CN107868147A - A kind of catalytic component, catalyst and its application for olefinic polymerization - Google Patents
A kind of catalytic component, catalyst and its application for olefinic polymerization Download PDFInfo
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- CN107868147A CN107868147A CN201610846996.7A CN201610846996A CN107868147A CN 107868147 A CN107868147 A CN 107868147A CN 201610846996 A CN201610846996 A CN 201610846996A CN 107868147 A CN107868147 A CN 107868147A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F10/06—Propene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
- C08F4/6465—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 containing silicium
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
- C08F4/6495—Catalysts containing a specific non-metal or metal-free compound organic containing nitrogen
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Abstract
The invention provides a kind of catalytic component for olefinic polymerization, including magnesium elements, titanium elements, halogen and internal electron donor, wherein, the internal electron donor includes the aromatic acid ester type compound shown in kitimine compound and Formula II shown in Formulas I,
Description
Technical field
The present invention relates to field of olefin polymerisation, and in particular to it is a kind of for the catalytic component of olefinic polymerization, catalyst and
It is applied.
Background technology
Olefin polymerization catalysis can be divided into three major types, i.e., traditional Ziegler-Natta catalyst, metallocene catalyst with
And non-metallocene catalyst.For traditional propylene polymerization Ziegler-Natta catalyst, electricity is given with catalyst
The development of donor compound, polyolefin catalyst are also continuously updated the replacement.TiCl of the research and development of catalyst from the first generation3/
AlCl3/AlEt2The TiCl of Cl systems and the second generation3/AlEt2Cl systems, to the third generation using magnesium chloride as carrier, monoesters or virtue
The TiCl that fragrant dibasic acid ester is internal electron donor, silane is external electron donor4·ED·MgCl2/AlR3ED systems and newly open
Two ethers of hair, the catalyst system that two esters are internal electron donor, the catalytic polymerization of catalyst are active and resulting
Polypropylene isotacticity have and be greatly improved very much.In the prior art, the titanium catalyst system for propylene polymerization is more
Using magnesium, titanium, halogen and electron donor as basis, wherein electron donor compound is essential in catalytic component
One of component.At present, it has been disclosed that a variety of electron donor compounds, such as monocarboxylic esters or multi-carboxylate, acid anhydrides, ketone, list
Ether or polyether, alcohol, amine etc. and its derivative.In recent years, disclosed in United States Patent (USP) US4971937 and European patent EP 0728769
The component for olefin polymerization catalyst in, employ special 1, the 3- diether compounds containing two ether groups
For electron donor, such as 2- isopropyl -2- isopentyl -1,3- dimethoxy propane, 2,2- diisobutyl -1,3- dimethoxy propanes
With 9,9- bis- (methoxyl methyl) fluorenes etc..Thereafter a kind of special dibasic aliphatic carboxylic acid ester compound, such as amber are disclosed again
Acid esters, malonate, glutarate etc. (referring to WO98/56830, WO98/56834, WO01/57099, WO01/63231 and
WO00/55215), the use of this kind of electron donor compound can not only improve the activity of catalyst, and gained acrylic polymers
Molecular weight distribution is substantially widened.Commercial Application is most widely aromatic dicarboxylic acids' esters at present, such as two positive fourth of phthalic acid
Ester (DNBP) or diisobutyl phthalate (DIBP) etc. (reference can be made to United States Patent (USP) US4784983), but such catalyst is deposited
Hydrogen response is poor, decay of activity is very fast the shortcomings of.
Most common non-metallocene olefin polymerization catalyst is the transient metal complex containing C=N class multidentate ligands, such as
Brookhart et al. has found diimine late transition metal complex in catalysis in olefine polymerization with higher catalytic activity first
(Johnson L.K.,Killian C.M.,Brookhart M.,J.Am.Chem.Soc.,1995,117,6414；Johnson
L.K.,Ecking S.M.,Brookhart M.,J.Am.Chem.Soc.,1996,118,267).Henceforth, to non-cyclopentadienyl gold
The research of category organic coordination compound causes the great interest of people.McConville et al. reported in 1996 a kind of chelant β-
Ti, Zr metal complex (such as formula 1) of diamines, it is the multidentate ligand of class containing N-N of first case highly active catalytic olefinic polymerization
Early transition metal complex (Scollard J.D., Mcconville D.H., Payne N.C., Vittal J.J,
Macromolecules,1996,29,5241；Scollard J.D.,Mcconville D.H.,J.Am.Chem.Soc.,
1996,118,10008)。
The non-metallocene olefin polymerization catalysis of β-Diamines complex (such as formula 2) and a kind of important part of class containing N-N
Agent.The characteristics of due to its structure, the steric hindrance and electronic effect of part be easy to by the change of the substituent on arylamine and
Be easy to regulate and control, the change of different metals and ligand environment, β-diamine based ligand can by different bonding modes with not
Corresponding metal complex is formed with metal compatibility, and such ligand compound has that synthesis is simple, is easy to carry out configuration aspects
Regulation and control the features such as, be ideal research structure and catalyst performance relation complex, therefore the part of the class formation
Compound cause people extensive concern (Bourget-Merle L., Lappert M.F., Severn J.R.,
Chem.Rev.,2002,102,3031；Kim W.K.,Fevola M.J.,Liable-Sands L.M.,Rheingold
A.L., Theopoid K.H., Organometallics, 1998,17,4541；Jin X.,Novak B.M.,
Macromolecules,2000,33,6205)。
Sinopec Beijing Chemical Research Institute polyethylene room discloses one-class bidentate part in patent CN00107258.7
Metal complex, for ethene and its copolymerization.Then respectively at patent CN02129548.4 (2002), patent
A kind of similar transition metal is disclosed in 200410086388.8 (2004) and patent 200710176588.6 (2007)
Composition catalyst, for ethene and its copolymerization.The He of patent 201010554473.8 of Chinese Academy of Sciences's Shanghai Institute of Organic Chemistry
201010108695.7 the multidentate ligand metallic catalyst of a kind of similar structures is disclosed, for ethene and its copolymerization system
The High molecular weight polyethylene of the standby ultralow degree of branching.
In above-mentioned related patent report, the catalyst for olefinic polymerization is corresponding ligand metal compound.
Up to now, there is not yet such ligand compound directly applies to the preparation of catalyst for polymerization of propylene and its gathered in propylene
Close the relevant report in terms of reaction.
The content of the invention
In view of above the deficiencies in the prior art, it is an object of the invention to develop a kind of catalyst group for olefinic polymerization
Divide and catalyst is applied with it.Compound internal electron donor (the ketimide as shown in following Formulas I is added in catalyst preparation process
Aromatic acid ester type compound shown in class compound and Formula II), form new catalytic polymerization system.Use the catalyst
For alkene especially propylene polymerization when, there is macrocyclic greater activity and hydrogen response, resulting polymers have
The characteristics of isotacticity is high, molecular weight distribution is wider.
The invention provides a kind of catalytic component for olefinic polymerization, including magnesium elements, titanium elements, halogen and interior give
Electron, wherein, the internal electron donor includes the aromatic acid esters shown described in kitimine compound and Formula II shown in Formulas I
Compound,
In Formulas I, R is hydroxyl, the C with or without halogen atom substituent1~C20Alkyl, take with or without halogen atom
Dai Ji C2~C20Alkenyl or the C with or without halogen atom substituent6~C30Aromatic radical；R1And R2It may be the same or different, point
Hydrogen, C independently are not1~C20Alkyl, C2~C20Alkenyl, C1~C20Alkoxy, C6~C30Aralkyl, C6~C30's
Alkaryl, C9~C40Polycyclic aromatic group, halogen atom or hydroxyl；A is (CR3R4)nOr hetero atom, wherein, R3And R4Can phase
It is same or different, it is separately hydrogen, C1~C20Alkyl, C2~C20Alkenyl, C6~C30Aralkyl, C6~C30Alkane virtue
Base or C9~C40Polycyclic aromatic group, the integer of n=0~6；
In Formula II, RIFor the C with or without halogen atom substituent1~C20Alkyl, with or without halogen atom substitute
The C of base2~C20Alkenyl, the C with or without halogen atom substituent2~C20Alkynyl or the C with or without halogen atom substituent6
~C30Alkaryl；RIIFor C1~C20Alkyl, C2~C20Alkenyl, C2~C20Alkynyl or C6~C30Alkaryl or ester
Base or amide groups；RIII、RIV、RVAnd RVIIt is identical or different, it is C1~C20Alkyl, C2~C20Alkenyl, C2~C20Alkynyl, C1~
C20Alkoxy, C6~C30Aralkyl, C6~C30Alkaryl, C9~C40Polycyclic aromatic group or halogen.
According to some embodiments, based on the weight of the catalytic component, the content of the magnesium elements is 5wt%-
50wt%, the contents of titanium elements are 1.0wt%-8.0wt%, and the content of halogen is 10wt%-70wt%, internal electron donor it is total
Content is 0.1wt%-20wt%.
According to some embodiments, the kitimine compound shown in the Formulas I and the aromatic acid esters shown in the Formula II
The mol ratio of compound is 1:(0.05-20), preferably 1:(0.1-10).
According to some embodiments, R is methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth
Base, amyl group, hexyl, hydroxyalkyl, phenyl, halobenzene base, alkyl-substituted phenyl, naphthyl, the base of xenyl or nitrogen-containing heterocgcies
Group.The group of the nitrogen-containing heterocgcies preferably group containing pyrroles, the group containing pyridine, the group of pyrimidine or the base containing quinoline
Group.
According to some embodiments, R1And R2Respectively methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding
Base, the tert-butyl group, amyl group.
According to some embodiments, A is (CR3R4)n, n 1,2,3 or 4.According to other embodiment, A is hetero atom, institute
It is preferably halogen, nitrogen, oxygen, phosphorus or silicon atom to state hetero atom.
In the present invention, the kitimine compound shown in Formulas I is preferably：4- fourths imido grpup -2 pentanone, the imines of 4- penta
Own imido grpup-the 2 pentanone of base -2 pentanone, 4-, the pungent imido grpup -2 pentanones of 4-, 4- [(1- methylols) tetrahydroform base] -2 pentanone,
4- hydroxypropyls imido grpup -2 pentanone, 4- hydroxyls ethyleneimine base -2 pentanone, 4- hydroxyls fourth imido grpup -2 pentanone, 4- isopropyl imido grpups -2- penta
Ketone, 4- (4- chlorobenzenes imido grpup) -2 pentanone, 4- (2,4 dichloro benzene imido grpup) -2 pentanone, 4- (4- trifluoromethylbenzene imines
Base) -2 pentanone, 4- phenyl imidos -2 pentanone, 4- (1- naphthalenes imido grpup) -2 pentanone, 4- (2- naphthalenes imido grpup) -2 pentanone, 4-
(2,6- imino dimethyl benzenes) -2 pentanone, 4- (2,6- diisopropyls phenyl imido) -2 pentanone, 4- (2,4,6- trimethylbenzenes
Imido grpup) -2 pentanone, 4- (8- quinoline imido grpup) -2 pentanone, 4- (4- quinoline imido grpup) -2 pentanone, 4- (3- quinoline imines
Base) -2 pentanone, 4- (the chloro- 6- hydroxyls phenyl imidos of 2-) -2 pentanone, 1,1,1- tri- fluoro- 4- (2,6- diisopropyl benzene imines
Base) -2 pentanone, 1,1,1- tri- fluoro- 4- (2,6- imino dimethyl benzenes) -2 pentanone, (2,6- dimethyl benzenes are sub- by 3- methyl -4-
Amido) -2 pentanone, 3- ethyls -4- (2,6- imino dimethyl benzenes) -2 pentanone, (2,6- dimethyl benzenes are sub- by 3- isopropyls -4-
Amido) -2 pentanone, 3- butyl -4- (2,6- imino dimethyl benzenes) -2 pentanone, (2,6- diisopropyl benzenes are sub- by 3- methyl -4-
Amido) -2 pentanone, 3- ethyls -4- (2,6- diisopropyls phenyl imido) -2 pentanone, 3- isopropyls -4- (2,6- diisopropyls
Phenyl imido) -2 pentanone, 3- butyl -4- (2,6- diisopropyls phenyl imido) -2 pentanone, 1- (2- furyls) -3- (2,6-
Diisopropyl phenyl imido) the fluoro- 1- butanone of -4,4,4- three, 1- (2- furyls) -3- (8- quinoline imido grpup) -4,4,4- three be fluoro-
1- butanone, the fluoro- 1- butanone of 1- (2- furyls) -3- (2,6- imino dimethyl benzenes) -4,4,4- three, 2- own imido grpup -4- heptan
Ketone, 2- isopropyl imido grpup -4- heptanone, the own imido grpup -2-HEPTANONEs of 4-, 4- isopropyls imido grpup -2-HEPTANONE, 4- (2- trimethylsilyls) second
Imido grpup -2 pentanone, 5- phenyl imido -3- heptanone, 5- (1- naphthalenes imido grpup) -3- heptanone, 5- (2- naphthalenes imido grpup) -3- heptanone,
5- (8- quinoline imido grpup) -3- heptanone, 5- (4- quinoline imido grpup) -3- heptanone, 5- (3- quinoline imido grpup) -3- heptanone, 5- (2,
6- diisopropyls phenyl imido) -3- heptanone, 5- (2,6- imino dimethyl benzenes) -3- heptanone, 5- fourth imido grpup -3- heptanone, 5-
(8- quinoline is sub- by isopropyl imido grpup -3- heptanone, 5- hydroxyl ethyleneimine base -3- heptanone, 5- hydroxyl fourth imido grpup -3- heptanone, 4- ethyls -5-
Amido) -3- heptanone, 4- methyl -5- (8- quinoline imido grpup) -3- heptanone, 4- ethyls -5- (1- naphthalenes imido grpup) -3- heptanone, 4- second
Base -5- (2- naphthalenes imido grpup) -3- heptanone, 4- ethyl -5- phenyl imido -3- heptanone, 4- butyl -5- phenyl imido -3- heptanone, 4-
Methyl -5- (2,6- diisopropyls phenyl imido) -3- heptanone, 4- ethyls -5- (2,6- diisopropyls phenyl imido) -3- heptanone,
4- isopropyls -5- (2,6- diisopropyls phenyl imido) -3- heptanone, 4- butyl -5- (2,6- diisopropyls phenyl imido) -3- heptan
Ketone, 4- methyl -5- (2,6- imino dimethyl benzenes) -3- heptanone, 4- ethyls -5- (2,6- imino dimethyl benzenes) -3- heptanone,
3- isopropyl imido grpup -5- octanones, 3- (2,6- diisopropyls phenyl imido) -5- octanones, 5- isopropyl imido grpup -3- octanones, 6- are different
Tetrahydroform base -4- octanones, 5- (2,6- diisopropyls phenyl imido) -2-HEPTANONE, 5- (2,4,6- trimethylbenzenes imido grpup) -2- heptan
Ketone, 4- methyl -5- (2,6- imino dimethyl benzenes) -2-HEPTANONE, 4- ethyls -6- (2,6- diisopropyls phenyl imido) -2- heptan
Ketone, 4- isopropyls -6- (2,6- diisopropyls phenyl imido) -2-HEPTANONE, 6- (2,6- imino dimethyl benzenes) -3- octanones, 3-
(2,6- diisopropyls phenyl imido) -1,3- diphenyl -1- acetone, 4- (2,6- diisopropyls phenyl imido) -4- phenyl -2- fourths
Ketone, 3- (2,6- imino dimethyl benzenes) -1,3- diphenyl -1- acetone, 3- (2,6- diisopropyls phenyl imido) -1- phenyl -
1- butanone, 3- (2,6- imino dimethyl benzenes) -1- phenyl -1- butanone, 3- (8- quinoline imido grpup) -1,3- diphenyl -1- third
One or more in ketone, 3- (3- quinoline imido grpup) -1,3- diphenyl -1- acetone.
According to some embodiments, RIFor methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth
Base, amyl group, isopentyl, neopentyl, hexyl, vinyl, pi-allyl, acetenyl, phenyl, halobenzene base, alkyl-substituted phenyl, naphthalene
Base or xenyl.
According to some embodiments, RIIFor methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth
Base, amyl group, isopentyl, neopentyl, hexyl, vinyl, pi-allyl, acetenyl, phenyl, halobenzene base, alkyl-substituted phenyl, naphthalene
Base, xenyl, ethoxycarbonyl, the third oxygen formoxyl, isopropyl oxygen formoxyl, fourth oxygen formoxyl, isobutyl oxygen formoxyl, own oxygen formyl
Base, dissident's oxygen formoxyl, new oxygen formoxyl, oxygen formoxyl in heptan, different oxygen in heptan formoxyl, new oxygen in heptan formoxyl, pungent oxygen formoxyl,
Different pungent oxygen formoxyl or new pungent oxygen formoxyl.
In the present invention, the aromatic acid ester type compound shown in Formula II is preferably：Ethyl benzoate, propyl benzoate, benzene
Butyl formate, amyl benzoate, hexyl-benzoate, benzoic acid heptyl ester, octyl benzoate, benzoic acid nonyl ester, n-decyl benzoate, benzene
Iso-butyl formate, isoamyl benzoate, benzoic acid dissident ester, benzoic acid isocyanate, the different monooctyl ester of benzoic acid, Isononyl benzoate,
Isodecyl benzoate, benzoic acid peopentyl ester, the benzoic acid newly new heptyl ester of own ester, benzoic acid, the new monooctyl ester of benzoic acid, the pungent nonyl of benzoic acid
The new last of the ten Heavenly stems ester of ester, benzoic acid, diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, O-phthalic
Sour di-n-butyl, amyl phthalate, di-iso-amyl phthalate, the peopentyl ester of phthalic acid two, O-phthalic
Sour dihexyl, dibutyl phthalate (DHP), dioctyl phthalate, dinonyl phthalate, the dissident of phthalic acid two
Ester, diisoheptyl phthalate, diisooctyl phthalate, diisononyl phthalate, 3- methylphthalic acids
Diisobutyl ester, 3- methylphthalic acids di-n-butyl, 3- methylphthalic acids diisoamyl ester, 3- methylphthalic acids two
N-pentyl ester, 3- methylphthalic acids di-isooctyl, 3- methylphthalic acids di-n-octyl, 3- ethyls phthalic acid two are different
Butyl ester, 3- ethyls n-butyl phthalate, 3- ethyls di-n-octyl phthalate, the isobutyl of 3- ethyls phthalic acid two
Ester, 3- ethyls amyl phthalate, 3- ethyls di-iso-amyl phthalate, the isobutyl of 3- propyl group phthalic acid two
Ester, 3- propyl group n-butyl phthalate, 3- chloro-o-phthalic acids diisobutyl ester, 3- butyl diisobutyl phthalate,
3- butyl n-butyl phthalate, 4- butyl n-butyl phthalate, 4- propyl group diisobutyl phthalate, 4-
Butyl di-iso-amyl phthalate, 4- chloro-o-phthalic acids di-n-butyl, 4- chloro-o-phthalic acids diisobutyl ester, 4- chlorine neighbour's benzene
One kind in dioctyl phthalate di-n-octyl, 4- methoxyl groups n-butyl phthalate and 4- methoxyl group diisobutyl phthalates
It is or a variety of.
The catalytic component provided by the invention can be prepared by following optional method：
Method 1：Magnesium halide is dissolved in the homogeneous solution that organic epoxy compound thing and organic phosphorus compound form, can also be added
Enter inert diluent.Above-mentioned homogeneous solution and titanium tetrahalide or derivatives thereof mix, and when thering is precipitation additive to deposit in reaction system
When, just have solids precipitation.The compound of the Formulas I and Formula II is attached on solids, then with titanium tetrahalide or inertia
Diluent treatment, obtain the ingredient of solid catalyst for including the compositions such as titanium, magnesium, halogen, electron donor.
The organic epoxy compound thing preferably includes C2~C15Aliphatic alkane, alkene, alkadienes, halogenated aliphatic alkene
At least one of hydrocarbon, the oxide of alkadienes, glycidol ether and inner ether.Particular compound for example epoxy butane, expoxy propane,
Oxirane, butadiene oxide, butadiene double oxide, epoxychloropropane, epoxy chlorobutane, epoxy chloropentane, methyl contracting
Water glycerin ether, diglycidyl ether, tetrahydrofuran, oxinane etc..More preferably include oxirane, expoxy propane, epoxy chlorine
Propane, tetrahydrofuran, oxinane.
The organic phosphorus compound preferably includes the hydrocarbyl carbonate or halogenated hydrocarbons base ester of orthophosphoric acid or phosphorous acid, organic phosphatization
The specific example of compound such as orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, orthophosphoric acid triamyl, orthophosphoric acid three
Own ester, the heptyl ester of orthophosphoric acid three, the monooctyl ester of orthophosphoric acid three, orthophosphoric acid triphenylmethyl methacrylate, Trimethyl phosphite, triethyl phosphite, phosphorous acid
Tributyl or phosphorous acid benzene methyl etc., more preferably orthophosphoric acid tributyl, orthophosphoric acid triethyl.
The inert diluent preferably is selected from C5~C20At least one of alkane, cycloalkane and aromatic hydrocarbons, such as hexane, heptan
Alkane, octane, decane, hexamethylene, benzene,toluene,xylene or derivatives thereof etc., more preferably including hexane, toluene.
Method 2：By magnesium halide or organo-magnesium compound, alcohol compound and titanate ester or halogenated titanium compound in inertia
Stirring is sufficiently mixed in solvent, cooling obtains carrier after heating or addition atent solvent obtains uniform alcohol adduct solution.Will be upper
State carrier or homogeneous solution and titanium tetrahalide or derivatives thereof to mix, heat temperature raising after a period of time is maintained under low temperature, adds institute
The compound of Formulas I and Formula II is stated, is then handled with titanium tetrahalide or inert diluent, finally by filtering, wash, after drying
To the ingredient of solid catalyst for including the compositions such as titanium, magnesium, halogen, electron donor.
The magnesium halide preferably includes magnesium dichloride, dibrominated magnesium, magnesium diiodide, methoxy magnesium chloride, ethyoxyl chlorination
At least one of magnesium, propoxyl group magnesium chloride, butoxy magnesium chloride etc., more preferably magnesium dichloride and/or ethyoxyl magnesium chloride.
The organo-magnesium compound preferably includes dimethyl magnesium, magnesium ethide, dipropyl magnesium, dibutylmagnesium, Methylethyl
Magnesium, methyl-propyl magnesium, methyl butyl magnesium, ethyl propyl magnesium, ethyl-butyl magnesium, dimethoxy magnesium, diethoxy magnesium, dipropoxy
At least one of magnesium, ethoxyethyl group magnesium, dibutoxy magnesium, two isobutoxy magnesium etc., more preferably dibutylmagnesium, magnesium ethide
Or diethoxy magnesium.
Method 3：Magnesium halide is dissolved in the homogeneous solution that organic epoxy compound thing and organic phosphorus compound form, can also be added
Enter inert diluent, add the compound of the Formulas I and Formula II.Above-mentioned solution and titanium tetrahalide or derivatives thereof are mixed, it is low
Temperature is lower to maintain heat temperature raising after a period of time, then is handled with titanium tetrahalide or inert diluent, last filtered, washing, dries
The solid catalyst for including the compositions such as titanium, magnesium, halogen, electron donor is obtained afterwards.
Method 4：Magnesium halide is dissolved in the homogeneous solution that organic epoxy compound thing and organic phosphorus compound form, can also be added
Enter inert diluent.Above-mentioned homogeneous solution and titanium tetrahalide or derivatives thereof mix, and when thering is precipitation additive to deposit in reaction system
When, just have solids precipitation.The compound of the Formula II is attached on solids, again with described after titanium tetrahalide is handled
Compound of formula I processing, then handled with inert diluent, finally obtain including titanium, magnesium, halogen after filtration, washing and drying
The solid catalyst of the compositions such as element, electron donor.
Present invention also offers a kind of catalyst for alkene particularly propylene polymerization, including：A) the catalyst group
Point；B) organo-aluminum compound；And C) organo-silicon compound.
Wherein, A) and B) be the catalyst necessary component, C) be the catalyst optional Component.
In the present invention, described organo-aluminum compound is selected from trialkylaluminium, dialkylaluminum chloride, alkyl aluminum chloride, alkane
Base aikyiaiurnirsoxan beta, preferably C1-C6Trialkyl aluminium chloride and dialkylaluminum chloride, as trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum,
Triisopropylaluminiuand, three n-butylaluminums, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, a chlorine two
At least one in aluminium ethide, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride.More preferably triethyl aluminum
And/or triisobutyl aluminium.
In the present invention, the component B) dosage can be this area conventional amount used.Usually, organic calorize
Compound B) with catalytic component A) mol ratio 5-2000 is calculated as with aluminium/titanium:1.
Organo-silicon compound of the present invention are preferably general formula R5 mSi(OR6)4-mShown compound, in formula, 0≤m in formula
≤ 3, R5And R6For identical or different alkyl, cycloalkyl, aryl, Lu Dai Wan Ji ﹑ amidos, R5Can also be halogen or hydrogen atom.
Preferably, the organo-silicon compound are selected from least one of following compound：Trimethylmethoxysilane, trimethyl ethoxy
Base silane, trimethyl phenoxysilane, three n-propyl methoxy silanes, dimethyldimethoxysil,ne, dipropyl dimethoxy
Silane, dibutyldimethoxysilane, diamyl dimethoxysilane, diisopropyl dimethoxy silane, diisobutyl diformazan
TMOS, dimethyldiethoxysilane, cyclohexyl methyl diethoxy silane, Cyclohexyl Methyl Dimethoxysilane, ring
Hexyl dimethyl methoxy silane, hexyl diethylmethoxysilane, dicyclopentyl dimethoxyl silane, cyclopenta diethyl first
TMOS, cyclopenta isopropyl dimethoxysilane, cyclopenta isobutyl group dimethoxysilane, 4- methylcyclohexylmethyls two
Methoxy silane, 4- methylcyclohexyl ethyldimethoxysilanes, 4- methylcyclohexyl propyldimethoxy-silanes, two (4- first
Butylcyclohexyl) dimethoxysilane, 4- methylcyclohexyl dicyclopentyldimetoxy silanes, 4- methyl cyclohexane cyclopentyl dimethoxys
Silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e,
Vinyltrimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes etc. are organic
Silicon compound, preferably selected from Cyclohexyl Methyl Dimethoxysilane, dicyclopentyl dimethoxyl silane and/or diisopropyl two
Methoxy silane.These organo-silicon compound can be used individually, and two or more can also be applied in combination.
In the present invention, the component C) dosage be not particularly limited.In situations where it is preferred, the organosilicon compound
Thing C) with catalytic component A) mol ratio be calculated as (0-500) with silicon/titanium:1.
Present invention also offers lead the catalytic component and catalyst in field of olefin polymerisation, especially propylene polymerization
Application in domain.
Beneficial effects of the present invention：Using catalyst of the present invention be used for alkene especially propylene polymerization when,
The hydrogen response of catalyst can significantly improve, and catalyst activity is higher and with long period activity, the molecule of resulting polymers
Measure wider distribution.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is unreceipted specific in embodiment
Condition person, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, it is
The conventional products of acquisition purchased in market can be passed through.
Method of testing：
1st, melt index (MI)：Determined according to GB/T3682-2000；
2nd, acrylic polymers isotacticity index (II)：Determined using heptane extraction process：The polymer samples that 2g is dried, are placed on
After being extracted 6 hours with boiling heptane in extractor, by the polymer weight (g) obtained by residue drying to constant weight and the ratio of 2 (g)
Value is isotacticity；
3rd, polymer molecular weight distribution MWD (MWD=Mw/Mn)：Using PL-GPC220, using trichloro-benzenes as solvent, 150
(standard specimen is determined at DEG C：Polystyrene, flow velocity：1.0mL/min, pillar：3x Plgel 10um MlxED-B 300x7.5nm).
4th, activity calculates：Catalyst activity=(the polyolefin quality of preparation)/(catalyst solid component quality) g/g.
Embodiment 1
Synthesize 4- (2,6- diisopropyls phenyl imido) -2 pentanone：In there-necked flask, nitrogen adds 2.00 grams after blowing row
Acetylacetone,2,4-pentanedione, 80 milliliters of isopropanols and 0.3 milliliter of glacial acetic acid, stir at room temperature.It is slowly added dropwise at room temperature into containing
50 milliliters of aqueous isopropanols of 3.54 grams of 2,6-DIPAs, add the temperature rising reflux reaction 16 after 4 hours of rear stirring reaction
Hour.Reaction solution obtains 3.52 grams of 4- (2,6- diisopropyl phenyl imido) -2- penta through being concentrated under reduced pressure after crossing column chromatography for separation
Ketone (yield 68%).1H-NMR(δ,ppm,TMS,CDCl3):7.63~7.60 (1H, m, ArH), 7.02~6.98 (2H, m,
), ArH 3.35~3.31 (2H, m, CH), 3.24~3.20 (2H, s, CH2), 2.10~2.07 (3H, s, CH3), 1.38~1.32
(6H,m,CH3), 1.25~1.21 (6H, m, CH3), 1.03~0.98 (3H, m, CH3)；Mass spectrum, FD-MS:259.
Embodiment 2
Synthesize 4- phenyl imidos -2 pentanone：In 250 milliliters of there-necked flask, nitrogen blows the acetyl of 2.00 grams of addition after row
Acetone, 60 milliliters of absolute ethyl alcohol and 15 milliliters of toluene, stir at room temperature.Be slowly added dropwise at room temperature into be dissolved in 40 milli
Rise 1.92 grams of aniline in ethanol solution, stirring reaction temperature rising reflux reaction 12 hours after 2 hours.Reaction solution is dense through depressurizing
Contracting, cross column chromatography for separation and obtain 2.03 grams of 4- phenyl imidos 2 pentanones (yield 58%).1H-NMR(δ,ppm,TMS,CDCl3):
7.96~7.90 (3H, m, ArH), 7.53~7.47 (2H, m, ArH), 3.22~3.18 (2H, s, CH2), 2.10~2.06 (3H,
s,CH3), 1.02~0.97 (3H, s, CH3)；Mass spectrum, FD-MS:175.
Embodiment 3
Synthesize 4- (2,6- imino dimethyl benzenes) -2 pentanone：In there-necked flask, nitrogen blows the second of 2.00 grams of addition after row
Acyl acetone, 80 milliliters of isopropanol and 0.2 milliliter of glacial acetic acid, stir at room temperature.It is slowly added dropwise at room temperature into containing
30 milliliters of aqueous isopropanols of 2.42 grams of 2,6- dimethylanilines, add rear stirring reaction after 2 hours temperature rising reflux reaction it is 18 small
When.Reaction solution is concentrated, and weak yellow liquid 1.42 grams of 4- (2,6- imino dimethyl benzene) -2- is obtained after crossing column chromatography for separation
Pentanone (yield 70%).1H-NMR(δ,ppm,TMS,CDCl3):7.62~7.59 (1H, m, ArH), 7.02~6.98 (2H, m,
), ArH 3.31~3.28 (2H, m, CH2), 2.54~2.51 (6H, m, CH3), 2.10~2.07 (3H, s, CH3), 1.04~0.99
(3H,s,CH3)；Mass spectrum, FD-MS:203.
Embodiment 4
Synthesize 4- (2- hydroxypropyls phenyl imido) -2 pentanone：In 250 milliliters of there-necked flasks, nitrogen adds 2.00 after blowing row
Gram acetylacetone,2,4-pentanedione, 80 milliliters of absolute ethyl alcohol and 30 milliliters of toluene, stir.It is slowly added dropwise at room temperature into containing 3.04 grams
40 milliliters of ethanol solutions of 2- hydroxypropyl aniline, after 4 hours temperature rising reflux reaction 24 hours for stirring reaction at room temperature.Reaction
Solution obtains 3.05 grams of 4- (2- hydroxypropyls phenyl imido) -2 pentanone (yield 58%) through being concentrated under reduced pressure after crossing column chromatography for separation
。1H-NMR(δ,ppm,TMS,CDCl3):7.66~7.64 (1H, m, ArH), 7.38~7.36 (2H, m, ArH), 7.08~7.06
(1H, m, ArH), 3.67~3.63 (1H, s, OH), 3.45~3.43 (2H, s, CH2), 3.15~3.13 (2H, s, CH2),2.65
~2.63 (2H, s, CH2), 2.14~2.12 (3H, s, CH3), 1.96~1.94 (3H, s, CH3), 1.45~1.42 (2H, m,
CH3)；Mass spectrum, FD-MS:233.
Embodiment 5
Synthesize compound 4- (2,4,6- trimethylbenzenes imido grpup) -2 pentanone：In there-necked flask, nitrogen adds after blowing row
2.00 grams of acetylacetone,2,4-pentanedione, 80 milliliters of absolute ethyl alcohol and 0.5 milliliter of glacial acetic acid, stir at room temperature.It is slow at room temperature
It is added dropwise to containing 2.70 gram 2,50 milliliters of ethanol solutions of 4,6- trimethylanilines, adds rear stirring reaction and heated up back after 2 hours
Stream reaction 36 hours.Reaction solution obtains 2.70 grams of 4- (2,4,6- trimethylbenzene imines through being concentrated under reduced pressure after crossing column chromatography for separation
Base) -2 pentanone (yield 62%).1H-NMR(δ,ppm,TMS,CDCl3):7.86~7.84 (2H, m, ArH), 3.28~3.24
(2H,m,CH2), 2.54~2.51 (9H, m, CH3), 2.12~2.08 (3H, s, CH3), 1.18~1.14 (3H, s, CH3)；Matter
Spectrum, FD-MS:217.Embodiment 6
Synthesize 4- (2,6- diisopropyls phenyl imido) -4- Phenyl 2 butanones：250 milliliter three after row is blown through nitrogen
In mouth bottle, 1.62 grams of benzoylacetone, 60 milliliters of isopropanol and 0.5 milliliter of formic acid are added, is stirred at room temperature.
1.77 grams of 2,6-DIPAs being dissolved in 40 milliliters of aqueous isopropanols are slowly added dropwise at room temperature, are stirred after adding anti-
Answer 4 hours, temperature rising reflux reacts 36 hours.Reaction solution obtains faint yellow solid after being concentrated under reduced pressure, after ethyl alcohol recrystallization
Obtain white crystal 2.02 grams (yields 63%).1H-NMR(δ,ppm,TMS,CDCl3):7.72~7.68 (3H, m, ArH), 7.46
~7.40 (3H, m, ArH), 7.02~6.98 (2H, m, ArH), 3.35~3.31 (2H, m, CH), 3.24~3.20 (2H, s,
CH2), 2.10~2.07 (3H, s, CH3), 1.38~1.32 (6H, m, CH3), 1.25~1.21 (6H, m, CH3)；Mass spectrum, FD-
MS:321。
Embodiment 7
Synthesize 3- (2,6- diisopropyl phenyl imido) -1,3- diphenyl -1- acetone：250 millis after row is blown through nitrogen
Rise in there-necked flask, add 2.24 grams of dibenzoyl methane, 80 milliliters of isopropanol and 0.5 milliliter of acetic acid, stir at room temperature
Mix uniformly.1.80 grams of 2,6-DIPAs being dissolved in 20 milliliters of aqueous isopropanols are slowly added dropwise at room temperature, add
Stirring reaction 2 hours afterwards, temperature rising reflux are cooled to room temperature after reacting 8 hours.Reaction solution obtains yellow solid after being concentrated under reduced pressure,
With obtaining light yellow crystal 2.65 grams (yields 69%) after ethyl alcohol recrystallization.1H-NMR(δ,ppm,TMS,CDCl3):7.86~
7.84 (2H, m, ArH), 7.68~7.63 (3H, m, ArH), 7.46~7.40 (3H, m, ArH), 7.32~7.28 (3H, m,
), ArH 7.02~6.98 (2H, m, ArH), 3.35~3.31 (2H, m, CH), 3.24~3.20 (2H, s, CH2), 1.28~1.25
(6H,m,CH3), 1.18~1.14 (6H, m, CH3)；Mass spectrum, FD-MS:383.
Embodiment 8
Synthesize 3- (2,6- diisopropyls phenyl imido) -1- phenyl -1- butanone：250 milliliter three after row is blown through nitrogen
In mouth bottle, 1.62 grams of benzoylacetone, 60 milliliters of isopropanol and 0.4 milliliter of formic acid are added, is stirred at room temperature.
1.77 grams of 2,6-DIPAs being dissolved in 40 milliliters of aqueous isopropanols are slowly added dropwise at room temperature, are stirred after adding anti-
Answer 12 hours, temperature rising reflux reacts 12 hours.Reaction solution obtains faint yellow solid after being concentrated under reduced pressure, after ethyl alcohol recrystallization
Obtain white crystal 1.28 grams (yields 40%).1H-NMR(δ,ppm,TMS,CDCl3):7.86~7.82 (3H, m, ArH), 7.46
~7.42 (2H, m, ArH), 7.26~7.14 (2H, m, ArH), 3.35~3.31 (2H, m, CH), 3.24~3.21 (2H, m,
CH2), 1.36~1.32 (6H, m, CH3), 1.24~1.21 (6H, m, CH3)；Mass spectrum, FD-MS:321.
Embodiment 9
Synthesize 5- (2,6- diisopropyls phenyl imido) -3- heptanone：In 250 milliliters of there-necked flasks after blowing row through nitrogen,
1.28 grams of 3,5- heptadione, 80 milliliters of isopropanol and 0.2 milliliter of acetic acid is added, is stirred at room temperature.Delay at room temperature
Slowly 1.78 grams of 2,6-DIPAs being dissolved in 20 milliliters of aqueous isopropanols are added dropwise to, add rear stirring reaction 2 hours,
Temperature rising reflux is cooled to room temperature after reacting 24 hours.Reaction solution obtains yellow liquid after being concentrated under reduced pressure, after crossing column chromatography for separation
Obtain weak yellow liquid 1.55 grams (yields 54%).1H-NMR(δ,ppm,TMS,CDCl3):7.66~7.64 (1H, m, ArH),
7.11~7.08 (2H, m, ArH), 3.31~3.28 (2H, m, CH), 3.22~3.18 (2H, s, CH2), 2.50~2.47 (2H,
m,CH2), 1.68~1.66 (2H, m, CH2), 1.28~1.25 (6H, m, CH3), 1.18~1.14 (6H, m, CH3), 1.12~
1.07(3H,t,CH3), 0.98~0.94 (3H, t, CH3)；Mass spectrum, FD-MS:287.
Embodiment 10
Synthesize 4- (1- naphthalenes imido grpup) -2 pentanone：In the there-necked flask after blowing row through nitrogen, 2.00 grams of levulinic is added
Ketone, 100 milliliters of toluene and 0.5 gram of p-methyl benzenesulfonic acid, stir at room temperature.It is slowly added dropwise at room temperature into containing 2.84 grams
The toluene solution of naphthalidine, divide water back flow reaction 24 hours.It is molten to add saturated sodium bicarbonate through removal of solvent under reduced pressure for reaction solution
100 milliliters of liquid stirs 2 hours.Extracted respectively three times with 50 milliliters of absolute ethers, merge organic phase, anhydrous sodium sulfate drying, remove
Solvent is removed, head product ethyl alcohol recrystallization, obtains 2.70 grams of 4- (1- naphthalenes imido grpup) -2 pentanone (yield 60%).1H-NMR(δ,
ppm,TMS,CDCl3):8.14~8.10 (3H, m, ArH), 7.86~7.82 (2H, m, ArH), 7.34~7.30 (2H, m,
), ArH 3.22~3.18 (2H, s, CH2), 2.10~2.07 (3H, s, CH3), 1.08~1.05 (3H, s, CH3)；Mass spectrum, FD-
MS:225。
Embodiment 11
Synthesize three fluoro- 2 pentanones of 4- (2,6- diisopropyls phenyl imido) -1,1,1-：There-necked flask after row is blown through nitrogen
In, 1,1,1- tri- fluoro- 2,4- pentanediones, 100 milliliters of toluene and the 0.35 gram of p-methyl benzenesulfonic acid of 1.54 grams of addition, at room temperature
Stir.It is slowly added dropwise and is reacted 24 hours into 1.78 grams of 2,6-DIPAs, reflux water-dividing at room temperature.It is cooled to room
Temperature, reaction solution add 100 milliliters of saturated sodium bicarbonate solution and stirred 2 hours through removal of solvent under reduced pressure.With 60 milliliters of anhydrous second
Ether extracts three times respectively, merges organic phase, and anhydrous sodium sulfate drying removes solvent, and head product obtains after column chromatography for separation
1.86 grams of weak yellow liquids (yield 60%).1H-NMR(δ,ppm,TMS,CDCl3):7.63~7.60 (1H, m, ArH), 7.06~
7.03 (2H, m, ArH), 3.36~3.32 (2H, m, CH), 3.22~3.18 (2H, s, CH2), 1.25~1.22 (6H, m, CH3),
1.16~1.13 (6H, m, CH3), 0.98~0.95 (3H, t, CH3)；Mass spectrum:FD-MS:313.
Embodiment 12
Synthesize 4- ethyls -5- (2,6- diisopropyls phenyl imido) -3- heptanone：250 milliliter three after row is blown through nitrogen
In mouth bottle, 2.56 grams of 3,5- heptadione, 80 milliliters of isopropanol and 0.3 milliliter of acetic acid are added, is stirred at room temperature.Room
3.56 grams of 2,6-DIPAs being dissolved in 40 milliliters of aqueous isopropanols are slowly added dropwise under temperature, add rear stirring reaction
2 hours, temperature rising reflux was cooled to room temperature after reacting 36 hours.Reaction solution obtains yellow liquid after being concentrated under reduced pressure, and crosses column chromatography
Weak yellow liquid 3.30 grams (yields 54%) is obtained after separation.1H-NMR(δ,ppm,TMS,CDCl3):7.65~7.62 (1H, m,
ArH), 7.16~7.12 (2H, m, ArH), 3.32~3.30 (1H, m, CH), 3.24~3.21 (2H, m, CH), 2.53~2.50
(2H,m,CH2), 1.86~1.82 (4H, m, CH2), 1.26~1.22 (6H, m, CH3), 1.18~1.14 (6H, m, CH3),1.10
~1.08 (3H, t, CH3), 0.90~0.86 (6H, m, CH3)；Mass spectrum, FD-MS:315.
Embodiment 13
Prepare catalytic component：In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, first are sequentially added
Benzene 95mL, epoxychloropropane 4ml and tributyl phosphate (TBP) 12.5mL, 50 DEG C are warming up under stirring, and maintained 2.5 hours.Treat
After solid is completely dissolved, phthalic anhydride 1.4g is added, continues to 1 hour, solution is cooled to less than -25 DEG C, 1 hour
Interior dropwise addition TiCl4, 80 DEG C are to slowly warm up to, gradually separates out solids.Addition DNBP (n-butyl phthalate, 0.003
Mole) and 4- (2,6- diisopropyl phenyl imido) -2 pentanone (0.006 mole), maintain temperature 1 hour.After heat filtering, add
Toluene 150mL, washing is secondary, obtains solid, adds toluene 100mL, stirs 30 minutes, is warming up to 110 DEG C, is washed three times
Wash, the time is respectively 10 minutes.Add hexane 60mL to wash twice, obtain catalytic component 7.2g, include Ti：3.7%th, Mg：
22.8%th, Cl：52.6%.
Embodiment 14
Prepare catalytic component：With embodiment 13,4- (2,6- diisopropyl phenyl imido) -2 pentanone is only replaced with into 4-
(2,6- imino dimethyl benzenes) -2 pentanone.
Embodiment 15
Prepare catalytic component：With embodiment 13,4- (2,6- diisopropyl phenyl imido) -2 pentanone is only replaced with into 4-
(2,4,6- trimethylbenzenes imido grpup) -2 pentanone.
Embodiment 16
Prepare catalytic component：It is identical with embodiment 13, only 4- (2,6- diisopropyl phenyl imido) -2 pentanone is replaced
For 5- (2,6- diisopropyls phenyl imido) -3- heptanone.
Embodiment 17
Prepare catalytic component：It is identical with embodiment 13, only 4- (2,6- diisopropyl phenyl imido) -2 pentanone is replaced
For 4- (1- naphthalenes imido grpup) -2 pentanone.
Embodiment 18
Prepare catalytic component：It is identical with embodiment 13, only 4- (2,6- diisopropyl phenyl imido) -2 pentanone is replaced
For 4- (2- hydroxypropyls phenyl imido) -2 pentanone.
Embodiment 19
Prepare catalytic component：With embodiment 13, DNBP is only replaced with into DIBP (diisobutyl phthalate).
Embodiment 20
Prepare catalytic component：In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, first are sequentially added
Benzene 95mL, epoxychloropropane 4ml and tributyl phosphate (TBP) 12.5mL, 50 DEG C are warming up under stirring, and maintained 2.5 hours.Treat
After solid is completely dissolved, phthalic anhydride 1.4g is added, continues to 1 hour, solution is cooled to less than -25 DEG C, 1 hour
Interior dropwise addition TiCl4, it is to slowly warm up to 80 DEG C.Gradually solids is separated out, adds DNBP (0.006 mole), maintains temperature 1 small
When.After heat filtering, toluene 150mL is added, washing is secondary, obtains solid, adds toluene 100mL, stirs 30 minutes, is warming up to
110 DEG C, washed three times, the time is respectively 10 minutes.Add hexane 60mL and 4- (2,6- diisopropyls phenyl imido) -2-
Pentanone (0.003 mole), stir 30 minutes.Reuse hexane 60mL to wash twice, obtain catalytic component 7.4g, include Ti：
3.8%th, Mg：23.8%th, Cl：53.6%.
Embodiment 21
Prepare catalytic component：In the reactor being sufficiently displaced from by high pure nitrogen, 300mLTiCl is added4, cooling
To -20 DEG C, add chlorination magnesium alcoholate carrier 7.0g (referring to patent CN1330086A).40 DEG C are warming up under stirring stage by stage
When, DNBP (0.003 mole) and 4- (2,6- diisopropyl phenyl imido) -2 pentanone (0.003 mole) is added, maintains temperature 2
Hour.TiCl is added after filtering4100mL, 110 DEG C are warming up to, is handled three times.Add hexane 60mL washings three times.
To catalytic component 7.2g, Ti is included：3.4%th, Mg：21.2%th, Cl：50.1%.
Embodiment 22
Prepare catalytic component：In the reactor being sufficiently displaced from by high pure nitrogen, add 300mLTiCl4, be cooled to-
20 DEG C, add magnesium ethylate 7.0g.When being warming up to 40 DEG C under stirring stage by stage, DNBP (0.003 mole) and 4- (2,6- bis- is added
Cumene imido grpup) -2 pentanone (0.003 mole), maintain temperature 3 hours.TiCl is added after filtering4100mL, it is warming up to
110 DEG C, handled three times.Add hexane 60mL washings three times.Catalytic component 6.7g is obtained, includes Ti：3.2%th, Mg：
24.6%th, Cl：54.3%.
Embodiment 23
Propylene polymerization：5L stainless steel cauldrons add AlEt after gaseous propylene is sufficiently displaced from32.5mL and methyl
Cyclohexyl dimethoxysilane (CHMMS) 5ml makes Al/Si (mol)=25.Add the solid constituent 10mg of the preparation of embodiment 13
And 1.2NL hydrogen, liquid propene 2.5L is passed through, is warming up to 70 DEG C, maintains this temperature 1 hour.Cooling, bleeds off pressure, discharge to obtain PP
Resin, it the results are shown in Table 1.
Embodiment 24
Propylene polymerization：With embodiment 23, the catalytic component being only prepared with embodiment 14 replaces therein urge
Agent component, the results are shown in Table 1.
Embodiment 25
Propylene polymerization：With embodiment 23, the catalytic component being only prepared with embodiment 15 replaces therein urge
Agent component, the results are shown in Table 1.
Embodiment 26
Propylene polymerization：With embodiment 23, the catalytic component being only prepared with embodiment 16 replaces therein urge
Agent component, the results are shown in Table 1.
Embodiment 27
Propylene polymerization：With embodiment 23, the catalytic component being only prepared with embodiment 17 replaces therein urge
Agent component, the results are shown in Table 1.
Embodiment 28
Propylene polymerization：With embodiment 23, the catalytic component being only prepared with embodiment 18 replaces therein urge
Agent component, the results are shown in Table 1.
Embodiment 29
Propylene polymerization：With embodiment 23, the catalytic component being only prepared with embodiment 19 replaces therein urge
Agent component, the results are shown in Table 1.
Embodiment 30
Propylene polymerization：With embodiment 23, the catalytic component being only prepared with embodiment 20 replaces therein urge
Agent component, the results are shown in Table 1.
Embodiment 31
Propylene polymerization：With embodiment 23, the catalytic component being only prepared with embodiment 21 replaces therein urge
Agent component, the results are shown in Table 1.
Embodiment 32
Propylene polymerization：With embodiment 23, the catalytic component being only prepared with embodiment 22 replaces therein urge
Agent component, the results are shown in Table 1.
Embodiment 33
Propylene polymerization：With embodiment 23, only polymerization reaction time is extended for 2 hours, the results are shown in Table 1.
Embodiment 34
Propylene polymerization：With embodiment 23, only polymerization reaction time is extended for 3 hours, the results are shown in Table 1.
Embodiment 35
Propylene polymerization：With embodiment 30, only polymerization reaction time is extended for 2 hours, the results are shown in Table 1.
Embodiment 36
Propylene polymerization：With embodiment 30, only polymerization reaction time is extended for 3 hours, the results are shown in Table 1.
Embodiment 37
Propylene polymerization：With embodiment 23, it is 7.2NL only by hydrogenation quantitative change, the results are shown in Table 1.
Comparative example 1
Prepare catalytic component：In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, first are sequentially added
Benzene 95mL, epoxychloropropane 4ml and tributyl phosphate (TBP) 12.5mL, 50 DEG C are warming up under stirring, and maintained 2.5 hours.Treat
After solid is completely dissolved, phthalic anhydride 1.4g is added, continues to 1 hour, solution is cooled to less than -25 DEG C, 1 hour
Interior dropwise addition TiCl4, 80 DEG C are to slowly warm up to, gradually separates out solids.DNBP (0.006 mole) is added, maintains temperature 1 small
When.After heat filtering, toluene 150mL is added, washing is secondary, obtains solid, adds toluene 100mL, is warming up to 110 DEG C, carries out three
Secondary washing, time are respectively 10 minutes.Hexane 60mL is added, is stirred 30 minutes, adds hexane 60mL washings three times.It is catalyzed
Agent component 7.4g, includes Ti：2.4%th, Mg：22.0%th, Cl：50.6%.
Propylene polymerization：5L stainless steel cauldrons add AlEt after gaseous propylene is sufficiently displaced from32.5mL and methyl
Cyclohexyl dimethoxysilane (CHMMS) 5ml makes Al/Si (mol)=25, add above-mentioned preparation solid constituent 10mg and
1.2NL hydrogen, liquid propene 2.5L is passed through, is warming up to 70 DEG C, maintain this temperature 1 hour, cooled, bleed off pressure, discharge to obtain PP resins,
It the results are shown in Table 1.
Comparative example 2
Propylene polymerization：5L stainless steel cauldrons add AlEt after gaseous propylene is sufficiently displaced from32.5mL and methyl
Cyclohexyl dimethoxysilane (CHMMS) 5ml makes Al/Si (mol)=25, adds the solid constituent 10mg of the preparation of comparative example 1
And 7.2NL hydrogen, liquid propene 2.5L is passed through, is warming up to 70 DEG C, maintains this temperature 1 hour, cools, bleeds off pressure, discharge to obtain PP
Resin, it the results are shown in Table 1.
Table 1
It can be seen that by above example and comparative example, when being used for propylene polymerization using catalyst of the present invention,
The hydrogen response of catalyst can significantly improve, and catalyst activity is higher and with long period activity, the molecule of resulting polymers
Measure wider distribution.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used 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 wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (11)
1. a kind of catalytic component for olefinic polymerization, including magnesium elements, titanium elements, halogen and internal electron donor, wherein, institute
Aromatic acid ester type compound of the internal electron donor shown in including the kitimine compound and Formula II shown in Formulas I is stated,
In Formulas I, R is hydroxyl, the C with or without halogen atom substituent1~C20Alkyl, with or without halogen atom substituent
C2~C20Alkenyl or the C with or without halogen atom substituent6~C20Aromatic radical；R1And R2It is identical or different, independently
Ground is hydrogen, C1~C20Alkyl, C2~C20Alkenyl, C1~C20Alkoxy, C6~C30Aralkyl, C6~C30Alkane virtue
Base, C9~C40Polycyclic aromatic group, halogen atom or hydroxyl；A is (CR3R4)nOr hetero atom, wherein, R3And R4It is identical or not
Together, it is separately hydrogen, C1~C20Alkyl, C2~C20Alkenyl, C6~C30Aralkyl, C6~C30Alkaryl or C9
~C40Polycyclic aromatic group, the integer of n=0~6；
In Formula II, RIFor the C with or without halogen atom substituent1~C20Alkyl, the C with or without halogen atom substituent2
~C20Alkenyl, the C with or without halogen atom substituent2~C20Alkynyl or the C with or without halogen atom substituent6~C30
Alkaryl；RIIFor C1~C20Alkyl, C2~C20Alkenyl, C2~C20Alkynyl or C6~C30Alkaryl or ester group or acyl
Amido；RIII、RIV、RVAnd RVIIt is identical or different, it is C1~C20Alkyl, C2~C20Alkenyl, C2~C20Alkynyl, C1~C20Alkane
Epoxide, C6~C30Aralkyl, C6~C30Alkaryl, C9~C40Polycyclic aromatic group or halogen.
2. catalytic component according to claim 1, it is characterised in that the weight based on the catalytic component, it is described
The content of magnesium elements is 5wt%-50wt%, and the content of titanium elements is 1.0wt%-8.0wt%, and the content of halogen is 10wt%-
70wt%, the content of internal electron donor is 0.1wt%-20wt%.
3. catalytic component according to claim 1 or 2, it is characterised in that R be methyl, ethyl, n-propyl, isopropyl,
Normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, hexyl, hydroxyalkyl, phenyl, halobenzene base, alkyl-substituted phenyl, naphthyl,
The group of xenyl or nitrogen-containing heterocgcies；The group of the nitrogen-containing heterocgcies preferably group containing pyrroles, the base containing pyridine
Group, the group of pyrimidine or the group containing quinoline；R1And R2Respectively methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group,
Sec-butyl, the tert-butyl group or amyl group.
4. according to the catalytic component described in any one in claim 1-3, it is characterised in that A is (CR3R4)n, n 1,2,
3 or 4.
5. according to the catalytic component described in any one in claim 1-4, it is characterised in that RIFor methyl, ethyl, positive third
Base, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, isopentyl, neopentyl, hexyl, vinyl, pi-allyl,
Acetenyl, phenyl, halobenzene base, alkyl-substituted phenyl, naphthyl or xenyl.
6. according to the catalytic component described in any one in claim 1-5, it is characterised in that RIIFor methyl, ethyl, positive third
Base, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, isopentyl, neopentyl, hexyl, vinyl, pi-allyl,
Acetenyl, phenyl, halobenzene base, alkyl-substituted phenyl, naphthyl, xenyl, ethoxycarbonyl, the third oxygen formoxyl, isopropyl oxygen first
Acyl group, fourth oxygen formoxyl, isobutyl oxygen formoxyl, own oxygen formoxyl, dissident's oxygen formoxyl, new oxygen formoxyl, oxygen formoxyl in heptan,
Different oxygen in heptan formoxyl, new oxygen in heptan formoxyl, pungent oxygen formoxyl, different pungent oxygen formoxyl or new pungent oxygen formoxyl.
7. according to the catalytic component described in any one in claim 1-6, it is characterised in that the imines shown in Formulas I
Compound is：Own imido grpup-the 2 pentanone of 4- fourths imido grpup -2 pentanone, penta imido grpups of 4- -2 pentanone, 4-, the pungent imido grpup -2- penta of 4-
Ketone, 4- [(1- methylols) tetrahydroform base] -2 pentanone, 4- hydroxypropyls imido grpup -2 pentanone, 4- hydroxyls ethyleneimine base -2 pentanone, 4- hydroxyls
Fourth imido grpup -2 pentanone, 4- isopropyls imido grpup -2 pentanone, 4- (4- chlorobenzenes imido grpup) -2 pentanone, 4- (2,4 dichloro benzene imines
Base) -2 pentanone, 4- (4- trifluoromethyls phenyl imido) -2 pentanone, 4- phenyl imidos -2 pentanone, 4- (1- naphthalenes imido grpup) -2-
(2,6- diisopropyl benzenes are sub- by pentanone, 4- (2- naphthalenes imido grpup) -2 pentanone, 4- (2,6- imino dimethyl benzenes) -2 pentanone, 4-
Amido) -2 pentanone, 4- (2,4,6- trimethylbenzenes imido grpup) -2 pentanone, 4- (8- quinoline imido grpup) -2 pentanone, 4- (4- quinolines
Quinoline imido grpup) -2 pentanone, 4- (3- quinoline imido grpup) -2 pentanone, 4- (the chloro- 6- hydroxyls phenyl imidos of 2-) -2 pentanone, 1,1,
Tri- fluoro- 4- of 1- (2,6- diisopropyls phenyl imido) -2 pentanone, 1,1,1- tri- fluoro- 4- (2,6- imino dimethyl benzenes) -2- penta
Ketone, 3- methyl -4- (2,6- imino dimethyl benzenes) -2 pentanone, 3- ethyls -4- (2,6- imino dimethyl benzenes) -2 pentanone,
3- isopropyls -4- (2,6- imino dimethyl benzenes) -2 pentanone, 3- butyl -4- (2,6- imino dimethyl benzenes) -2 pentanone,
3- methyl -4- (2,6- diisopropyls phenyl imido) -2 pentanone, 3- ethyls -4- (2,6- diisopropyls phenyl imido) -2- penta
Ketone, 3- isopropyls -4- (2,6- diisopropyls phenyl imido) -2 pentanone, 3- butyl -4- (2,6- diisopropyls phenyl imido) -
2 pentanone, the fluoro- 1- butanone of 1- (2- furyls) -3- (2,6- diisopropyls phenyl imido) -4,4,4- three, 1- (2- furyls) -
The fluoro- 1- butanone of 3- (8- quinoline imido grpup) -4,4,4- three, 1- (2- furyls) -3- (2,6- imino dimethyl benzenes) -4,4,4-
Three fluoro- 1- butanone, the own imido grpup -4- heptanone of 2-, 2- isopropyl imido grpup -4- heptanone, the own imido grpup -2-HEPTANONEs of 4-, 4- isopropyls are sub-
Amido -2-HEPTANONE, 4- (2- trimethylsilyls) ethyleneimines base -2 pentanone, 5- phenyl imido -3- heptanone, 5- (1- naphthalenes imido grpup) -3-
Heptanone, 5- (2- naphthalenes imido grpup) -3- heptanone, 5- (8- quinoline imido grpup) -3- heptanone, 5- (4- quinoline imido grpup) -3- heptanone, 5-
(3- quinoline imido grpup) -3- heptanone, 5- (2,6- diisopropyls phenyl imido) -3- heptanone, 5- (2,6- imino dimethyl benzenes) -
3- heptanone, 5- fourth imido grpup -3- heptanone, 5- isopropyl imido grpup -3- heptanone, 5- hydroxyl ethyleneimine base -3- heptanone, 5- hydroxyl fourth imines
Base -3- heptanone, 4- ethyls -5- (8- quinoline imido grpup) -3- heptanone, 4- methyl -5- (8- quinoline imido grpup) -3- heptanone, 4- second
Base -5- (1- naphthalenes imido grpup) -3- heptanone, 4- ethyls -5- (2- naphthalenes imido grpup) -3- heptanone, 4- ethyls -5- phenyl imido -3- heptan
Ketone, 4- butyl -5- phenyl imido -3- heptanone, 4- methyl -5- (2,6- diisopropyls phenyl imido) -3- heptanone, 4- ethyls -5-
(2,6- diisopropyls phenyl imido) -3- heptanone, 4- isopropyls -5- (2,6- diisopropyls phenyl imido) -3- heptanone, 4- fourths
Base -5- (2,6- diisopropyls phenyl imido) -3- heptanone, 4- methyl -5- (2,6- imino dimethyl benzenes) -3- heptanone, 4- second
Base -5- (2,6- imino dimethyl benzenes) -3- heptanone, 3- isopropyl imido grpup -5- octanones, 3- (2,6- diisopropyl benzene imines
Base) -5- octanones, 5- isopropyl imido grpup -3- octanones, 6- isopropyl imido grpup -4- octanones, 5- (2,6- diisopropyls phenyl imido) -
2-HEPTANONE, 5- (2,4,6- trimethylbenzenes imido grpup) -2-HEPTANONE, 4- methyl -5- (2,6- imino dimethyl benzenes) -2-HEPTANONE,
4- ethyls -6- (2,6- diisopropyls phenyl imido) -2-HEPTANONE, 4- isopropyls -6- (2,6- diisopropyls phenyl imido) -2- heptan
Ketone, 6- (2,6- imino dimethyl benzenes) -3- octanones, 3- (2,6- diisopropyls phenyl imido) -1,3- diphenyl -1- acetone,
4- (2,6- diisopropyls phenyl imido) -4- Phenyl 2 butanones, 3- (2,6- imino dimethyl benzenes) -1,3- diphenyl -1- third
Ketone, 3- (2,6- diisopropyls phenyl imido) -1- phenyl -1- butanone, 3- (2,6- imino dimethyl benzenes) -1- phenyl -1- fourths
In ketone, 3- (8- quinoline imido grpup) -1,3- diphenyl -1- acetone and 3- (3- quinoline imido grpup) -1,3- diphenyl -1- acetone
It is one or more.
8. according to the catalytic component described in any one in claim 1-7, it is characterised in that the aromatic esters shown in Formula II
Class compound is：Ethyl benzoate, propyl benzoate, butyl benzoate, amyl benzoate, hexyl-benzoate, benzoic acid heptyl ester,
Octyl benzoate, benzoic acid nonyl ester, n-decyl benzoate, isobutyl benzoate, isoamyl benzoate, benzoic acid dissident ester, benzene first
The different monooctyl ester of sour isocyanate, benzoic acid, Isononyl benzoate, isodecyl benzoate, benzoic acid peopentyl ester, benzoic acid newly own ester, benzene
The new heptyl ester of formic acid, the new monooctyl ester of benzoic acid, the pungent nonyl ester of benzoic acid, the new last of the ten Heavenly stems ester of benzoic acid, diethyl phthalate, phthalic acid
Dipropyl, diisobutyl phthalate, n-butyl phthalate, amyl phthalate, phthalic acid two
Isopentyl ester, the peopentyl ester of phthalic acid two, DHP, dibutyl phthalate (DHP), dioctyl phthalate,
Dinonyl phthalate, o-phthalic acid ester, diisoheptyl phthalate, diisooctyl phthalate, neighbour
Phthalic acid dinonyl, 3- methylphthalic acids diisobutyl ester, 3- methylphthalic acids di-n-butyl, 3- methyl neighbour's benzene
Dioctyl phthalate diisoamyl ester, the n-pentyl ester of 3- methylphthalic acids two, 3- methylphthalic acids di-isooctyl, 3- methyl neighbours benzene two
Formic acid di-n-octyl, 3- ethyls diisobutyl phthalate, 3- ethyls n-butyl phthalate, 3- ethyl O-phthalics
Sour di-n-octyl, 3- ethyls diisobutyl phthalate, 3- ethyls amyl phthalate, 3- ethyl phthalic acids
Diisoamyl ester, 3- propyl group diisobutyl phthalate, 3- propyl group n-butyl phthalate, 3- chloro-o-phthalic acids two are different
Butyl ester, 3- butyl diisobutyl phthalate, 3- butyl n-butyl phthalate, two positive fourth of 4- butyl phthalic acid
Ester, 4- propyl group diisobutyl phthalate, 4- butyl di-iso-amyl phthalate, 4- chloro-o-phthalic acids di-n-butyl,
4- chloro-o-phthalic acids diisobutyl ester, 4- chloro-o-phthalic acids di-n-octyl, 4- methoxyl groups n-butyl phthalate and 4-
One or more in methoxyl group diisobutyl phthalate.
9. according to the catalytic component any one of claim 1-8, it is characterised in that the kitimine shown in Formulas I
The mol ratio of compound and the aromatic acid ester type compound shown in Formula II is 1:(0.05~20), preferably 1:(0.1~10).
10. a kind of catalyst for olefinic polymerization, including：
A) the catalytic component as described in any one in claim 1-9；B) organo-aluminum compound；And optionally C) organic
Silicon compound.
11. the catalyst described in catalytic component or claim 10 according to any one in claim 1-9 is in alkene
Application in hydrocarbon particularly propylene polymerization field.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610846996.7A CN107868147B (en) | 2016-09-23 | 2016-09-23 | Catalyst component for olefin polymerization, catalyst and application thereof |
| EP17852431.0A EP3517553B1 (en) | 2016-09-23 | 2017-09-22 | Catalyst component for use in olefin polymerization, catalyst, and applications thereof |
| FIEP17852431.0T FI3517553T3 (en) | 2016-09-23 | 2017-09-22 | Catalyst component for use in olefin polymerization, catalyst, and applications thereof |
| PCT/CN2017/103045 WO2018054363A1 (en) | 2016-09-23 | 2017-09-22 | Catalyst component for use in olefin polymerization, catalyst, and applications thereof |
| ES17852431T ES2969670T3 (en) | 2016-09-23 | 2017-09-22 | Catalyst component for use in olefin polymerization, catalyst, and applications thereof |
| KR1020197011222A KR102397320B1 (en) | 2016-09-23 | 2017-09-22 | Catalyst components for olefin polymerization, catalysts and uses thereof |
| RU2019111854A RU2758673C2 (en) | 2016-09-23 | 2017-09-22 | Catalyst component for olefin polymerization, catalyst and their application |
| US16/336,103 US10662268B2 (en) | 2016-09-23 | 2017-09-22 | Catalyst component for olefin polymerization, catalyst, and use thereof |
| JP2019515879A JP7178992B2 (en) | 2016-09-23 | 2017-09-22 | Catalyst components for olefin polymerization, catalysts and their applications |
| SA519401394A SA519401394B1 (en) | 2016-09-23 | 2019-03-23 | Catalyst Component for Olefin Polymerization, Catalyst, and Use Thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112759674A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and application thereof |
| CN112759677A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization, catalyst and application thereof |
| CN112759673A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization, catalyst component and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453179A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Propylene random copolymer |
| CN105085732A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and catalyst thereof |
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2016
- 2016-09-23 CN CN201610846996.7A patent/CN107868147B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453179A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Propylene random copolymer |
| CN105085732A (en) * | 2014-04-24 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and catalyst thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759674A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and application thereof |
| CN112759677A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization, catalyst and application thereof |
| CN112759673A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization, catalyst component and application thereof |
| CN112759673B (en) * | 2019-10-21 | 2023-02-28 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization, catalyst component and application thereof |
| CN112759674B (en) * | 2019-10-21 | 2023-04-11 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst and application thereof |
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