CN105085730B - It is a kind of for the catalytic component of olefinic polymerization, preparation method and its catalyst - Google Patents
It is a kind of for the catalytic component of olefinic polymerization, preparation method and its catalyst Download PDFInfo
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Abstract
The invention discloses a kind of catalytic component for olefinic polymerization, including internal electron donor compound shown in titanium, magnesium, halogen and general formula IV,In formula, R is selected from hydrogen, hydroxyl and substituted or unsubstituted C1~C30Alkyl, be preferably selected from hydrogen, hydroxyl and substituted or unsubstituted C1~C20Alkyl, C6~C30Aryl, C6~C30Heteroaryl, C7‑C30Alkaryl and C7‑C30Aralkyl；R1、R2It is identical or different, it is selected from hydrogen and substituted or unsubstituted C1~C20Alkyl, be preferably selected from hydrogen and substituted or unsubstituted C1~C20Alkyl, C6~C20Aryl, C7‑C20Alkaryl and C7‑C20Aralkyl.According to the present invention, olefinic polymerization is used for as internal electron donor compound using general formula IV compound represented, catalytic activity is high, decay of activity is slow, and high melt index, the molecular weight distribution of resulting polymer are wide, isotacticity is high.
Description
Technical field
The present invention relates to a kind of field of olefin polymerisation, and in particular to a kind of catalytic component for olefinic polymerization.This hair
The bright preparation method for further relating to above-mentioned catalytic component and the catalyst containing the catalytic component.
Background technique
Olefin polymerization catalysis generally can be divided into three categories: traditional Ziegler-Natta catalyst, metallocene catalyst
And non-metallocene catalyst.For traditional propylene polymerization Ziegler-Natta catalyst, the prior art is used for propylene
The titanium catalyst system of polymerization is mostly using magnesium, titanium, halogen and electron donor as basis, and wherein electron donor compound is to urge
One of essential component in agent component.With the development of the electron donor compound in catalyst, polyolefin catalyst
Also it is continuously updated the replacement, researches and develops the TiCl from the first generation3AlCl3/AlEt2The TiCl of Cl system and the second generation3/AlEt2Cl
System, to the third generation be internal electron donor using magnesium chloride as carrier, monoesters or aromatic dibasic acid ester, silane is external electron donor
TiCl4·ED·MgCl2/AlR3ED system and two ethers newly developed, the caltalyst that two esters are internal electron donor
System, the catalytic polymerization activity of catalyst and the isotacticity of resulting polymers are all greatly increased.At present
A variety of internal electron donor compounds are disclosed, such as monocarboxylic esters or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine
Deng and its derivative, wherein more the most commonly used is aromatic dicarboxylic acids' esters, such as n-butyl phthalate or adjacent benzene two
Diisobutyl formate etc., reference can be made to United States Patent (USP) US4784983.0728769 institute of United States Patent (USP) US4971937 and European patent EP
In the disclosed component for olefin polymerization catalyst, using special containing there are two 1,3-, bis- ethers of ether group
Conjunction object is electron donor, such as 2- isopropyl -2- isopentyl -1,3- dimethoxy propane, 2,2- diisobutyl -1,3- dimethoxy
Propane and 9,9- bis- (methoxyl methyl) fluorenes etc..Thereafter a kind of special dibasic aliphatic carboxylic acid ester compound is disclosed again, such as
Succinate, malonate, glutarate etc. are (referring to WO98/56830, WO98/56834, WO01/57099, WO01/63231
And WO00/55215).But there is also deficiencies for current internal electron donor compound, although such as two ethers catalyst activity are higher,
The higher polymer of isotacticity can be also obtained without external electron donor, the hydrogen response of catalyst is excellent, but molecular weight distribution
It is relatively narrow, and decay of activity is very fast；And two esters catalyst polymerize in addition to the wider feature of the molecular weight distribution of resulting polymers
The rigid-tough balance of object is also preferable, but the hydrogen response of catalyst is slightly poor etc..
The present invention is desirable to provide a kind of raw catelyst component and catalyst, the catalyst catalytic activity with higher and
Macrocyclic activity stability, high melt index, the molecular weight distribution of resulting polymer are wide, isotacticity is high, have wide
Application prospect.
Summary of the invention
It is an object of the invention to aiming at the shortcomings in the prior art, provide a kind of catalyst group for olefinic polymerization
Point, preparation method and the catalyst containing the catalytic component.The catalyst provided according to the present invention is used for olefinic polymerization, especially
When it is propylene polymerization, activity, capacity of orientation, hydrogen response and stability (decay of activity is slow) with higher, institute
Obtaining polymer has wider molecular weight distribution, higher melt index and isotacticity.
According to an aspect of the invention, there is provided a kind of catalytic component for olefinic polymerization, including titanium, magnesium, halogen
Element and internal electron donor compound shown in general formula IV,
In formula, R is selected from hydrogen, hydroxyl and substituted or unsubstituted C1~C30Alkyl, be preferably selected from hydrogen, hydroxyl and substitution or
Unsubstituted C1~C20Alkyl, C6~C30Aryl, C6~C30Heteroaryl, C7-C30Alkaryl and C7-C30Aralkyl
Base；R1、R2It is identical or different, it is selected from hydrogen and substituted or unsubstituted C1~C20Alkyl, be preferably selected from hydrogen and substituted or unsubstituted
C1~C20Alkyl, C6~C20Aryl, C7-C20Alkaryl and C7-C20Aralkyl.
In a specific embodiment of above-mentioned catalytic component, the R is selected from and is preferably selected from hydrogen, hydroxyl, C1~C10
Alkyl and the C that replaces of halogen or hydroxyl6-C10Aryl, C6~C15Heteroaryl, C7~C15Aralkyl and C7~C15's
Alkaryl；R1、R2It is identical or different, it is selected from hydrogen, C1~C10Alkyl, phenyl, C7-C20Alkaryl and C7-C20Aralkyl.
Catalyst according to the invention component (or ingredient of solid catalyst, catalyst solid constituent), it is described substituted
C1~C30Alkyl, C1~C20Alkyl, C1~C20Alkyl, C6~C30Aryl, C6~C30Heteroaryl, C7-C30Alkane
Aryl and C7-C30The group that replaces of aralkyl etc., refer to that the atom in the group is substituted, such as the alkyl, ring group,
Hydrogen atom on aryl or alkaryl etc. is optionally replaced by halogen (miscellaneous) atom, alkyl or alkoxy, on the main chain
Carbon atom is optionally exchanged for heteroatoms.The alkyl can also contain double bond etc..
In a specific embodiment of above-mentioned catalytic component, the choosing of internal electron donor compound shown in the general formula IV
From N- butylidene aniline, 2,6- dimethyl-N-butylidene aniline, 4- chlorine N- butylidene aniline, N- (2- methyl propylene) aniline,
N- butylidene para-bromoaniline, 2,6- diisopropyl-N- (2- methyl propylene) aniline, 2,6- diisopropyl-N- butylidene aniline,
4- trifluoromethyl-N- butylidene aniline, 2,4,6- trimethyl-N- butylidene aniline, N- (2- methyl propylene) -1- butylamine, N-
(2- methyl propylene) -2- butylamine, N- hexylidene -1- hexylamine, N- hexylidene -1- octylame, N- pentylidene -1- octylame, 2,6- bis-
Isopropyl-N- heptamethylene aniline, 2,6- diisopropyl-N- (2,2- diphenylethylene) aniline, 2,6- dimethyl-N-(2,2-
Diphenylethylene) aniline, N- (2- phenyl-ethylene) -8- amido quinoline, N- butylidene -3- amido quinoline, 2,6- dimethyl -
N- hexylidene aniline, 2,6- diisopropyl-N- hexylidene aniline, 2,6- diisopropyl-N- (2- methyl propylene) aniline, 2,6-
Dimethyl-N-- (2- methyl propylene) aniline, 2,6- diisopropyl-N- (diphenyl methylene) aniline, 2,6- dimethyl-N-(two
Benzylidene) aniline, 2,6- diisopropyl-N- (2- phenyl-ethylene) aniline, 2,6- dimethyl-N-(2- phenyl-ethylene) benzene
Amine, 4- methyl-N- (3- heptamethylene) aniline, N- heptamethylene aniline, 2,6- diisopropyl-N- pentylidene aniline, 2,6- diisopropyl
Base-N- (2- pentylidene) aniline, N- (3- pentylidene)-naphthalidine, N- (4- heptamethylene)-naphthalidine, 4- hydroxy-n-hexichol methylene
Base-naphthalidine, N- diphenyl methylene benzylamine, N- (2- phenyl-ethylene) benzylamine, 2,6- dimethyl-N-(2,2- diphenyl Asia second
Base) aniline, 2,6- diisopropyl N- (2,2- diphenylethylene) aniline, N- (2,2- diphenylethylene) aniline, N- (2,2-
Diphenylethylene) one of -8- amido quinoline and N- (2,2- diphenylethylene) -3- amido quinoline or a variety of.
In another specific embodiment of above-mentioned catalytic component, in the catalytic component, except shown in general formula IV
It include the second internal electron donor compound in the catalytic component outside internal electron donor compound.Electron in described second
Body compound such as can be selected from least one of ester, ether, ketone and amine, be preferably selected from polybasic carboxylic acid esters compound, diol ester ester
At least one of class compound and diether compound.
One specific embodiment of catalytic component according to the present invention, catalyst described in compound shown in general formula IV
Weight percentage in component is 0.05~20%, preferably 0.5~15%, more preferably 2~10% and/or described the
Weight percentage of two external donor compounds in the catalytic component is 0.01~20%, preferably 1~15%.
In the catalytic component, the content of the titanium is 1.0~8.0wt%, and the content of magnesium is 5~50wt%, halogen
The content of element is 10~70wt%, it is preferable that the content of the titanium is 20~50wt%, and the content of magnesium is 10~30wt%, halogen
Cellulose content is 15~40wt%.
Another specific embodiment of the catalytic component according to the present invention, by the inclusion of the method system of following steps
It is standby:
1) magnesium compound is dissolved in the solvent body of organic epoxy compound object, organic phosphorus compound and inert diluent composition
It in system, is mixed after forming homogeneous solution with titanium compound, in the presence of precipitation additive, solids is precipitated；
2) solids of above-mentioned precipitation is handled using internal electron donor compound, loads with it on solids,
Optionally solids is handled with titanium compound and inert diluent again, obtains the catalytic component, wherein in described
Electron donor compound includes internal electron donor compound shown in general formula IV.
A specific embodiment according to the present invention, the internal electron donor compound further include selected from ester, ether, ketone and amine
At least one of.Preferably, the internal electron donor compound includes diol-lipid compound, polybasic carboxylic acid esters and two
Ether compound.
In the present invention, polybasic carboxylic acid esters of the polybasic carboxylic acid esters compound as disclosed in including CN85100997
Compound, related content are introduced into the present invention as reference, such as 2,3- bis- (2- ethyl-butyl) succinic acid diethyl esters, 2,3-
Diethyl -2- isopropyl succinic acid diethyl ester, 2,3- diisopropyl succinic acid diethyl ester, 2,3- di-t-butyl succinic acid two
Ethyl ester, 2,3- diisobutyl succinic acid diethyl ester, 2,3- (double trimethyl silyls) succinic acid diethyl ester, 2- (3,
3,3- trifluoro propyl) -3- methylsuccinic acid diethyl ester, 2,3- di neo-pentyl succinic acid diethyl ester, 2,3- diisoamyl amber
Amber acid diethyl ester, 2,3- (1- trifluoromethyl-ethyl) succinic acid diethyl ester, 2- isopropyl -3- isobutyl group succinic acid diethyl
Base ester, 2- tert-butyl -3- isopropyl succinic acid diethyl ester, 2- isopropyl -3- cyclohexyl succinic acid diethyl ester, 2- isoamyl
Base -3- cyclohexyl succinic acid diethyl ester, 2,2,3,3- tetramethyl succinic acid diethyl ester, 2,2,3,3- tetraethyl succinic acid two
Ethyl ester, 2,2,3,3- tetrapropyl succinic acid diethyl ester, 2,3- diethyl -2,3- diisopropyl disuccinic acid diethyl ester,
Bis- (2- ethyl-butyl) the succinic acid diisobutyl esters of 2,3-, 2,3- diethyl -2- isopropyl di-iso-octyl succinate, 2,3- bis- are different
Propyl succinic acid diisobutyl ester, 2,3- di-t-butyl succinic acid diisobutyl ester, 2,3- diisobutyl succinic acid diisobutyl ester,
2,3- (double trimethyl silyls) succinic acid diisobutyl ester, two isobutyl of 2- (3,3,3- trifluoro propyl) -3- methylsuccinic acid
Base ester, 2,3- di neo-pentyl succinic acid diisobutyl ester, 2,3- diisoamyl succinic acid diisobutyl ester, 2,3- (1- fluoroform
Base-ethyl) succinic acid diisobutyl ester, 2- isopropyl -3- isobutyl group succinic acid diisobutyl ester, 2- tert-butyl -3- isopropyl
Succinic acid diisobutyl ester, 2- isopropyl -3- cyclohexyl succinic acid diisobutyl ester, 2- isopentyl -3- cyclohexyl succinic acid two
Isobutyl, 2,2,3,3- tetramethyl succinic acid diisobutyl ester, 2,2,3,3- tetraethyl succinic acid diisobutyl ester, 2,2,3,
3- tetrapropyl succinic acid diisobutyl ester, 2,3- diethyl -2,3- diisopropyl disuccinic acid diisobutyl ester；It is preferably selected from 2,
3- diisopropyl succinic acid diethyl ester, 2,3- di-t-butyl succinic acid diethyl ester, 2,3- diisobutyl succinic acid diethyl
Ester and 2,3- diisopropyl di-iso-octyl succinate.The glycol ester compounds, such as two in patent disclosure CN101885789A
Alcohol ester ester, related content are introduced into the present invention, particular compound such as 2- isopropyl -2- isopentyl -1,3 dipropylene
Ester, 2,4-PD dibenzoate, 3- methyl -2,4-PD dibenzoate, 3- ethyl -2,4-PD dibenzoic acid
Ester, 2,2- dimethyl -2,4-PD dibenzoate, 3,5- heptandiol dibenzoate, 4- methyl -3,5- heptandiol hexichol
Formic acid esters and 4- ethyl -3,5- heptandiol dibenzoate, are preferably selected from 2,4- glycol dibenzoate, 3,5 heptandiols two
- 3,5 heptandiol dibenzoate of benzoic ether and 4- ethyl.The diether compound can also be in the art common two
Ether compound, such as 1,3- diether compound.Particular compound such as 2- isopropyl -1,3- dimethoxy propane, butyl -1 2-,
3- dimethoxy propane, 2- cyclohexyl -1,3- dimethoxy propane, 2- benzyl -1,3- dimethoxy propane, 2- phenyl -1,3-
Dimethoxy propane, 2- (1- naphthalene) -1,3- dimethoxy propane, 2- isopropyl -2- isopentyl -1,3- dimethoxy propane,
2- isopropyl -2- isobutyl group -1,3- dimethoxy propane, 2- isopropyl -2- butyl -1,3- dimethoxy propane, bis- ring of 2,2-
Amyl -1,3- hexichol acyloxy propane, 2,2- dicyclohexyl -1,3- dimethoxy propane, 2,2- dibutyl -1,3- dimethoxy
Propane, 2,2- diisobutyl -1,3- dimethoxy propane, 2,2- diisopropyl -1,3- dimethoxy propane, 2,2- diethyl -
1,3- dimethoxy propane, 2- ethyl -2- butyl -1,3- dimethoxy propane, 2,4- dimethoxy pentane, 3- ethyl -2,4-
Dimethoxy pentane, 3- methyl -2,4- dimethoxy pentane, 3- propyl -2,4- dimethoxy pentane, 3- isopropyl -2,4- two
Methyl amylether, 3,5- dimethoxy heptane, 4- ethyl -3,5- dimethoxy heptane, 4- propyl -3,5- dimethoxy heptane,
4- isopropyl -3,5- dimethoxy heptane, 9,9- dimethoxy-methyl fluorenes, 9,9- dimethoxy-methyl -4- tert-butyl fluorenes, 9,9-
Dimethoxy-methyl -4- propyl fluorenes, 9,9- dimethoxy-methyl -1,2,3,4- tetrahydro fluorenes, dimethoxy-methyl -1,2,3 9,9-,
4,5,6,7,8- octahydro fluorenes, two phenylpropyl alcohol indenes of 9,9- dimethoxy-methyl -2,3,6,7-, 9,9- dimethoxy-methyl -1,8- dichloro
Fluorenes, two norbornadiene of 7,7- dimethoxy-methyl -2,5-, 1,4- dimethoxy-butane, 2,3- diisopropyl -1,4- dimethoxy
Base butane, 2,3- dibutyl -1,4- dimethoxy-butane, 1,2- dimethoxy benzene, 3- ethyl -1,2- dimethoxy benzene, 4- fourth
Base -1,2- dimethoxy benzene, 1,8- dimethoxy-naphthalene, 2- ethyl -1,8- dimethoxy-naphthalene, 2- propyl -1,8- dimethoxy-naphthalene,
2- butyl -1,8- dimethoxy-naphthalene, 4- butyl -1,8- dimethoxy-naphthalene, 4- isobutyl group -1,8- dimethoxy-naphthalene, 4- isopropyl -
One of 1,8- dimethoxy-naphthalene and 4- propyl -1,8- dimethoxy-naphthalene are a variety of.
Precipitation additive used in the method for the present invention is not particularly limited, as long as can make solid particle that molding be precipitated.
Adducible example has: at least one of organic acid anhydride, organic acid, ester, ether and ketone.The specific example of the organic acid anhydride
It can be at least one of acetic anhydride, phthalic anhydride, succinic anhydride and maleic anhydride etc., the tool of the organic acid
Body example can be at least one of acetic acid, propionic acid, butyric acid, acrylic acid and methacrylic acid etc., the specific example of the ester
It can be dibutyl phthalate, 2,4-PD dibenzoate, 3- ethyl -2,4-PD dibenzoate, 2,3-
Diisopropyl -1,4- butanediol dibenzoate, 3,5- heptandiol dibenzoate and 4- ethyl -3,5- heptandiol dibenzoic acid
At least one of ester, the specific example of the ether can be methyl ether, ether, propyl ether, butyl ether, amyl ether, 2- isopropyl -2- isoamyl
Base dimethoxy propane and 9, at least one of 9- (dimethoxy methyl) fluorenes, the ketone can be acetone, methyl ethyl ketone and hexichol
At least one of ketone.
In another specific embodiment according to the present invention, the magnesium compound is selected from magnesium dihalide, alkoxy Mei ﹑ alkyl
One of halogen atom is by alkoxy or halogenated in the hydrate or alcohol adduct and magnesium dihalide molecular formula of Mei ﹑ magnesium dihalide
Or mixtures thereof one of derivative that alkoxy is replaced, magnesium compound are preferably selected from magnesium dihalide and its alcohol adduct and alkane
Oxygroup magnesium.
The titanium compound is that general formula is TiXn(OR)4-n, R is C in formula1~C20Alkyl, X is halogen, n=0~4.Example
Such as: titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen
Base titanium, one ethanolato-titanium of trichlorine.
The organic epoxy compound object includes C2~C8Aliphatic olefin, alkadienes, halogenated aliphatic alkene, diene
At least one of oxide, glycidol ether and inner ether of hydrocarbon.Particular compound is such as: ethylene oxide, propylene oxide, epoxy fourth
Alkane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether, diglycidyl ether, tetrahydro furan
It mutters.
The organic phosphorus compound used can be orthophosphoric acid or the hydrocarbyl carbonate or halogenated hydrocarbons base ester of phosphorous acid, this is organic
The specific example of phosphorus compound can be enumerated: orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, orthophosphoric acid triphen
Ester, Trimethyl phosphite, triethyl phosphite, tributyl phosphite or phosphorous acid benzene methyl etc., preferably orthophosphoric acid tributyl.Institute
The inert diluent can be selected from C6~C10Alkane or at least one of aromatic hydrocarbons, be preferably selected from hexane, heptan
At least one of alkane, octane, decane, benzene,toluene,xylene or derivatives thereof etc..
Another specific embodiment of the method according to the present invention, in terms of every mole of magnesium, the organic epoxy compound object
Amount be 0.2~10 mole, the amount of the organic phosphorus compound is 0.1~3 mole, and the amount of the titanium compound is 0.2~50
Mole, the amount of the precipitation additive is 0~15 mole.
In a concrete application example, in terms of every mole of magnesium, the dosage of compound shown in the general formula IV is 0.001~10
Mole, preferably 0.001-5mol, more preferable 0.02-5mol.In a preferred embodiment, compound shown in the general formula IV
Dosage is 0.02-2mol.0~10 mole, preferably 0-5mol, more preferable 0.001- of the amount of second internal electron donor compound
5mol。
Method according to the present invention, it is described " optionally solids to be carried out with titanium compound and/or inert diluent
Processing " refers to can be as needed, is used with or without titanium compound and/or inert diluent handles solids.
According to the present invention, the range being directed to, such as the restriction of group, the restriction of content or dosage, including it is upper and lower
Any specific limit value between limit value, it may include the range between any two value between upper limit value and lower limit value.
According to another aspect of the present invention, a kind of catalyst for olefinic polymerization, including following components are provided:
A. above-mentioned catalytic component or the catalytic component of above method preparation；
B. organo-aluminum compound；
C. optionally, external electron donor organo-silicon compound.
The olefin polymerization catalysis according to the present invention, the organo-aluminum compound as co-catalyst can be olefinic polymerization
The organo-aluminum compound of the common various co-catalysts that can be used as Ziegler-natta catalyst in field.It is preferred that described have
Machine aluminium compound is general formula AlR'nX3-nShown in organo-aluminum compound, wherein R' be selected from hydrogen, C1-C20Alkyl；X is halogen,
N is the integer of 1-3.
In above-mentioned catalyst, the organo-aluminum compound preferably is selected from least one of following compound: trimethyl aluminium,
Triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chlorine two
At least one of aluminium isobutyl, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride.More preferable triethyl aluminum and/or triisobutyl
Aluminium.
In above-mentioned catalyst, the dosage of the organo-aluminum compound can be the conventional amount used of this field.Generally, described
The molar ratio of organo-aluminum compound b and catalytic component a is calculated as 20-800:1 with aluminium/titanium.
In above-mentioned catalyst, " optionally, the external electron donor organo-silicon compound " mean that the catalyst can wrap
The reaction product of a containing component and b also may include the reaction product of component a, b and c.The olefinic polymerization catalysis according to the present invention
Agent, the external electron donor component can be various external electron donors known in the industry, be not particularly limited.
In above-mentioned catalyst, the external electron donor organo-silicon compound are preferably general formula R3 mSi(OR4)4-mShown in change
Close object, in formula, 0≤m≤3, R in formula3And R4For alkyl of the same race or different, naphthenic base, aryl, Lu Dai Wan Ji ﹑ amido, R3?
It can be halogen or hydrogen atom.Preferably, the organo-silicon compound are selected from least one of following compound: trimethyl first
Oxysilane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxy
Silane, cyclohexyl methyl diethoxy silane, Cyclohexylmethyldimethoxysilane, dimethoxydiphenylsilane, diphenyl
Diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, the organosilicon compounds such as vinyltrimethoxysilane
Object is preferably selected from Cyclohexyl Methyl Dimethoxysilane and diisopropyl dimethoxy silane.These organo-silicon compound can
To use individually, two or more can also be applied in combination.
The dosage of the olefin polymerization catalysis according to the present invention, external electron donor is not particularly limited.In preferred feelings
Under condition, the molar ratio of the organo-silicon compound c and catalytic component a are calculated as 0-100:1 with silicon/titanium.
According to another aspect of the present invention, a kind of method for olefinic polymerization is provided, the alkene is above-mentioned
Catalytic component, the above method preparation the catalytic component or above-mentioned catalyst in the presence of polymerize.
Olefine polymerizing process according to the present invention can be not only used for the homopolymerization of alkene, it can also be used to the copolymerization of alkene.
According to the present invention, the general formula of the alkene is CH2=CHR, R are hydrogen or C1-C12Alkyl, preferably hydrogen or C1-C6
Alkyl.As the alkene is preferably selected from least one of following compound: ethylene, propylene, 1- n-butene, 1- n-pentene,
The positive octene of 1- n-hexylene, 1- and 4-methyl-1-pentene；More preferably propylene.
According to the present invention, olefinic polymerization is used for as internal electron donor compound using general formula IV compound represented, urged
Change activity is high, decay of activity is slow, and high melt index, the molecular weight distribution of resulting polymer are wide, isotacticity is high.According to the present invention
The catalyst of offer, catalytic activity is high and stability is good, and catalyst hydrogen response is good；The mobility and processing of resulting polymers
Performance is good.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but does not constitute any limitation of the invention.
Test method
1. polymer isotacticity (%): with the heptane extraxtion method measurement of boiling.
2. melt index (g/10min): being measured according to ASTMD1238-99.
3. polymer molecular weight distribution (Mw/Mn): being measured with the gel permeation chromatograph that Waters company manufactures, solvent is used
1,2,4- trichloro-benzenes, styrene are standard specimen；The nmr analysis of compound is polymerize with Bruke dmx300MHz nmr determination
The 1H-NMR of object, solvent: deuterated chloroform, TMS are internal standard, temperature 275K.
(1) synthesis of compound
Embodiment 1
In one 250 milliliters of there-necked flask, 100 milliliters of isopropanol, 3.67 grams of 2,6-DIPA is added
With 0.1 milliliter of glacial acetic acid, the at room temperature mixed solution of 1.44 grams of agitation and dropping of n-butanal and 15 milliliters of isopropanols.It drips
It is stirred to react at room temperature 2 hours after finishing, temperature rising reflux reacts 30 hours.Reaction solution is after being concentrated under reduced pressure by column chromatography point
From solvent is ethyl acetate/petroleum ether (1:50), obtains 3.28 grams (yield 71%) of orange product 2,6- bis- is different
Propyl-N- butylidene aniline.1H-NMR(δ,ppm,TMS,CDCl3): 7.86~7.67 (3H, m, ArH), 7.36 (1H, s, CH=
), N 3.20~3.38 (2H, m, CH), 1.74~1.96 (4H, m, CH2), 1.06~1.42 (12H, m, CH2), 0.90~1.02
(3H,t,CH3)；Mass spectrum, FD-mass spectrometry:231.
Embodiment 2
In one 250 milliliters of there-necked flask, be added 100 milliliters of isopropanol, 2.53 grams of 2,6- dimethylaniline and
1.44 grams of n-butanal and 0.1 milliliter of glacial acetic acid are stirred to react 4 hours at room temperature, and temperature rising reflux reacts 36 hours.React molten
Liquid crosses column chromatography for separation after being concentrated under reduced pressure, and solvent is ethyl acetate/petroleum ether (1:50), obtains 2.60 grams (yields 74%)
Orange product 2,6- dimethyl-N-butylidene aniline.1H-NMR(δ,ppm,TMS,CDCl3): 7.73~7.58 (3H,
M, ArH), 7.43 (1H, s, CH=N), 2.60~2.82 (6H, s, CH3), 1.35~1.63 (4H, m, CH2), 0.90~1.10
(3H,t,CH3)；Mass spectrum, FD-mass spectrometry:175.
Embodiment 3
In a there-necked flask, 1.90 grams of 2,2- diphenyl acetaldehyde and 100 milliliters of isopropanol is added.It is added with stirring
(1.92 grams) and 0.1 milliliter of glacial acetic acid of 2,6-DIPA, are stirred to react 2 hours at room temperature, temperature rising reflux reaction
24 hours.Solid is precipitated after cooling, is recrystallized with the mixed solvent of ether and ethyl alcohol, product 2,6- diisopropyl-are obtained
N- (2,2- diphenylethylene) aniline (1.52 grams, yield 71%).1H-NMR(δ,ppm,TMS,CDCl3): 7.86~7.55
(10H, m, ArH), 7.42 (1H, s, CH=N), 7.12~7.28 (3H, ArH), 4.46 (1H, m, CH), 3.20~3.36 (2H,
M, CH), 1.23~1.36 (6H, d, CH3), 0.98~1.20 (6H, d, CH3)；Mass spectrum, FD-mass spectrometry:355.
Embodiment 4
In a there-necked flask, 1.20 grams of phenylacetaldehyde and 80 milliliters of methanol is added.It is added with stirring 2,6- diisopropyl
(1.93 grams) and 0.1 milliliter of glacial acetic acid of base aniline, are stirred to react 4 hours at room temperature, and temperature rising reflux reacts 32 hours.It is cooling
Solvent is removed after to room temperature, head product is purified with silicagel column, and solvent is ethyl acetate/petroleum ether (1:50), product 2 is obtained,
6- diisopropyl-N- (2- phenyl-ethylene) aniline (2.12 grams, yield 76%).1H-NMR(δ,ppm,TMS,CDCl3):7.76
~7.55 (5H, m, ArH), 7.46 (1H, s, CH=N), 7.12~7.28 (3H, ArH), 4.16 (2H, s, CH2), 3.42~
3.65 (2H, m, CH), 1.23~1.36 (6H, d, CH3), 0.98~1.20 (6H, d, CH3)；Mass spectrum, FD-mass
spectrometry:279。
Embodiment 5
In a there-necked flask, 1.20 grams of phenylacetaldehyde and 80 milliliters of ethyl alcohol is added.It is added with stirring 8- aminoquinoline
(1.44 grams) and 0.1 milliliter of glacial acetic acid, is stirred to react 2 hours at room temperature, and temperature rising reflux reacts 30 hours.After being cooled to room temperature
Solvent, head product silicagel column separating-purifying are removed, solvent is ethyl acetate/petroleum ether (1:30), obtains product N- (2- benzene
Base ethylidene) -8- amido quinoline (2.08 grams, yield 85%).1H-NMR(δ,ppm,TMS,CDCl3): 8.60~8.86 (1H, m,
), ArH 7.96~7.65 (5H, m, ArH), 7.60~7.56 (5H, m, ArH), 7.46 (1H, m, CH=N), 2.86 (2H, m,
CH2)；Mass spectrum, FD-mass spectrometry:246.
Embodiment 6
In a there-necked flask, 1.14 grams of 3- heptanone and 80 milliliters of isopropanol is added.It is different to be added with stirring 2,6- bis-
(1.93 grams) and 0.1 milliliter of glacial acetic acid of propyl aniline, are stirred to react 4 hours at room temperature, and temperature rising reflux reacts 36 hours.It is cold
But to solvent is removed after room temperature, head product is purified with silicagel column, and solvent is ethyl acetate/petroleum ether (1:50), obtains product
2,6- diisopropyl-N- (3- heptamethylene) aniline (1.58 grams, yield 58%).1H-NMR(δ,ppm,TMS,CDCl3), 7.88~
7.60 (3H, m, ArH), 7.48 (1H, m, CH=N), 3.42 (2H, m, CH), 1.62~1.84 (4H, m, CH2), 1.42~1.56
(4H, m, CH), 1.06~1.38 (12H, m, CH3), 0.90~1.10 (3H, t, CH3)；Mass spectrum, FD-mass
spectrometry:273。
(2) embodiment of the preparation of catalyst solid constituent (i.e. catalytic component)
Embodiment 7
In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate are sequentially added
Alkane 4ml, tributyl phosphate (TBP) 12.5mL are warming up to 50 DEG C, and maintain 2.5 hours under stirring, after solid is completely dissolved,
Phthalic anhydride 1.4g is added, continues to 1 hour, solution is cooled to -25 DEG C hereinafter, TiCl is added dropwise in 1 hour4, delay
Slowly 80 DEG C are warming up to, gradually solids is precipitated, DNBP (n-butyl phthalate, 0.003 mole) and the knot is added
The compound 2 of structure IV, 6- diisopropyl-N- butylidene aniline (0.003 mole) maintain temperature 1 hour, after heat filtering, are added
Toluene 150mL, washing is secondary, obtains solid, and toluene 100mL is added, and stirs 30 minutes, is warming up to 110 DEG C, is washed three times
It washs, the time is respectively 10 minutes, adds hexane 60mL and washes twice, and obtains solids 7.9g (catalyst solid constituent), contain Ti:
3.3%, Mg:23.6%, Cl:50.4%.
Embodiment 8
Same as Example 7, only by the compound 2 in embodiment 7,6- diisopropyl-N- butylidene aniline is changed to 2,
6- diisopropyl-N- (2- phenyl-ethylene) aniline.
Embodiment 9
It is same as Example 7, the compound 2 in embodiment 7 is only used, 6- diisopropyl-N- butylidene aniline is changed to 2,
6- dimethyl-N-(2,2- diphenylethylene) aniline.
Embodiment 10
Same as Example 7, only by the compound 2 in embodiment 7,6- diisopropyl-N- butylidene aniline is changed to N-
(2- phenyl-ethylene) -8- amido quinoline.
Embodiment 11
Same as Example 7, only by the compound 2 in embodiment 7,6- diisopropyl-N- butylidene aniline is changed to 2,
6- dimethyl-N-butylidene aniline.
Embodiment 12
Same as Example 7, only by the compound 2 in embodiment, 6- diisopropyl-N- butylidene aniline is changed to 2,6-
Diisopropyl-N- (2,2- diphenylethylene) aniline.
Embodiment 13
It is same as Example 7, the compound DNBP in embodiment 7 is only changed to 2,4-, bis- benzoyloxy pentane.
Embodiment 14
It is same as Example 7, only 2- isopropyl -2- isopentyl -1,3- bis- is changed to the compound DNBP in embodiment
Methoxy propane.
Embodiment 15
It is same as Example 7, only 2,4- dibutyl diethyl maleate is changed to the compound DNBP in embodiment 7.
Embodiment 16
It is same as Example 7, only 3,5-, bis- benzoyloxy heptane is changed to the compound DNBP in embodiment.
Embodiment 17
It is same as Example 7, only with the compound 2 in embodiment, the addition quantitative change of 6- diisopropyl-N- butylidene aniline
It is 0.006 mole.
Embodiment 18
It is same as Example 7, only with the compound 2 in embodiment, the addition quantitative change of 6- diisopropyl-N- butylidene aniline
It is 0.0015 mole.
Embodiment 19
In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate are sequentially added
Alkane 4ml, tributyl phosphate (TBP) 12.5mL are warming up to 50 DEG C, and maintain 2.5 hours under stirring, after solid is completely dissolved,
Phthalic anhydride 1.4g is added, continues to 1 hour, solution is cooled to -25 DEG C hereinafter, TiCl is added dropwise in 1 hour4, delay
Slowly 80 DEG C are warming up to, gradually solids is precipitated, be added 2,4-, bis- benzoyloxy pentane (0.006 mole), maintain temperature 1 small
When, after heat filtering, toluene 150mL is added, washs secondary, obtains solid, toluene 100mL is added, stir 30 minutes, be warming up to
It 110 DEG C, is washed three times, the time is respectively 10 minutes, adds the compound 2 of hexane 60mL and the structure, 6- diisopropyl
Base-N- butylidene aniline (0.006 mole) stirs 30 minutes, and hexane 60mL is added and washes twice, obtains solids 7.9g and (urges
Agent solid component), contain Ti:3.7%, Mg:26.1%, Cl:52.8%.
(3) polymerization experiment
Embodiment 20
Volume is the stainless steel cauldron of 5L, and after gaseous propylene is sufficiently displaced from, AlEt is added32.5mL, methylcyclohexyl
Dimethoxysilane (CHMMS) 5ml makes Al/Si (mol)=25, add above-described embodiment 7 preparation solid component 10mg with
And 1.2NL hydrogen, it is passed through liquid propene 2.5L, is warming up to 70 DEG C, maintains this temperature 1 hour, cools down, bleeds off pressure, discharge to obtain PP tree
Rouge, active 36500g/gCat., the isotacticity 97.1% (subordinate list 1) of resulting polymers.
Embodiment 21
With embodiment 20, only with urging in catalyst solid constituent alternative embodiment synthesized in above-described embodiment 8
Agent solid component, concrete outcome see attached list 1.
Embodiment 22
With embodiment 20, only with urging in catalyst solid constituent alternative embodiment synthesized in above-described embodiment 9
Agent solid component, concrete outcome see attached list 1.
Embodiment 23
With embodiment 20, only with urging in catalyst solid constituent alternative embodiment synthesized in above-described embodiment 10
Agent solid component.Concrete outcome sees attached list 1.
Embodiment 24
With embodiment 20, only with urging in catalyst solid constituent alternative embodiment synthesized in above-described embodiment 11
Agent solid component, concrete outcome see attached list 1.
Embodiment 25
With embodiment 20, only with urging in catalyst solid constituent alternative embodiment synthesized in above-described embodiment 12
Agent solid component, concrete outcome see attached list 1.
Embodiment 26
With embodiment 20, only with urging in catalyst solid constituent alternative embodiment synthesized in above-described embodiment 13
Agent solid component, concrete outcome see attached list 1.
Embodiment 27
With embodiment 20, only with urging in catalyst solid constituent alternative embodiment synthesized in above-described embodiment 14
Agent solid component, concrete outcome see attached list 1.
Embodiment 28
With embodiment 20, only with urging in catalyst solid constituent alternative embodiment synthesized in above-described embodiment 15
Agent solid component, concrete outcome see attached list 1.
Embodiment 29
With embodiment 20, only with urging in catalyst solid constituent alternative embodiment synthesized in above-described embodiment 16
Agent solid component, concrete outcome see attached list 1.
Embodiment 30
With embodiment 20, only with urging in catalyst solid constituent alternative embodiment synthesized in above-described embodiment 17
Agent solid component, concrete outcome see attached list 1.
Embodiment 31
With embodiment 20, only with urging in catalyst solid constituent alternative embodiment synthesized in above-described embodiment 18
Agent solid component, concrete outcome see attached list 1.
Embodiment 32
With embodiment 20, only with urging in catalyst solid constituent alternative embodiment synthesized in above-described embodiment 19
Agent solid component, concrete outcome see attached list 1.
Embodiment 33
With embodiment 20, only the polymerization reaction time in embodiment is extended for 2 hours, concrete outcome sees attached list 1.
Embodiment 34
With embodiment 20, only the polymerization reaction time in embodiment is extended for 3 hours, concrete outcome sees attached list 1.
Embodiment 35
With embodiment 24, only the polymerization reaction time in embodiment is extended for 2 hours, concrete outcome sees attached list 1.
Embodiment 36
With embodiment 24, only the polymerization reaction time in embodiment is extended for 3 hours, concrete outcome sees attached list 1.
Embodiment 37
With embodiment 20, in embodiment plus hydrogen amount is only become into 7.2NL, concrete outcome sees attached list 1.
Comparative example 1
In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate are sequentially added
Alkane 4ml, tributyl phosphate (TBP) 12.5mL are warming up to 50 DEG C, and maintain 2.5 hours under stirring, after solid is completely dissolved,
Phthalic anhydride 1.4g is added, continues to 1 hour, solution is cooled to -25 DEG C hereinafter, TiCl is added dropwise in 1 hour4, delay
Slowly 80 DEG C are warming up to, gradually solids is precipitated, be added DNBP (0.006 mole), maintained temperature 1 hour, after heat filtering, is added
Toluene 150mL, washing is secondary, obtains solid, and toluene 100mL is added, and stirs 30 minutes, is warming up to 110 DEG C, is washed three times
It washs, the time is respectively 10 minutes.Hexane 60mL is added to wash twice, obtains solids 7.4g (catalyst solid constituent), contains Ti:
2.8%, Mg:22.0%, Cl:50.6%.
Volume is the stainless steel cauldron of 5L, and after gaseous propylene is sufficiently displaced from, AlEt is added32.5mL, methylcyclohexyl
Dimethoxysilane (CHMMS) 5ml makes Al/Si (mol)=25, adds the solid component 10mg and 1.2NL of above-mentioned preparation
Hydrogen is passed through liquid propene 2.5L, is warming up to 70 DEG C, maintains this temperature 1 hour, and cooling is bled off pressure, discharge to obtain PP resin, as a result
See attached list 1.
Subordinate list 1
From table 1 it follows that the catalyst provided according to the present invention, compared with the prior art, having higher catalysis
Activity, decay of activity is slow, namely the stability with longer cycle；Obtained polymer has high isotacticity, higher
Melt index and wider molecular weight distribution, this also means that obtained polymer has better mechanical performance, mobility
And processing performance.Meanwhile the catalyst provided according to the present invention hydrogen response also with higher.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (19)
1. a kind of catalytic component for olefinic polymerization, including internal electron donor chemical combination shown in titanium, magnesium, halogen and general formula IV
Object,
In formula, R is selected from C6~C30Aryl, C6~C15Heteroaryl and C7~C15Alkaryl；R1Selected from hydrogen and unsubstituted C1
~C20Alkyl；R2Selected from hydrogen, unsubstituted C1~C20Alkyl and substituted or unsubstituted C7-C20Aralkyl；Wherein, R1
And R2It is not simultaneously hydrogen.
2. catalytic component according to claim 1, which is characterized in that R1Selected from hydrogen；R2Selected from C7-C20Aralkyl.
3. catalytic component according to claim 1, which is characterized in that internal electron donor chemical combination shown in the general formula IV
Object is selected from N- butylidene aniline, 2,6- dimethyl-N-butylidene aniline, 2,6- diisopropyl-N- butylidene aniline, 2,4,6- tri-
Methyl-N- butylidene aniline, 2,6- diisopropyl-N- heptamethylene aniline, N- (2- phenyl-ethylene) -8- amido quinoline, N- are sub-
Butyl -3- amido quinoline, 2,6- dimethyl-N-hexylidene aniline, 2,6- diisopropyl-N- hexylidene aniline, 2,6- diisopropyl
Base-N- (2- phenyl-ethylene) aniline, 2,6- dimethyl-N-(2- phenyl-ethylene) aniline, 4- methyl-N- (3- heptamethylene) benzene
Amine, N- heptamethylene aniline, 2,6- diisopropyl-N- pentylidene aniline, 2,6- diisopropyl-N- (2- pentylidene) aniline, N- (3-
Pentylidene) one of-naphthalidine and N- (4- heptamethylene)-naphthalidine or a variety of.
4. a kind of catalytic component for olefinic polymerization, including internal electron donor chemical combination shown in titanium, magnesium, halogen and general formula IV
Object,
Internal electron donor compound shown in the general formula IV is selected from 2,6- diisopropyl-N- (2,2- diphenylethylene) benzene
Amine, 2,6- dimethyl-N-(2,2- diphenylethylene) aniline, 2,6- diisopropyl-N- (diphenyl methylene) aniline, 2,6- bis-
Methyl-N- (diphenyl methylene) aniline, N- (2,2- diphenylethylene) aniline, N- (2,2- diphenylethylene) -8- amido
One of quinoline and N- (2,2- diphenylethylene) -3- amido quinoline are a variety of.
5. catalytic component described in any one of -4 according to claim 1, which is characterized in that wrapped in the catalytic component
The second internal electron donor compound is included, second internal electron donor compound is selected from least one of ester, ether, ketone and amine.
6. catalytic component according to claim 5, which is characterized in that second internal electron donor compound is selected from more
At least one of first carboxylic acid ester compound, diol-lipid compound and diether compound.
7. catalytic component described in any one of -4 according to claim 1, which is characterized in that compound shown in general formula IV exists
Weight percentage in the catalytic component is 0.05~20% and/or second internal electron donor compound is in institute
Stating the weight percentage in catalytic component is 0.01~20%.
8. catalytic component described in any one of -4 according to claim 1, which is characterized in that compound shown in general formula IV exists
Weight percentage in the catalytic component is 0.5~15% and/or second internal electron donor compound is described
Weight percentage in catalytic component is 1~15%.
9. catalytic component described in any one of -4 according to claim 1, which is characterized in that compound shown in general formula IV exists
Weight percentage in the catalytic component is 2~10%.
10. catalytic component described in any one of -4 according to claim 1 is prepared by the inclusion of the method for following steps:
1) magnesium compound is dissolved in the dicyandiamide solution of organic epoxy compound object, organic phosphorus compound and inert diluent composition
In, it is mixed after forming homogeneous solution with titanium compound, in the presence of precipitation additive, solids is precipitated；
2) solids of above-mentioned precipitation is handled using internal electron donor compound, loads with it on solids, then appoint
Selection of land titanium compound and/or inert diluent handle solids, obtain the catalytic component, the interior electron
Body compound includes general formula IV compound represented.
11. catalytic component according to claim 10, which is characterized in that the internal electron donor compound includes second
Internal electron donor compound, second internal electron donor compound are selected from least one of ester, ether, ketone and amine.
12. catalytic component according to claim 11, which is characterized in that second internal electron donor compound is selected from
At least one of polybasic carboxylic acid esters compound, diol-lipid compound and diether compound.
13. catalytic component according to claim 10, which is characterized in that in terms of every mole of magnesium, shown in the general formula IV
The dosage of compound is 0.001~10 mole；And/or second 0~10 mole of amount of internal electron donor compound.
14. catalytic component according to claim 13, which is characterized in that in terms of every mole of magnesium, shown in the general formula IV
The dosage of compound is 0.001-5mol；And/or second internal electron donor compound amount 0-5mol.
15. catalytic component according to claim 13, which is characterized in that in terms of every mole of magnesium, shown in the general formula IV
The dosage of compound is 0.02-5mol；And/or second internal electron donor compound amount 0.001-5mol.
16. a kind of catalyst for olefinic polymerization comprising the reaction product of following components:
A. catalytic component described in any one of claim 1-15；
B. organo-aluminum compound；
C. optionally, organo-silicon compound.
17. catalyst according to claim 16, which is characterized in that the organo-aluminum compound b's and catalytic component a
Molar ratio is calculated as the molar ratio of the 10-800:1 and/or organo-silicon compound c and catalytic component a with aluminium/titanium with silicon/titanium
It is calculated as 0-100:1.
18. a kind of method for olefinic polymerization, alkene catalytic component described in any one of claim 1~15
Or it is polymerize in the presence of catalyst described in claim 16 or 17.
19. according to the method for claim 18, which is characterized in that the alkene is selected from ethylene and propylene.
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| CN201410168805.7A CN105085730B (en) | 2014-04-24 | 2014-04-24 | It is a kind of for the catalytic component of olefinic polymerization, preparation method and its catalyst |
| US15/306,247 US10184017B2 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for propene polymerization, preparation method thereof, and catalyst containing the same |
| JP2016564254A JP6698032B2 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for propene polymerization, process for its preparation and catalyst containing it |
| ES15782393T ES2882951T3 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for propylene polymerization, method of preparation thereof and catalyst having the same |
| EP15782393.1A EP3135699B1 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for propylene polymerization, preparation method therefor and catalyst having same |
| KR1020167032803A KR102305567B1 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for propylene polymerization, preparation method therefor and catalyst having same |
| RU2016145950A RU2690192C2 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for polymerisation of propene, method for production thereof and catalyst containing thereof |
| CA2947095A CA2947095C (en) | 2014-04-24 | 2015-04-24 | Catalyst component for propene polymerization, preparation method thereof, and catalyst containing the same |
| MYPI2016703902A MY177142A (en) | 2014-04-24 | 2015-04-24 | Catalyst component for propene polymerization, preparation method thereof, and catalyst containing the same |
| PCT/CN2015/077379 WO2015161825A1 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for propylene polymerization, preparation method therefor and catalyst having same |
| SG11201608923UA SG11201608923UA (en) | 2014-04-24 | 2015-04-24 | Catalyst component for propylene polymerization, preparation method therefor and catalyst having same |
| SA516380133A SA516380133B1 (en) | 2014-04-24 | 2016-10-24 | Catalyst Component for Propylene Polymerization, Preparation method therefor and Catalyst having same |
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