CN105384854B - A kind of catalytic component for vinyl polymerization, catalyst and preparation method thereof - Google Patents
A kind of catalytic component for vinyl polymerization, catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of catalytic components for vinyl polymerization, include the reactant of following components：(1) magnesium compound；(2) organic alcohol compound；(3) ortho acid esters electron donor；(4) titanium-containing compound；(5) at least one is without active hydrogen organo-silicon compound.The catalyst is higher with catalytic activity, polymer bulk density is high, and polymer particle size is evenly distributed, the few feature of fine powder, suitable for the slurry polymerization processes and gas-phase polymerization process of ethylene.
Description
Technical field
The present invention relates to a kind of catalyst for olefinic polymerization, are particularly used for the catalyst group of vinyl polymerization
Divide, the preparation method of catalyst and the catalyst.
Background technology
It occupies an leading position it is well known that the caltalyst of the compound containing Ti/Mg ties up in the industrialized production of polyolefin,
Research core concentrates on the polymerization activity of catalyst, the particle shape of catalyst and particle diameter distribution and the hydrogen tune of catalyst is quick
Perception and copolymerization performance etc..And in the slurry polymerization processes of ethylene, in addition to requiring catalyst that should have higher catalytic activity,
It is highly important to control the polyvinyl particle size produced and particle diameter distribution.In olefinic polymerization, especially ethylene
Sluny polymerization process in, it is easy to generate thinner polymer particle, this fine powder is easy to produce static electricity, causes " airborne dust " existing
As also easily luming sometimes, causing the blocking of equipment pipe.In the prior art, in order to obtain have uniform particle diameter and compared with
The catalyst of good particle shape, people's generally use two classes method below prepare catalyst.
The first is that the magnesium compounds such as magnesium chloride are dissolved in certain solvents to obtain homogeneous solution, then again by the solution
With titanium compound and optionally electron donor mixes, and consolidating containing magnesium, titanium and optional electron donor is obtained by the method for precipitation
Body object, and obtain catalyst granules after the solids is handled with excessive liquid titanium compound.Such as CN1099041A,
Disclosed in CN1229092.The shortcomings that this conventional method is the grain size of catalyst granules and particle diameter distribution is entirely to pass through
For the recrystallization process of precipitation process, that is, magnesium carrier ingredient come what is controlled, stability is more difficult to control.
Second is directly carried on catalyst activity component on inert carrier such as silica gel, due to the particle of silica gel
Diameter is easy to control, and particle shape is preferable, therefore evengranular catalyst particle can be obtained.But due to active on carrier
The load capacity of component is restricted, therefore Ti content is relatively low in catalyst made from this method, and polymerization activity is not high.Such as：
Using magnesium chloride, silica as carrier in CN1268520, titanium tetrachloride is active component, and the preparation method of catalyst is as follows：It will
MgCl2In tetrahydrofuran with TiCl4Reaction, then with through the processed SiO of alkyl aluminum2It mixes, is made and urges after removing tetrahydrofuran
Agent component.When for vinyl polymerization, since the Ti content in catalyst is relatively low, to which polymerization activity is relatively low.Therefore, this
Although catalyst system can be used for the gas-phase fluidized bed polymerization process of ethylene, but since lower catalytic activity is difficult to be suitable for second
In the slurry polymerization processes of alkene.
The inventors discovered that ortho acid esters electron donor is added, compounded with organosilicon compound, catalyst is easy
It settling out, catalyst can not only keep higher catalytic activity, and the bulk density of resulting polymers improves a lot,
Conducive to the load of raising ethylene polymerization plants.
Invention content
The technical problem to be solved in the present invention is to provide a kind of preparation method of catalytic component for vinyl polymerization and
Its catalyst is compounded by the way that two different electron donors are added, and the catalyst of gained has preferable catalytic activity, institute
It is high to obtain polymer bulk density, polymer particle size distribution is concentrated, and fine powder is few.
A kind of catalytic component for vinyl polymerization of the present invention, includes the reaction product of following components：(1) magnesium
Compound；(2) organic alcohol compound；(3) ortho acid esters electron donor；(4) titanium-containing compound；(5) at least one is without active hydrogen
Organo-silicon compound.
A kind of catalytic component for vinyl polymerization of the present invention, is prepared from the following steps：
(1) by magnesium halide be dissolved in the dicyandiamide solution containing organic epoxide and organic phosphorus compound formed uniformly it is molten
Liquid, solution temperature are 50~90 DEG C；During forming solution or solution formed after be added organic alcohol compound, reaction is certain
Time, obtain reaction solution；
(2) above-mentioned solution is added to ortho acid esters electron donor at a temperature of -30 DEG C~0 DEG C, reacts the regular hour；
Haptoreaction is carried out in -15 DEG C~30 DEG C and titanium compound.And mixture is to slowly warm up to 30~60 DEG C, it is added at least one
Without active hydrogen organo-silicon compound, the regular hour is reacted, solids is gradually precipitated and is formed particle, mixture is slowly heated up
To 60~120 DEG C, the reaction was continued the regular hour；
(3) said mixture is removed into unreacted reactant and solvent, and is washed using inert diluent, obtain solid catalyst
Component.
The general formula of the titanium compound is Ti (OR1)aX1 b, R in formula1It is 1~14 aliphatic group or virtue for carbon atom number
Race's alkyl, X1For halogen, a is 0,1 or 2, and b is 0 to 4 integer, a+b=3 or 4；It is preferred that titanium tetrachloride, titanium tetrabromide, the tetraiodo
Change titanium, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, titanium trichloride, dichlorodiethyl oxygroup titanium, one ethoxy of trichlorine
Or mixtures thereof one kind in base titanium.
The general formula of the ortho acid esters electron donor is R2C(OR3)3, wherein R2And R3It is identical or different, R2For hydrogen
Or carbon atom number is 1~10 alkyl or alkoxy, R3It is 1~10 alkyl for carbon atom number；The ortho acid esters electron
Body is selected from original methyl carbonate, tetraethyl orthocarbonate, tetrapropyl orthocarbonate, four butyl ester of orthocarbonic acid, trimethyl orthoformate, ortho-acetic acid
Trimethyl, former propionic acid trimethyl, trimethyl orthobutyrate, former isobutyric acid trimethyl, original acid methyl ester, triethly orthoacetate, original
Propionic acid triethyl, original acid triethyl, orthovaleric acid triethyl, original acid triethyl, tripropyl orthoformate, three isopropyl of orthoformic acid
One or more of ester, orthoformic acid tri-n-butyl.It is preferred that tetraethyl orthocarbonate, tetrapropyl orthocarbonate, four fourth of orthocarbonic acid
Ester, triethly orthoacetate, original acid triethyl.
The general formula without active hydrogen organo-silicon compound is R4 xR5 ySi(OR6)Z, wherein R4、R5、R6It is identical or not
Together, R4And R5The alkyl or halogen that respectively carbon atom number is 1~10, R6It is 1~10 alkyl, wherein x for carbon atom number, y, z are
Positive integer, 0≤x≤2,0≤y≤2,0≤z≤4, and x+y+z=4；Particular compound is selected from silicon tetrachloride, silicon bromide, four
Methoxy silane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four (2- ethyl hexyl oxies) silane, ethyl three
Methoxy silane, ethyl triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, n-propyl triethoxy
Silane, n-propyl trimethoxy silane, ruthenium trimethoxysilane, ruthenium triethoxysilane, cyclopentyl-trimethoxy-silane,
Cyclopenta triethoxysilane, 2- methylcyclopentyls trimethoxy silane, 2,3- dimethylcyclopentyls trimethoxy silane, hexamethylene
Base trimethoxy silane, cyclohexyltriethyloxysilane, methyltrimethoxysilane, methyltriethoxysilane, three second of ethyl
Oxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, normal-butyl front three
Oxysilane, ne-butyltriethoxysilaneand, trimethoxysilane, isobutyl triethoxy silane, three second of cyclohexyl
Oxysilane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, a chlorine trimethoxy silicon
Alkane, a chlorine triethoxysilane, three isopropoxy silane of ethyl, vinyltributoxysilane, trimethyl phenoxysilane, first
Base triolefin npropoxysilane, vinyl triacyloxysilanes, dimethyldimethoxysil,ne, dimethyl diethoxysilane, two
Isopropyl dimethoxysilane, diisopropyldiethoxysilane, tertbutyl methyl dimethoxysilane, tertbutyl methyl diethyl
Oxysilane, tertiary pentyl methyldiethoxysilane, dicyclopentyl dimethoxyl silane, bicyclopentyl diethoxy silane, first
Cyclopentyl diethoxy silane, methylcyclopentyl dimethoxysilane, trimethylmethoxysilane, front three base oxethyl silicon
Alkane, three cyclopenta methoxy silanes, three cyclopenta Ethoxysilanes, dicyclopentylmethyl methoxy silane and cyclopenta dimethyl
Methoxy silane etc. is one such or several is used in mixed way.It is preferred that tetraethoxysilane, tetramethoxy-silicane, four butoxy silicon
Alkane.
Magnesium compound of the present invention is the solvent that magnesium halide is dissolved in organic epoxy compound object, organic phosphorus compound
Compound formed in system, the compound are the solution of a homogeneous transparent.Wherein the magnesium halide is selected from magnesium dihalide
Or the complex compound of the water of magnesium dihalide, alcohol or electron donor.Specific compound is such as：Magnesium dichloride, dibrominated magnesium, bifluoride
Magnesium, magnesium diiodide etc., wherein it is preferred that magnesium dichloride；The complex compound of the water of the magnesium dihalide, alcohol or electron donor includes two
The complexing of the compounds such as magnesium halide and water, methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, hexanol, isooctanol, ammonia, hydroxyl ammonia, ether, ester
Object；The magnesium halide can be used alone or as a mixture.
The organic epoxy compound object is selected from carbon atom number in 2~8 aliphatic olefin, alkadienes or halogenated aliphatic group
At least one of the oxide of alkene or alkadienes, glycidol ether and inner ether.Specifically such as：Ethylene oxide, propylene oxide, ring
Oxygen butane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether, diglycidyl ether etc..
The organic phosphorus compound is the hydrocarbyl carbonate or halogenated hydrocarbons base ester of orthophosphoric acid or phosphorous acid.Specifically such as：Orthophosphoric acid
Trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, Trimethyl phosphite, triethyl phosphite, tributyl phosphite etc..Its
In in terms of every mole of magnesium halide, organic epoxy compound object：0.2~10.0mol, preferably 0.3~4.0mol；Organic phosphorus compound:
0.1~10.0mol, preferably 0.2~4.0mol.
In order to keep dissolving more abundant, inert diluent is can be optionally added in the dicyandiamide solution, usual this inertia
Diluent includes arene compounds or alkane derivative, arene compounds include benzene,toluene,xylene, monochlor-benzene,
Dichlorobenzene, trichloro-benzene, monochlorotoluene and its derivative；Alkane includes the linear paraffin, branched paraffin or ring of 3~20 carbon
One kind in alkane or their mixture, such as butane, pentane, hexane, hexamethylene, heptane etc., as long as contributing to magnesium halide molten
Solution can use.Above-mentioned inert diluent can be used alone, and also can be used in combination.
The organic alcohol compound includes the straight chain that carbon atom number is 1~10, the alcohol or carbon atom of branch or naphthenic base
Number is 6~20 alcohol containing aryl.The example of alcohol includes fatty alcohol：Methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol, third
Triol, hexanol, 2- methyl anyl alcohols, 2- ethyl butanols, n-heptanol, n-octyl alcohol, decyl alcohol etc.；Cyclic alkanol, such as cyclohexanol, methyl cyclohexane
Alcohol etc.；Aromatic alcohol, such as benzyl alcohol, methylbenzyl alcohol, ɑ-methylbenzyl alcohol, ɑ, ɑ-dimethylphenylcarbinol etc..Wherein preferred alcohol,
Butanol, 2-Ethylhexyl Alcohol, glycerine.The ratio of each alcohol in alcohol composition is not particularly limited.
For ratio between each reactant in terms of every mole of magnesium halide in magnesium compound, the dosage of Organic Alcohol is usually 0~6
Mole, preferably 0~2 mole；The dosage of titanium compound is usually 1~20 mole, preferably 1~15 mole；Ortho acid esters electron
The dosage of body is usually 0.01~2 mole, preferably 0.01~1 mole；The dosage of no active hydrogen organo-silicon compound is usually
0.01~2 mole, preferably 0.01~1 mole.
The present invention also provides a kind of catalyst for vinyl polymerization, including：(1) described above to be used for vinyl polymerization
Catalytic component；(2) organo-aluminum compound.The general formula of the organo-aluminum compound is AlR7 nX3-n, R in formula7For hydrogen or
The alkyl that carbon atom number is 1~20, X are halogen, and n is the integer of 0 n≤3 <.
The present invention also provides a kind of preparation methods of the catalytic component for vinyl polymerization, include the following steps：
(1) by magnesium halide be dissolved in the dicyandiamide solution containing organic epoxide and organic phosphorus compound formed uniformly it is molten
Liquid；During forming solution or solution formed after be added organic alcohol compound, react the regular hour, obtain reacting molten
Liquid；
(2) above-mentioned solution is added to ortho acid esters electron donor at a temperature of -30 DEG C~0 DEG C, reacts the regular hour；
Haptoreaction is carried out in -15 DEG C~30 DEG C and titanium compound.And mixture is to slowly warm up to 30~60 DEG C, it is added at least one
Silicon compound reacts the regular hour, and solids is gradually precipitated and is formed particle, mixture is to slowly warm up to 60~120 DEG C,
The reaction was continued the regular hour；
(3) said mixture is removed into unreacted reactant and solvent, and is washed using inert diluent, obtain solid catalyst
Component.
Slurry polymerization can be used when polymerization, gas-phase polymerization can also be used.
Slurry polymerization medium includes：Iso-butane, hexane, heptane, hexamethylene, naphtha, raffinate oil, hydrogasoline, kerosene,
The atent solvents such as the aliphatic saturated hydrocarbons such as benzene,toluene,xylene or aromatic hydrocarbon.
In order to adjust the molecular weight of final polymer, molecular weight regulator is made using hydrogen.
Catalyst of the present invention is higher with catalytic activity, polymer bulk density is high, and polymer particle size is evenly distributed, fine powder
It is few, suitable for the slurry polymerization processes and gas-phase polymerization process of ethylene.
Specific implementation mode
Following embodiment is to be described to more detailed citing of the invention, but the invention is not limited in these embodiments.
Embodiment 1
(1) preparation of catalytic component
In the reactor being sufficiently displaced from by high pure nitrogen, 4.0g magnesium dichlorides, toluene 80ml, epoxy are sequentially added
Chloropropane 2.2ml, tributyl phosphate 6.0ml, ethyl alcohol 3.6ml, are warming up to 70 DEG C under stirring, when solid be completely dissolved to be formed it is uniform
Solution after, reacted 2 hours at 70 DEG C.The system is cooled to -15 DEG C, tetraethyl orthocarbonate 1.0ml, reaction 0.5 is added
Hour.Then 60ml titanium tetrachlorides are slowly added dropwise, react 15 minutes；- 5 DEG C are to slowly warm up to, tetraethyl orthosilicate 3.0ml is added,
Reaction 0.5 hour.85 DEG C are to slowly warm up to, is reacted 2 hours.Stop stirring, stand, suspension is layered quickly, and it is clear to extract upper layer
Night, hexane wash four times.High pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity.
(2) 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 solid catalyst of above-mentioned preparation is added in aluminium 1.0ml, is warming up to 80 DEG C, and being passed through hydrogen makes pressure in kettle reach 0.60Mpa, then
Being passed through ethylene makes stagnation pressure in kettle reach 1.00Mpa (gauge pressure), polymerize 2 hours under the conditions of 80 DEG C, polymerization result is shown in Table 1.
Embodiment 2
(1) synthesis of catalyst is the same as embodiment 1.Only tetraethyl orthocarbonate is changed to 1.5ml, and tetraethyl orthosilicate dosage is
2.5ml。
(2) vinyl polymerization is the same as embodiment 1.Polymerization result is shown in Table 1.
Embodiment 3
(1) synthesis of catalyst is the same as embodiment 1.Only tetraethyl orthocarbonate is changed to tetrapropyl orthocarbonate, and dosage is kept
1.2ml, tetraethyl orthosilicate dosage are 3.0ml.
(2) vinyl polymerization is the same as embodiment 1.Polymerization result is shown in Table 1.
Embodiment 4
(1) synthesis of catalyst is the same as embodiment 1.Only tetraethyl orthocarbonate is changed to original acid triethyl, and dosage is
1.1ml, tetraethyl orthosilicate dosage are changed to 3.0ml.
(2) vinyl polymerization is the same as embodiment 1.Polymerization result is shown in Table 1.
Comparative example 1
(1) synthesis of catalytic component is prepared by 1 the method for CN1958620 embodiments.
(2) for vinyl polymerization condition with embodiment 1, polymerization result is shown in Table 1.
Comparative example 2
(1) synthesis of catalyst is the same as embodiment 1.Tetraethyl orthocarbonate dosage is changed to 2.6ml, and tetraethyl orthosilicate dosage is changed to
0。
(2) vinyl polymerization is the same as embodiment 1.Polymerization result is shown in Table 1.
1 polymerization result of table
It is different that from the experimental data of comparative example the preparation process introducing of catalyst of the present invention is can be seen that from 1 embodiment of table
Electron donor is compounded, and catalyst activity keeps higher level, polymer bulk density to increase significantly.
Claims (10)
1. a kind of catalytic component for vinyl polymerization includes the reaction product of following components：(1) magnesium compound；(2) organic
Alcoholic compound；(3) ortho acid esters electron donor；(4) titanium-containing compound；(5) at least one is without active hydrogen organo-silicon compound；
It is Ti (OR that the titanium-containing compound, which is selected from general formula,1)aX1 bTitanium compound, four titanium butoxides, purity titanium tetraethoxide and a chlorine
At least one of triethoxy titanium, R in formula1It is 1~14 aliphatic group or aromatic hydrocarbyl, X for carbon atom number1For halogen, a
It is 0,1 or 2, b is 0 to 4 integer, a+b=3 or 4；
It is R that the ortho acid esters electron donor, which is selected from general formula,2C(OR3)3Ortho acid esters electron donor or former three second of benzoic acid
Ester, wherein R2And R3It is identical or different, R2It is 1~10 alkyl or alkoxy, R for hydrogen or carbon atom number3It is for carbon atom number
1~10 alkyl；
The general formula without active hydrogen organo-silicon compound is R4 xR5 ySi(OR6)Z, wherein R4、R5、R6It is identical or different, R4
And R5The alkyl or halogen that respectively carbon atom number is 1~10, R6It is 1~10 alkyl, wherein x for carbon atom number, y, z are just whole
Number, 0≤x≤2,0≤y≤2,0≤z≤4, and x+y+z=4；
The magnesium compound is that magnesium halide is dissolved in institute's shape in the dicyandiamide solution of organic epoxy compound object, organic phosphorus compound
At compound.
2. a kind of catalytic component for vinyl polymerization is prepared from the following steps：(1) magnesium halide is dissolved in containing organic
Homogeneous solution is formed in the dicyandiamide solution of epoxide and organic phosphorus compound, during forming solution or solution is formed
After be added organic alcohol compound, react the regular hour, obtain reaction solution；(2) by above-mentioned solution in -30 DEG C~0 DEG C temperature
Lower addition ortho acid esters electron donor is reacted, and then carries out haptoreaction in -15 DEG C~30 DEG C and titanium compound；And it will mix
It closes object and is to slowly warm up to 30~60 DEG C, be added at least one without active hydrogen organo-silicon compound, reaction regular hour, solids
It is gradually precipitated and is formed particle, mixture is to slowly warm up to 60~120 DEG C, the reaction was continued the regular hour；It (3) will be above-mentioned mixed
It closes object and removes unreacted reactant and solvent, and washed using inert diluent, obtain ingredient of solid catalyst；
It is R that the ortho acid esters electron donor, which is selected from general formula,2C(OR3)3Ortho acid esters electron donor or former three second of benzoic acid
Ester, wherein R2And R3It is identical or different, R2It is 1~10 alkyl or alkoxy, R for hydrogen or carbon atom number3It is for carbon atom number
1~10 alkyl；The general formula without active hydrogen organo-silicon compound is R4 xR5 ySi(OR6)Z, wherein R4、R5、R6It is identical or
Difference, R4And R5The alkyl or halogen that respectively carbon atom number is 1~10, R6It is 1~10 alkyl, wherein x, y, z for carbon atom number
For positive integer, 0≤x≤2,0≤y≤2,0≤z≤4, and x+y+z=4.
3. a kind of catalytic component for vinyl polymerization according to claim 1 or 2, it is characterised in that the ortho acid
Esters electron donor is selected from tetraethyl orthocarbonate, tetrapropyl orthocarbonate, four butyl ester of orthocarbonic acid, triethly orthoacetate, former benzoic acid
Triethyl.
4. a kind of catalytic component for vinyl polymerization according to claim 1 or 2, it is characterised in that the no work
It sprinkles hydrogen organo-silicon compound and is selected from tetraethoxysilane, tetramethoxy-silicane, four butoxy silanes.
5. a kind of catalytic component for vinyl polymerization according to claim 1 or 2, it is characterised in that with magnesium compound
In every mole of magnesium halide meter, the dosage of Organic Alcohol is 0~6 mole, and the dosage of titanium compound is 1~20 mole, ortho acid esters
The dosage of electron donor is 0.01~2 mole, and the dosage of no active hydrogen organo-silicon compound is 0.01~2 mole.
6. a kind of catalytic component for vinyl polymerization according to claim 5, it is characterised in that in magnesium compound
Every mole of magnesium halide meter, the dosage of Organic Alcohol is 0~2 mole, the dosage of ortho acid esters electron donor be O.01~1 mole,
The dosage of no active hydrogen organo-silicon compound is 0.01~1 mole, and the dosage of titanium compound is 1~15 mole.
7. a kind of catalytic component for vinyl polymerization according to claim 1, it is characterised in that the Organic Alcohol
Compound includes the alcohol of straight chain, branch or naphthenic base that carbon atom number is 1~10 or carbon atom number is 6~20 containing aryl
Alcohol.
8. a kind of catalytic component for vinyl polymerization according to claim 1, it is characterised in that described contains titanizing
It includes titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, trichlorine to close object
Change or mixtures thereof one kind in titanium, dichlorodiethyl oxygroup titanium, one ethanolato-titanium of trichlorine.
9. a kind of preparation method of catalytic component for vinyl polymerization described in one of claim 1-8, including following step
Suddenly：
(1) magnesium halide is dissolved in the dicyandiamide solution containing organic epoxide and organic phosphorus compound and forms magnesium compound
Homogeneous solution, during forming solution or solution formed after be added organic alcohol compound, react the regular hour, obtain anti-
Answer solution；
(2) ortho acid esters electron donor is added in above-mentioned solution to react at a temperature of -30 DEG C~0 DEG C, then -15 DEG C~
30 DEG C carry out haptoreaction with titanium compound；And mixture is to slowly warm up to 30~60 DEG C, at least one is added without active hydrogen
Organo-silicon compound react the regular hour, and solids is gradually precipitated and formed particle, mixture is to slowly warm up to 60~
120 DEG C, the reaction was continued the regular hour；
(3) said mixture is removed into unreacted reactant and solvent, and is washed using inert diluent, obtain solid catalyst group
Point.
10. a kind of catalyst for vinyl polymerization, including：
(1) catalytic component for vinyl polymerization described in one of claim 1-8；
(2) organo-aluminum compound.
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| CN107344974B (en) | 2016-05-04 | 2020-06-09 | 中国石油天然气股份有限公司 | Olefin coordination polymerization catalyst, preparation method and application |
| CN108467442B (en) | 2018-02-11 | 2021-06-01 | 中国石油天然气股份有限公司 | Olefin coordination polymerization catalyst and application thereof |
| CN115746177B (en) * | 2021-09-03 | 2024-03-26 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization and olefin polymerization method |
| CN115746182B (en) * | 2021-09-03 | 2024-03-26 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization and olefin polymerization method |
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| CN1675255A (en) * | 2002-08-19 | 2005-09-28 | 宇部兴产株式会社 | Catalyst for polymerization or copolymerization of alpha-olefin, catalyst component therefor, and method for polymerization of alpha-olefin using the catalyst |
| CN102295717A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Catalyst compound used for vinyl polymerization reaction and catalyst thereof |
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| CN1675255A (en) * | 2002-08-19 | 2005-09-28 | 宇部兴产株式会社 | Catalyst for polymerization or copolymerization of alpha-olefin, catalyst component therefor, and method for polymerization of alpha-olefin using the catalyst |
| CN102295717A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Catalyst compound used for vinyl polymerization reaction and catalyst thereof |
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