtained above is cooled to room temperature, the 200mL that temperature remains -20 DEG C is then added dropwise in 1 hour
In titanium tetrachloride.So that mixture temperature is kept at -20 DEG C after dripping off 1 hour, system is then warming up to 110 in 3 hours
DEG C, 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, then to solid
Middle addition 70ml titanium tetrachlorides and 80ml hexanes, reaction carries out heat filtering after 0.5 hour to obtained solid, then with hexane to solid
Body catalyst is fully washed, until inspection does not measure the titanium compound of precipitation in cleaning solution, obtained after dry good fluidity,
Particle diameter distribution uniformly, in spherical solid catalyst.
(2) for polymerization with embodiment 1, polymerization result is shown in Table 1.
Embodiment 10
(1) preparation of catalytic component：
In the reactor being sufficiently displaced from by nitrogen, 5g magnesium dichlorides, 50ml n-decanes, 23ml dimethyl-pentens is added
Alcohol, stirring are warming up to 130 DEG C, and isothermal reaction 3h, solid is completely dissolved to form homogeneous and transparent solution.70 DEG C are cooled to, is added
1.2ml propyl alcohol, isothermal reaction 1 hour are cooled to 50 DEG C, and 1- chloro-2-ethoxy ethane 3.2ml are added, and react 2h, obtain uniform
Solution.Uniform solution obtained above is cooled to room temperature, being then added dropwise to temperature in 1 hour remains -20 DEG C
In 200mL titanium tetrachlorides.So that mixture temperature is kept at -20 DEG C after dripping off 1 hour, then system heats up in 3 hours
It is kept for 2 hours to 110 DEG C, and by this temperature.After reaction when 2 is small, to the progress heat filtering separation of the solid of generation, then to
20ml titanium tetrachlorides and 80ml hexanes are added in solid, reaction carries out heat filtering to obtained solid after 0.5 hour, then uses hexane
Solid catalyst is fully washed, until inspection does not measure the titanium compound of precipitation in cleaning solution, is flowed after dry
Property is good, particle diameter distribution is uniform, in spherical solid catalyst.
(2) for polymerization with embodiment 1, polymerization result is shown in Table 1.
Embodiment 11
(1) preparation of catalytic component：
In the reactor being sufficiently displaced from by nitrogen, addition 5g magnesium dichlorides, 50ml n-decanes, 23ml isooctanol,
Stirring is warming up to 130 DEG C, and isothermal reaction 3h, solid is completely dissolved to form homogeneous and transparent solution.70 DEG C are cooled to, is added
1.2ml ethyl alcohol, isothermal reaction 1 hour are cooled to 50 DEG C, and tetra ethoxy methane 3.2ml is added, and react 2h, obtain uniform solution.
Uniform solution obtained above is cooled to room temperature, the 150mL that temperature remains -20 DEG C is then added dropwise in 1 hour
In titanium tetrachloride.So that mixture temperature is kept at -20 DEG C after dripping off 1 hour, system is then warming up to 110 in 3 hours
DEG C, 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, then to solid
Middle addition 30ml titanium tetrachlorides and 80ml hexanes, reaction carries out heat filtering after 0.5 hour to obtained solid, then with hexane to solid
Body catalyst is fully washed, until inspection does not measure the titanium compound of precipitation in cleaning solution, obtained after dry good fluidity,
Particle diameter distribution uniformly, in spherical solid catalyst.
(2) for polymerization with embodiment 1, polymerization result is shown in Table 1.
Comparative example 1
Catalytic component is made with method same as Example 1, the difference is that being not added with tetra ethoxy methane.Catalyst
Difficulty is precipitated, solid is difficult sedimentation, fails to form catalyst.
Comparative example 2
Catalytic component is made with method same as Example 1, the difference is that tetra ethoxy methane is changed to four ethoxies
Base silane, for polymerization with embodiment 1, vinyl polymerization the results are shown in Table 1.
Comparative example 3
(1) preparation of catalytic component：
In the reactor being sufficiently displaced from by nitrogen, addition 5g magnesium dichlorides, 50ml n-decanes, 23ml isooctanol,
Stirring is warming up to 130 DEG C, and isothermal reaction 3h, solid is completely dissolved to form homogeneous and transparent solution.70 DEG C are cooled to, is added
1.2ml ethyl alcohol, isothermal reaction 1 hour are cooled to 50 DEG C, and tetra ethoxy methane 3.2ml is added, and react 2h, obtain uniform solution.
Uniform solution obtained above is cooled to room temperature, the 200mL that temperature remains -20 DEG C is then added dropwise in 1 hour
In four titanium butoxides.So that mixture temperature is kept at -20 DEG C after dripping off 1 hour, is then warming up to system in 3 hours
110 DEG C, 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, then uses oneself
Alkane fully washs solid catalyst, until inspection does not measure the titanium compound of precipitation in cleaning solution, is flowed after dry
Dynamic property is good, particle diameter distribution is uniform, in spherical solid catalyst.
(2) for polymerization with embodiment 1, polymerization result is shown in Table 1.
Comparative example 4
Catalytic component is made with method same as Example 1, the difference is that being not added with ethyl alcohol.Polymerization is the same as implementation
Example 5, polymerization result is shown in Table 1.
Comparative example 5
(1) preparation of catalytic component：
In the reaction kettle of 1.6L, be added 200mL white oils, 8.0g (0.08mol) magnesium chloride, 3g (0.01mol) octadecyl alcolol,
95mL (1.6mol) ethyl alcohol, 9.8mL (0.08mol) 2,2-dimethoxypropane, are warming up to 90 DEG C under stiring.Isothermal reaction 1
After hour, by mixture stirring at low speed (stir speed (S.S.) is 400 revs/min) dispersion 30 minutes, to be emulsified.And in above-mentioned breast
Change and 35mL (0.45mol) epoxychloropropane is added in product, react press filtration after half an hour, time of filter pressing is 9 minutes.By press filtration
Product is washed 5 times with hexane, press filtration after having washed every time, and press filtration process total time is 20 minutes.Finally product vacuum is dried,
Obtain carrier for olefin polymerization catalyst.
In the glass reaction bottle of 300mL, the titanium tetrachloride of 100mL is added, is cooled to -20 DEG C, by 40 grams of previous step systems
Standby carrier for olefin polymerization catalyst is added thereto, and stirs 30min at -20 DEG C.Later, start to be to slowly warm up to 110 DEG C,
The diisobutyl phthalate of 1.5mL is added in temperature-rise period, liquid is filtered off after maintaining 30min at 110 DEG C.Then,
Titanium tetrachloride is added to wash 2 times, is finally washed 3 times with hexane, olefin polymerization catalysis is obtained after dry.
(2) for polymerization with embodiment 1, polymerization result is shown in Table 1.
The addition that can be seen that form renovation agent from the aggregated data of table 1 improves the forming precipitation process of catalyst,
The particle diameter distribution of 1 obtained polymer of embodiment will be narrower than comparative example 2, and the fine powder content (200 mesh of ＞) of polymer is
0.2%, hence it is evident that be less than the 2.1% of comparative example 2.Polymer particle diameter distribution is significantly wider than embodiment in comparative example 5, and wherein contains thin
Point more, particle diameter distribution is uneven.By being compared to embodiment 5 and comparative example 4 as can be seen that ethyl alcohol is added in embodiment 5
Afterwards, catalyst melt index of (P hydrogen=0.73MPa) resulting polymers under high hydrogen polymerizing condition greatly improves, from 147g/
10min is increased to 452g/10min, is 3.07 times of the catalyst that comparative example 4 is not added with ethyl alcohol preparation, it will be apparent that improve catalysis
The hydrogen response of agent.
Table 1
Beneficial effects of the present invention：
Prepared catalyst of the present invention is suitable for the homopolymerization of ethylene and the copolymerization of ethylene and other alpha-olefins
Slurry process, vapor phase method, solwution method etc. can be used in polymerization methods, wherein being best with slurry process.Propylene, fourth can be used in alpha-olefin
Alkene, amylene, hexene, octene, 4- methyl 1- amylenes etc..The catalyst is compared with existing catalyst, its advantage is that catalyst particles
Grain size distribution is uniform, and particle diameter distribution is narrow, and fine polymer powder content is low, while also having good hydrogen response.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding change and deformations, but these corresponding change and deformations can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (15)
1. a kind of preparation method for vinyl polymerization or the catalytic component of combined polymerization, which is characterized in that this method includes such as
Lower step：
(1) by magnesium compound be dissolved in carbon atom quantity be 6~20 alcohols solvent in, formed solution, solution temperature be 100~
150℃；
(2) alcohol and form renovation agent of the carbon atom number less than or equal to 5 are added in above-mentioned solution, is reacted, reaction temperature
Degree is 30~100 DEG C；
(3) at a temperature of -30 DEG C~10 DEG C, above-mentioned reaction solution is added dropwise in titanium compound and is reacted, then heats to 90
DEG C~120 DEG C, solid is precipitated；
(4) the reaction was continued for the mixture of addition inert diluent and titanium compound in step (3) obtained solid, and it is heavy to obtain solid
It forms sediment；And
(5) catalytic component is obtained with precipitation in inert diluent washing step (4)；
Wherein, titanium compound general formula is Ti (OR)4-nXn, R is the alkyl that carbon atom number is less than 6 in formula, and X is halogen, and n is 0~4
Integer；
Wherein, the form renovation agent is diethoxymethane, acton, tetra ethoxy methane, 1,1- diethoxies
Base ethane, 1,2- diethoxyethane, 1- chloro-2-ethoxies ethane, the chloro- 1,1,1- triethoxy ethanes of 2-, bis- chloroethenes of 1,2-
Oxygroup ethane, 1- ethoxy propanes, 2,2- di ethyl propyl ethers, 1,1,1- triethoxies propane and 1,1,3,3- tetraethoxies third
One or more of formed group of alkane.
2. the preparation method according to claim 1 for vinyl polymerization or the catalytic component of combined polymerization, feature exists
In the magnesium compound is magnesium dihalide, the hydrate of magnesium dihalide, the alcohol adduct of magnesium dihalide, alkyl magnesium halide and hydrocarbon
One or more of formed group of oxygroup magnesium halide.
3. the preparation method according to claim 1 for vinyl polymerization or the catalytic component of combined polymerization, feature exists
In, the alcohol that the carbon atom number is 6~20 be hexanol, it is 2- methyl anyl alcohols, 2- ethyl butanols, enanthol, 2-Ethylhexyl Alcohol, pungent
One or more of alcohol, decyl alcohol, dodecanol, tetradecanol and the formed group of octadecanol.
4. the preparation method according to claim 1 for vinyl polymerization or the catalytic component of combined polymerization, feature exists
In the alcohol of, the carbon atom number less than or equal to 5 be methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol and amylalcohol institute group
At one or more of group.
5. the preparation method according to claim 1 for vinyl polymerization or the catalytic component of combined polymerization, feature exists
In the titanium compound is titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, a chlorine triethoxy titanium, dichloro
One or more of diethoxy titanium and the formed group of one ethanolato-titanium of trichlorine.
6. the preparation method according to claim 1 or 3 for vinyl polymerization or the catalytic component of combined polymerization, feature
It is, the molar ratio of alcohol and magnesium compound that the carbon atom number is 6~20 is 2~6.
7. the preparation method according to claim 1 or 4 for vinyl polymerization or the catalytic component of combined polymerization, feature
It is, the molar ratio of alcohol of the carbon atom number less than or equal to 5 and magnesium compound is 0.2~5.
8. the preparation method according to claim 1 for vinyl polymerization or the catalytic component of combined polymerization, feature exists
In the molar ratio of the form renovation agent and magnesium compound is 0.05~2.
9. being used for the preparation method of vinyl polymerization or the catalytic component of combined polymerization, feature according to claim 1 or 5
It is, the molar ratio of the titanium compound and magnesium compound is 20~50, titanium compound and titanizing in step (4) in step (3)
The molar ratio for closing object is 1~10.
10. the preparation method according to claim 1 for vinyl polymerization or the catalytic component of combined polymerization, feature exists
In the addition inert diluent in step (1).
11. prepared by a kind of any preparation method of claims 1 to 10 is used for vinyl polymerization or the catalytic component of combined polymerization.
12. a kind of catalyst being used for vinyl polymerization or combined polymerization, which is characterized in that the catalyst includes following component：
(1) catalytic component described in claim 11；And
(2) organo-aluminum compound, general formula AlR1 nX3-n, R in formula1It is halogen, n 1,2 or 3 for alkyl, X；
The proportioning of component (2) and component (1), with aluminium titanium molar ratio computing, aluminium:Titanium is 50~500.
13. the catalyst according to claim 12 for being used for vinyl polymerization or combined polymerization, which is characterized in that described is organic
Aluminium compound by triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, ethyl aluminum dichloride and sesquialter ethylmercury chloride aluminium group in groups
One or more of group.
14. the preparation method described in a kind of claim 12 for vinyl polymerization or the catalyst of combined polymerization, which is characterized in that should
The preparation method of Components of Catalysts (1) includes the following steps：
(1) by magnesium compound be dissolved in carbon atom quantity be 6~20 alcohols solvent in, formed solution, solution temperature be 100~
150℃；
(2) alcohol and form renovation agent of the carbon atom number less than or equal to 5 are added in above-mentioned solution, is reacted, reaction temperature
Degree is 30~100 DEG C；
(3) at a temperature of -30 DEG C~10 DEG C, above-mentioned reaction solution is added dropwise in titanium compound and is reacted, then heats to 90
DEG C~120 DEG C, solid is precipitated；
(4) the reaction was continued for the mixture of addition inert diluent and titanium compound in step (3) obtained solid, and it is heavy to obtain solid
It forms sediment；And
(5) catalytic component is obtained with precipitation in inert diluent washing step (4)；
Wherein, titanium compound general formula is Ti (OR)4-nXn, R is the alkyl that carbon atom number is less than 6 in formula, and X is halogen, and n is 0~4
Integer；
Wherein, the form renovation agent is diethoxymethane, acton, tetra ethoxy methane, 1,1- diethoxies
Base ethane, 1,2- diethoxyethane, 1- chloro-2-ethoxies ethane, the chloro- 1,1,1- triethoxy ethanes of 2-, bis- chloroethenes of 1,2-
Oxygroup ethane, 1- ethoxy propanes, 2,2- di ethyl propyl ethers, 1,1,1- triethoxies propane and 1,1,3,3- tetraethoxies third
One or more of formed group of alkane.
15. the catalyst for being used for vinyl polymerization or combined polymerization described in claim 12 is in ethylene polymerization or copolymerization
In application.
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