CN105085726B - A kind of catalytic component and catalyst for olefinic polymerization - Google Patents
A kind of catalytic component and catalyst for olefinic polymerization Download PDFInfo
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- CN105085726B CN105085726B CN201410168579.2A CN201410168579A CN105085726B CN 105085726 B CN105085726 B CN 105085726B CN 201410168579 A CN201410168579 A CN 201410168579A CN 105085726 B CN105085726 B CN 105085726B
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Abstract
The invention discloses a kind of catalytic component for olefinic polymerization, it includes following components：Magnesium, titanium, halogen and internal electron donor, described internal electron donor include at least one internal electron donor compound a and at least one internal electron donor compound b；Wherein, described at least one internal electron donor compound a is selected from the fragrant group with imine moiety shown in formula (I)：Described at least one internal electron donor compound b is selected from the diolate compound shown in formula (II)：
Description
Technical field
The present invention relates to a kind of catalytic component and catalyst, and in particular to a kind of catalytic component for olefinic polymerization
And catalyst.
Background technology
Olefin polymerization catalysis can be divided into three major types：Traditional Ziegler-Natta catalyst, metallocene catalyst and
Non-metallocene catalyst.For traditional propylene polymerization Ziegler-Natta catalyst, with the electron in catalyst
The development of body compound, polyolefin catalyst is also continuously updated the replacement.TiCl of the research and development of catalyst from the first generation3AlCl3/
AlEt2The TiCl of Cl systems and the second generation3/AlEt2Cl systems, the magnesium chloride to the third generation is carrier, monoesters or aromatic dibasic acid
The TiCl that ester is electron donor, silane is external electron donor4·ED·MgCl2/AlR3ED systems and two alkyd newly developed
Esters, two esters are the catalyst system of electron donor, the catalytic polymerization activity of Ziegler-Natta catalyst and institute
Polypropylene isotacticity is obtained all to be greatly improved.
In the prior art, for olefinic polymerization, in particular for propylene polymerization titanium catalyst system more than with magnesium, titanium,
Halogen and electron donor as basis, wherein electron donor compound be essential component in catalytic component it
One, it to change Ziegler-Natta catalyst catalytic activity, isotacticity and crystallinity, control polymer average molecular
Other performances of Mass Distribution and polymer have large effect.
At present, it has been disclosed that a variety of electron donor compounds, such as monocarboxylic esters or multi-carboxylate, acid anhydrides, ketone, monoether
Or polyether, alcohol, amine etc. and its derivative, wherein more conventional is aromatic dicarboxylic acids' esters, for example phthalic acid two is being just
Butyl ester (DNBP) or diisobutyl phthalate (DIBP) etc., reference can be made to United States Patent (USP) US4784983.United States Patent (USP)
In US4971937 and the component for olefin polymerization catalyst disclosed in European patent EP 0728769, it is special to employ
1, the 3- diolate classes compound containing two ether groups be electron donor, such as 2- isopropyls -2- isopentyl -1,3- diformazans
Epoxide propane, 2,2- diisobutyl -1,3- dimethoxy propanes and 9,9- bis- (methoxyl methyl) fluorenes etc..Thereafter a class is disclosed again
Special dibasic aliphatic carboxylic acid ester compound, such as succinate, malonate, glutarate (referring to WO98/56830,
WO98/56834, WO01/57099, WO01/63231 and WO00/55215), the use of this kind of electron donor compound not only may be used
The activity of catalyst is improved, and the molecular weight distribution of gained acrylic polymers has been widened.
But this area still needs to be made improvements to Ziegler-Natta catalyst and its catalytic component, to cause it
With higher catalyst activity and capacity of orientation, and make it that the molecular weight distribution of resulting polymers is wider.
The present invention is desirable to provide a kind of catalytic activity is high, hydrogen response is high, resulting polymers isotacticities are high and molecule
Measure the catalytic component and catalyst for olefinic polymerization of wider distribution.
The content of the invention
An object of the present invention is a kind of catalytic component for olefinic polymerization of offer, and it includes at least one virtue
Imine internal electron donor compound and at least one diolate type internal electron donor compound.
A further object of the present invention is to provide a kind of catalyst for olefines polymerizing for including the catalytic component.
A further object of the present invention is to provide a kind of pre-polymerized catalyst, and described pre-polymerized catalyst is comprising described
Catalytic component carries out the prepolymer obtained by prepolymerization with alkene.
A further object of the present invention is to provide a kind of catalytic component, catalyst or pre-polymerized catalyst in olefinic polymerization
Application in reaction.
According to an aspect of the present invention, the invention provides a kind of catalytic component for olefinic polymerization, it is included
Following components：Magnesium, titanium, halogen and internal electron donor, described internal electron donor include electron at least one fragrant imine
Body compound a and at least one diolate type internal electron donor compound b.Wherein, in described catalytic component, formula
(I) weight percentage of the internal electron donor compound a shown in is 0.01~20%, the interior electron shown in formula (II)
Body compound b weight percentage is 0.01~20%.
According to another aspect of the invention, the invention provides a kind of catalyst for olefinic polymerization, it is comprising following
Component：
A. it is described comprising being given at least one virtue imine internal electron donor compound a and at least one diolate type
Electron compound b catalytic component；
B. as the organo-aluminum compound of co-catalyst；With
C. optionally, external electron donor component, described external electron donor is preferably organo-silicon compound.
According to another aspect of the present invention, present invention also offers a kind of pre-polymerized catalyst, it includes described catalysis
Agent component carries out the prepolymer obtained by prepolymerization with alkene.
According to a further aspect of the invention, catalytic component, catalyst or prepolymerization are stated present invention also offers described
Application of the catalyst in olefinic polyreaction.
The present invention changes diolate type internal electron donor compound by fragrant imine internal electron donor compound
Catalytic kineticses behavior, using the catalysis that the catalytic component to be formed is compounded comprising both internal electron donor compounds
Agent, in olefinic polyreaction, especially propylene polymerization, not only the catalytic activity of catalyst is high and decay is slow, hydrogen response
Height, and the isotacticity of resulting polymers is higher, and molecular weight distribution is wider so that the application of resulting polymers is more wide
It is general.
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 advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, be
Can be by the conventional products of acquisition purchased in market.
According to an aspect of the present invention, the invention provides a kind of catalytic component for olefinic polymerization, it is included
Following components：Magnesium, titanium, halogen and internal electron donor, described internal electron donor include at least one internal electron donor compound a
With at least one internal electron donor compound b.Wherein, described at least one internal electron donor compound a is selected from formula (I) institute
The fragrant group with imine moiety shown：
According to the specific embodiment of the present invention, in described internal electron donor compound a formula (I), R1Selected from C1
~C20Alkyl, C6~C20Aromatic radical, C7~C20Aralkyl, C7~C20Alkaryl and C9~C20Condensed ring alkyl；R2Selected from hydrogen and
C1~C20Alkyl；R3-R7It is identical or different, independently selected from hydrogen, halogen atom, hydroxyl, C1~C20Alkyl, C1~C20Alkoxy
And C2~C12Alkylene, R3-R7Between optionally bonded cyclization.
In a preferred embodiment of the invention, in described internal electron donor compound a formula (I), R1Selected from C1
~C8Alkyl, phenyl, substituted-phenyl, benzyl, naphthyl and quinolyl；R2Selected from hydrogen and C1~C6Alkyl；R3-R7It is identical or different,
Independently selected from hydrogen, halogen atom, hydroxyl, C1~C6Alkyl, C1~C6Alkoxy, phenyl, substituted-phenyl and C2~C6Alkylene,
R3-R7Between optionally bonded cyclization.
Can be used as the example of heretofore described internal electron donor compound a fragrant group with imine moiety includes but does not limit
In：2- (phenyl imido) methyl -4-TBP, 2- (phenyl imido) methyl -4,6- DI-tert-butylphenol compounds, 2- (benzene imines
Base) methyl -4- chlorophenols, 2- (phenyl imido) methyl -4- fluorophenols, 2- (phenyl imido) methyl -4,6- chlorophenesic acids, 2-
(phenyl imido) methyl -4- methylphenols, 2- (phenyl imido) methyl -4- isopropyl-phenols, 2- (phenyl imido) methylphenol,
2- (phenyl imido) methyl 4-phenyls phenol, 2- (2,6- diisopropyls phenyl imido) methyl -4,6- xylenols, 2- (2,
6- diisopropyls phenyl imido) methyl -6- phenylphenols, 2- (2,6- diisopropyls phenyl imido) methyl -4- isopropyl-phenols,
2- (fourth imido grpup) methyl -4-TBP, 2- (fourth imido grpup) methyl -4,6- DI-tert-butylphenol compounds, 2- (own imido grpup)
Methyl -4-TBP, 2- (own imido grpup) methyl -4,6- DI-tert-butylphenol compounds], the tertiary fourths of 2- (pungent imido grpup) methyl -4-
Base phenol, 2- (pungent imido grpup) methyl -4,6- DI-tert-butylphenol compounds, 2- (2,6- diisopropyls phenyl imido) tertiary fourths of methyl -4-
Base phenol, 2- (2,6- diisopropyls phenyl imido) methyl -4,6- DI-tert-butylphenol compounds, 2- (phenyl imido) methyl -4,6- two
Tert-butyl phenol, 2- (phenyl imido) methyl-6-tert-butylphenol, 2- (2,6- diisopropyls phenyl imido) methyl -4,6- two
Methylphenol, 2- (2,6- imino dimethyl benzenes) methyl -4- DI-tert-butylphenol compounds, 2- (2,6- imino dimethyl benzenes) first
Base -4,6- DI-tert-butylphenol compounds, N- (2- methoxyl group -5- tert-butyl benzenes methylene) -2,6- diisopropyl anilines, N- (2- methoxies
Base -5- tert-butyl benzenes methylene) -2,6- dimethylanilines, 2- (2,6- imino dimethyl benzenes) methyl -4- methoxyl group -6- uncles
Butylphenol, N- benzylidene -2,6- diisopropyl anilines, 2- (4- chlorobenzenes imido grpup) methyl -4,6- DI-tert-butylphenol compounds, N-
To chlorobenzene methylene -2,6- diisopropyl anilines, N- (4- tert-butyl benzenes methylene) -2,6- diisopropyl anilines, N- benzene methylenes
Base -2,6- dimethylanilines, N- (2,4 dichloro benzene methylene) -2,6- dimethylanilines, N- (3,5- di-tert-butyl methylenes
Base) aniline, N- (2,4,6- trifluoros benzylidene) -2,6- dimethylanilines, [2- (2,3,4,5,6- phenyl-pentafluorides imido grpup) first
Base -4,6- DI-tert-butylphenol compounds, N- (2- methoxynaphthalenes methylene) -2,6- diisopropyl anilines, 2- (2,6- diisopropyl benzenes
Imido grpup) methylphenol, 2- (2,6- imino dimethyl benzenes) methyl-6-tert-butylphenol, 2- (2,6- diisopropyl benzene imines
Base) methyl-6-tert-butylphenol, N- (2- methoxyl group -3- tert-butyl benzenes methylene) -2,6- diisopropyl anilines, N- (3,5-
Di-t-butyl benzylidene)-naphthalidine, N- (3,5- di-t-butyls benzylidene) -2- naphthylamines, 2- (2- naphthalenes imido grpup) methylbenzene
Phenol, 2- (4- quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds, 2- (3- quinoline imido grpup) methyl -4,6- di-tert-butyls
Phenol, 2- (8- quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds, N- (2- naphthals) -2,6- diisopropyl anilines, N-
(1- naphthals) -2,6- diisopropyl anilines, N- (1- naphthals) -2,6- dimethylanilines, N- (2- anthracenes methylene) -
2,6- diisopropyl anilines, N- (1- anthracenes methylene) -2,6- dimethylanilines, 2- (2- benzyls imido grpup) -4,6- di-tert-butyls
Phenol, 2- (hydroxyl of 3,5- di-t-butyls -2) benzyl imido grpup phenol and 2- (hydroxyl of 3,5- di-t-butyls -2) benzyl imido grpup -1- naphthalenes
One or more in phenol.
In a preferred embodiment of the invention, described internal electron donor compound a is particularly preferably sub- selected from 2- benzene
Aminomethyl -4-TBP, 2- (phenyl imido methyl) phenol, 2- (2,6- diisopropyls phenyl imido) methyl -4- uncles
Butylphenol, 2- phenyl imidos methyl-6-tert-butylphenol, 2- phenyl imido methyl -4,6- DI-tert-butylphenol compounds, 2- (2,6-
Diisopropyl phenyl imido) methyl -4,6- DI-tert-butylphenol compounds, 2- (2,6- diisopropyls phenyl imido) methylphenol, 2-
(2,6- imino dimethyl benzenes) methyl-6-tert-butylphenol, 2- (2,6- imino dimethyl benzenes) methyl -4- tert-butyl benzenes
Phenol, 2- (4- quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds, 2- (8- quinoline imido grpup) methyl -4,6- di-tert-butyls
Phenol, 2- (2,3,4,5,6- phenyl-pentafluorides imido grpup) methyl -4,6- DI-tert-butylphenol compounds and 2- (own imido grpup) methyl -4,6- two
One or more in tert-butyl phenol.
Described at least one internal electron donor compound b is selected from the diolate compound shown in formula (II)：
According to the specific embodiment of the present invention, in described internal electron donor compound b formula (II), R1' and
R2' identical or different, independently selected from C1~C20Alkyl, C6~C20Aromatic radical, C7~C20Aralkyl and C7~C20Alkaryl；
R3'~R6' identical or different, independently selected from hydrogen, C1~C20Alkyl, C6~C20Aromatic radical and C2~C12Alkylene；RⅠAnd RⅡ
It is identical or different, independently selected from hydrogen, C1~C20Alkyl, C1~C20Cycloalkyl, C6~C20Aromatic radical, C7~C20Aralkyl
Base, C9~C20Condensed ring alkyl and C2~C12Alkylene；R3 '~R6 ', RⅠAnd RⅡBetween optionally bonded cyclization；N is 0~10
Integer.
In a preferred embodiment of the invention, in described internal electron donor compound b formula (II), R1' and
R2' identical or different, independently selected from C1~C6Alkyl, phenyl, substituted-phenyl and cinnamyl；R3'~R6' identical or different,
Independently selected from hydrogen, C1~C6Alkyl, phenyl, substituted-phenyl and C2~C6Alkylene；RⅠAnd RⅡIt is identical or different, independently select
From hydrogen, C1~C6Alkyl, C1~C6Cycloalkyl, benzyl, phenyl, substituted-phenyl, naphthyl and C2~C6Alkylene；R3'~R6’、 RⅠ
And RⅡBetween optionally bonded cyclization；N is 0~2 integer.
Can be used as the example of heretofore described internal electron donor compound b diolate type compound is included but not
It is limited to：The benzoyloxy propane of 2- isopropyls -1,3- two, the benzoyloxy propane of 2- butyl -1,3- two, 2- cyclohexyl -1,3- hexichol
Carboxyphenyl propane, the benzoyloxy propane of 2- benzyls -1,3- two, the benzoyloxy propane of 2- phenyl -1,3- two, 2- (1- naphthyls) -1,
The benzoyloxy propane of 3- bis-, 2- isopropyl -1,3- diethyl carboxyls propane, the benzoyloxies of 2- isopropyl -2- isopentyl -1,3- two
Propane, the benzoyloxy propane of 2- isopropyl -2- isobutyl groups -1,3- two, (the 4- butyl benzenes of 2- isopropyl -2- isopentyl -1,3- two
Carboxyphenyl) propane, 2- isopropyl -2- isopentyl -1,3- dipropyl carboxyls propane, 2- isopropyl -2- butyl -1,3- hexichol first carboxylics
Base propane, 2- isopropyl -2- isopentyl -1- benzoyloxy -3- fourth carboxyls propane, 2- isopropyl -2- isopentyl -1- benzene first carboxylics
Base -3- Chinese cassia tree carboxyls propane, 2- isopropyl -2- isopentyl -1- benzoyloxy -3- second carboxyls propane, 2,2- bicyclopentyl -1,
3- hexichol carboxyls propane, 2,2- dicyclohexyl -1,3- hexichol carboxyls propane, 2,2- dibutyl -1,3- hexichol carboxyls propane, 2,2-
Diisobutyl -1,3- hexichol carboxyls propane, 2,2- diisopropyl -1,3- hexichol carboxyls propane, 2,2- diethyl -1,3- hexichol
Carboxyl propane, 2- ethyl -2- butyl -1,3- hexichol carboxyls propane, the benzoyloxy pentanes of 2,4- bis-, 3- ethyl -2,4- hexichol first
Carboxyl pentane, the benzoyloxy pentanes of 3- methyl -2,4- two, the benzoyloxy pentanes of 3- propyl group -2,4- two, 3- isopropyls -2,4- two
Benzoyloxy pentane, 2,4- bis- (2- propyl group benzoyloxy) pentane, 2,4- bis- (4- propyl group benzoyloxy) pentane, 2,4- bis- (2,
4- dimethyl benzenes carboxyphenyl) pentane, 2,4- bis- (2,4 dichloro benzene carboxyphenyl) pentane, 2,4- bis- (4- chlorobenzenes carboxyphenyl) pentane,
2,4- bis- (4- cumenes carboxyphenyl) pentane, 2,4- bis- (4- butyl benzoyloxy) pentane, (the 4- isobutyl-benzene first carboxylics of 2,4- bis-
Base) pentane, the benzoyloxy heptane of 3,5- bis-, the benzoyloxy heptane of 4- ethyls -3,5- two, 4- propyl group -3,5- two benzoyloxy heptan
Alkane, the benzoyloxy heptane of 4- isopropyls -3,5- two, 3,5- bis- (4- propyl group benzoyloxy) heptane, (the 4- cumene first of 3,5- bis-
Carboxyl) heptane, 3,5- bis- (4- isobutyl-benzenes carboxyphenyl) heptane, 3,5- bis- (4- butyl benzoyloxy) heptane, 2- benzene first carboxylics
Base -4- (4- isobutyl-benzenes carboxyphenyl) pentane, 2- benzoyloxies -4- (4- butyl benzoyloxy) pentane, 2- benzoyloxies -4-
(4- propyl group benzoyloxy) pentane, 3- benzoyloxies -5- (4- isobutyl-benzenes carboxyphenyl) heptane, 3- benzoyloxies -5- (4- butyl
Benzoyloxy) heptane, 3- benzoyloxies -5- (4- propyl group benzoyloxy) heptane, the benzoyloxy methyl fluorenes of 9,9- bis-, 9,9- bis-
(the third carboxymethyl group) fluorenes, 9,9- bis- (isobutyl carboxymethyl group) fluorenes, 9,9- bis- (fourth carboxymethyl group) fluorenes, the benzoyloxy first of 9,9- bis-
Base -4- tert-butyl groups fluorenes, the benzoyloxy methyl -4- propyl group fluorenes of 9,9- bis-, the benzoyloxy methyl isophthalic acids of 9,9- bis-, 2,3,4- tetrahydrochysenes fluorenes,
The benzoyloxy methyl isophthalic acids of 9,9- bis-, 2,3,4,5,6,7,8- octahydros fluorenes, the phenylpropyl alcohols of bis- benzoyloxy methyl -2,3,6,7- of 9,9- two
Indenes, the benzoyloxy methyl isophthalic acids of 9,9- bis-, 8- dichloros fluorenes, the norbornadienes of bis- benzoyloxy methyl -2,5- of 7,7- two, 1,4- hexichol
Carboxyphenyl butane, the benzoyloxy butane of 2,3- diisopropyls -1,4- two, the benzoyloxy butane of 2,3- dibutyl -1,4- two, 1,
The benzoyloxy benzene of 2- bis-, the benzoyloxy benzene of 3- ethyls -1,2- two, the benzoyloxy benzene of 4- butyl -1,2- two, the benzoyloxies of 1,8- bis-
Naphthalene, the benzoyloxy naphthalenes of 2- ethyls -1,8- two, the benzoyloxy naphthalenes of 2- propyl group -1,8- two, the benzoyloxy naphthalenes of 2- butyl -1,8- two,
The benzoyloxy naphthalenes of 4- butyl -1,8- two, the benzoyloxy naphthalenes of 4- isobutyl groups -1,8- two, the benzoyloxy naphthalenes of 4- isopropyls -1,8- two,
One or more in the benzoyloxy naphthalenes of 2- propyl group -1,8- two and the benzoyloxy naphthalenes of 4- propyl group -1,8- two.
In a preferred embodiment of the invention, described internal electron donor compound b is particularly preferably selected from 2,4- bis-
Benzoyloxy pentane and the benzoyloxy pentanes of 2,4- bis-.
Internal electron donor compound b shown in formula of (II) of the present invention includes the polynary carboxylic disclosed in CN85100997
Acid esters compound, its disclosed related content is incorporated by reference into this patent.
In a preferred embodiment of the invention, in described catalytic component, the interior electron shown in formula (I) is led to
The weight percentage of body compound a is 0.01~20%, preferably 1~15%, more preferably 2~10%；Formula (II) institute
The internal electron donor compound b shown weight percentage is 0.01~20%, preferably 1~15%.
According to a preferred embodiment of the present invention, in described catalytic component, the internal electron donor compound a
Mol ratio with the internal electron donor compound b is generally with 1:10~10:1, preferably 0.5:1~2:1.
The preparation method of above two catalyst component can be well-known to those skilled in the art in itself.It can use
Make any one method that the preparation method of the catalytic component of the present invention includes but is not limited in following methods I~IV：
Method I：Magnesium halide is dissolved in organic epoxy compound thing and organic phosphorus compound formation homogeneous solution, can also be added
Atent solvent；The homogeneous solution is mixed with titanium compound；In the presence of having precipitation additive in reaction system, solids analysis
Go out；Internal electron donor compound b is attached on gained solids, first handled with titanium compound or atent solvent, then with described
Internal electron donor compound a processing, obtain including the compositions such as titanium, magnesium, halogen and at least two internal electron donor compounds
Catalytic component.
Method II：Alkoxyl magnesium or alkoxy-magnesium chloride are suspended in atent solvent and form suspension, above-mentioned suspension
Solution obtains solids with titanium compound mixing contact.Again by internal electron donor compound b together with internal electron donor compound a
Contacted with solids, obtain including the catalytic component of the compositions such as titanium, magnesium, halogen and at least two internal electron donor compounds.
Method III：By magnesium halide or organo-magnesium compound, alcohol compound and titanate ester or halogenated titanium compound lazy
Property solvent in be sufficiently mixed stirring, then heat after cooling obtain ball-type carrier or add atent solvent obtain uniform alcohol adduct
Solution.Above-mentioned carrier or homogeneous solution and titanium tetrahalide or derivatives thereof are mixed, maintains to heat after a period of time under low temperature and rises
Temperature, adds internal electron donor compound b and internal electron donor compound a, then is handled with titanium tetrahalide or inert diluent, then
With described internal electron donor compound a processing, eventually pass filtering, washing, dry after obtain including titanium, magnesium, halogen and extremely
The catalytic component of the compositions such as few two kinds of internal electron donor compounds.
Method IV：Magnesium halide is dissolved in organic epoxy compound thing and organic phosphorus compound formation homogeneous solution, can also be added
Enter atent solvent, then add internal electron donor compound b and internal electron donor compound a.By above-mentioned solution and titanium compound
Mixing, maintains heat temperature raising after a period of time under low temperature, then with titanium compound or atent solvent processing, eventually pass filter, washing,
Obtain including the catalytic component of titanium, magnesium, halogen and at least two internal electron donor compounds after drying.
In methods described I~IV, described organic epoxy compound thing may be selected from aliphatic olefin, alkadienes or halo fat
At least one of oxide, glycidol ether and inner ether of fat group alkene or alkadienes, can be used as organic machine ring of the present invention
Oxygen compound example includes but is not limited to：Oxirane, expoxy propane, epoxy butane, butadiene oxide, butadiene dual oxide
One or more in thing, epoxychloropropane, methyl glycidyl ether, diglycidyl ether and tetrahydrofuran.
In methods described I~IV, described organic phosphorus compound may be selected from the hydrocarbyl carbonate or halogen of orthophosphoric acid or phosphorous acid
For hydrocarbyl carbonate, the organic phosphorus compound example that can be used as the present invention includes but is not limited to：Orthophosphoric acid trimethyl, the second of orthophosphoric acid three
Ester, orthophosphoric acid tributyl, orthophosphoric acid triphenylmethyl methacrylate, Trimethyl phosphite, triethyl phosphite, tributyl phosphite, phosphorous acid benzene
One or more in methyl esters.
In methods described I~IV, described atent solvent may be selected from C1~C20Alkane, cycloalkane and aromatic hydrocarbons in one
Plant or several.The atent solvent example that can be used as the present invention includes but is not limited to：Hexane, heptane, octane, decane, benzene, toluene,
One or more in dimethylbenzene and its derivative.
In methods described I~IV, described precipitation additive may be selected from organic acid anhydride, organic acid, ether and ketone at least
It is a kind of.
In methods described I~IV, the formula of described titanium compound can be TiXn(OR)4-n, R can be carbon in formula
Atomicity is 1~20 alkyl, and X can be halogen, and n is 0~4 integer.Can be used as the titanium compound example of the present invention includes
But it is not limited to：Titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro
One or more in diethoxy titanium, the ethanolato-titanium of trichlorine one.
In methods described I~IV, described magnesium halide can be the complexing of the water and alcohol of magnesium dihalide or magnesium dihalide
Thing, the magnesium halide example that can be used as the present invention includes but is not limited to：Magnesium dichloride, dibrominated magnesium, one kind in magnesium diiodide or
It is a variety of.
In methods described I~IV, in terms of every mole of magnesium, internal electron donor compound a consumption rubs for 0.001~15
You, preferably 0.002~5 mole；Described internal electron donor compound b consumption is 0.001~10 mole, preferably 0.002
~3 moles.
In the catalytic component, described internal electron donor is except at least one internal electron donor compound a and at least
Outside a kind of internal electron donor compound b, it can also include but is not limited to：The other skilled in the art such as ester, ether, ketone and amine
Known compound.
According to the specific embodiment of the present invention, the content of the magnesium described in catalytic component is 10~40wt%, excellent
Elect 20~30wt% as；The content of described titanium is 1.5~10.0wt%, preferably 2.0~6.0wt%；Described halogen
Content is 30~70wt%, preferably 40~60wt%.
According to another aspect of the invention, the invention provides a kind of catalyst for olefinic polymerization, it is comprising following
Component：
A. it is described comprising being given at least one virtue imine internal electron donor compound a and at least one diolate type
Electron compound b catalytic component；
B. as the organo-aluminum compound of co-catalyst；With
C. optionally, external electron donor component, described external electron donor is preferably organo-silicon compound.
Can be known in those skilled in the art as the organo-aluminum compound of Invention cocata lysts.Described has
Machine aluminium compound component formula can be AlRnX3-nCompound, R is independently selected from hydrogen, C in formula1-20Alkyl, C6-20Aromatic radical
And C6-20Aralkyl；X is independently selected from halogen atom, preferably chlorine or bromine；N meets the integer of 0 ＜ n≤3.It can be used as the present invention's
Organo-aluminum compound example includes but is not limited to：Trialkylaluminium, such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three normal-butyls
Aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium；Alkyl aluminium hydride, such as a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum；Alkyl aluminum chlorination
Thing, such as aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylization aluminium, the one or more of ethyl aluminum dichloride.
In a preferred embodiment of the invention, described organo-aluminum compound component is trialkylaluminium, preferably three
Aluminium ethide.
Can be known in those skilled in the art as external electron donor of the present invention.Described outer electron
Body compound can be selected from monocarboxylic acid, polybasic carboxylic acid, carboxylic acid anhydrides, carboxylate, ketone, ether, lactone, organic phosphorus compound and organic
One or more in silicon compound, preferred formula is RnSi(OR′)4-nOrgano-silicon compound, wherein n meets 0≤n≤3
Integer, R and R ' are identical or different, independently selected from alkyl, cycloalkyl, aryl, haloalkyl and amido, and R can also be halogen
Atom or hydrogen atom.The organo-silicon compound example that can be used as the present invention includes but is not limited to：Methylcyclohexyl dimethoxy silicon
Alkane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, diphenyl diformazan
TMOS, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, the 2- ethyl piperidine base -2- tert-butyl groups two
Methoxy silane, (the fluoro- 2- propyl group of 1,1,1- tri-) -2- ethyl piperidine base dimethoxysilanes and (the fluoro- 2- propyl group of 1,1,1- tri-) -
One or more in methyl dimethoxysilane.
In a preferred embodiment of the invention, the external electron donor component is preferably methylcyclohexyl dimethoxy
Silane.
In a preferred embodiment of the invention, the organo-aluminum compound B and catalytic component A mol ratio with
Aluminium/titanium is calculated as 10~800:1, and/or the organo-silicon compound C and catalytic component A mol ratio be calculated as 0 with silicon/titanium~
200:1。
According to another aspect of the present invention there is provided a kind of pre-polymerized catalyst for olefinic polymerization, including it is upper
The catalytic component and alkene of stating method preparation carry out the prepolymer obtained by prepolymerization.Pre-polymerization multiple is poly- for 0.1~1000g alkene
Compound/g catalytic components.The prepolymerized alkene of progress is preferably ethene or propylene.Prepolymerization can be according to known
Technology carried out in gas phase or liquid phase.Prepolymerization step can online be carried out as a part for continuous polymerization process, also may be used
Individually carried out in batch process.
According to a further aspect of the invention, present invention also offers above-mentioned catalytic component, catalyst or prepolymerization
Application of the catalyst in olefinic polyreaction.
The catalytic component and catalyst of the present invention is suitable for the polymerization of alkene, and the formula that is particularly suitable for use in is CH2=CHR's
Olefinic polyreaction, wherein R are the hydrocarbyl group of hydrogen or 1-12 carbon atom.Olefinic polyreaction is according to known polymerization
Carry out, can be carried out in liquid phase or gas phase, can also be carried out under the operation that liquid and gas polymerization stage is combined.Using normal
Rule technology carries out the polymerization of alkene, and the alkene is preferably ethene and propylene.The polymerization of propylene can be according to people in the art
Method known to member is carried out, in liquid monomer or monomer in the solution of atent solvent, or in the gas phase, or by gas-liquid
Polymerization mix technique in phase is operated.Polymerization temperature is generally 0 DEG C~150 DEG C, and polymerization pressure is normal pressure or higher.
In the course of the polymerization process, available hydrogen is added to the molecular weight that polymer is adjusted in polymer reactor as polymerizable molecular amount conditioning agent
And melt index.
In the present invention, term " halogen atom " refers to fluorine, chlorine, bromine and iodine.
In the present invention, term " substituted-phenyl " refers to that part or all of H is by such as alkyl, cycloalkyl, alcoxyl on phenyl
The phenyl group that the substitution of the other groups such as base, hydroxyl, halogen atom is obtained.
In the present invention, term " condensed ring alkyl " refers to that two or more carbocyclic rings or heterocycle are formed with shared ring side
Polycyclic organic group, the example includes but is not limited to polycyclic aromatic alkyl, condensed ring aliphatic group, benzene-fused heterocyclic base and bridged ring
Base.
Method of testing
1. polymer isotacticity (%)：Determined with the heptane extraxtion method of boiling.
2. melt index (g/10min)：Determined according to ASTMD1238-99.
3. polymer molecular weight is distributed (Mw/Mn)：The gel permeation chromatograph manufactured with Waters companies is determined, and solvent is used
1,2,4- trichloro-benzenes, styrene is standard specimen；The nmr analysis of compound are poly- with Bruke dmx300MHz nmr determinations
The 1H-NMR of compound；Solvent：Deuterochloroform, TMS is internal standard, temperature 275K.
It is internal electron donor compound a synthetic example below
Embodiment 1：The synthesis of compound 2- phenyl imidos methyl -4-TBP
In one 250 milliliters of there-necked flask, 40 milliliters of ethanol, 0.94 gram of aniline and the tertiary fourths of 1.78 grams of 3- are added
Base salicylide, at room temperature stirring reaction 24 hours.Above-mentioned stirring reaction solution adds 40 milliliters of ethanol after being concentrated under reduced pressure,
Reaction 12 hours is stirred at room temperature.Gained reaction solution is crossed into column chromatography after being concentrated under reduced pressure and obtains 1.83 grams of (yields
72.3%) orange product (2- phenyl imidos methyl -4-TBP).
1H-NMR(δ,ppm,TMS,CDCl3):8.64 (1H, s, CH=N), 7.96~7.86 (3H, m, ArH), 7.83~
7.56(5H, m,ArH),3.71(1H,s,OH),1.35(9H,m,CH3)；Mass spectrum, FD-mass spectrometry:253.
Or prepared using following methods：
In one 250 milliliters of there-necked flask, 1.78 grams of 3- tert-butyl groups salicylide and 70 milliliters of ethanol is added.Stirring
The lower aniline and 0.1 milliliter of formic acid for adding 0.94 gram, stirring reaction 0.5 hour, is warming up to 100 DEG C of back flow reactions 16 at room temperature
Hour.Then solvent is removed, head product is purified with silicagel column, solvent is hexane/ether (30：1) 2.12 grams of (2- benzene, are obtained
Imines ylmethyl -4-TBP), yield 83.7%.
1H-NMR(δ,ppm,TMS,CDCl3):8.64 (1H, s, CH=N), 7.96~7.86 (3H, m, ArH), 7.83~
7.56(5H, m,ArH),3.71(1H,s,OH),1.35(9H,m,CH3)；Mass spectrum, FD-mass spectrometry:253.
Embodiment 2：The synthesis of compound 2- (phenyl imido methyl) phenol
In a there-necked flask, 1.22 grams of salicylide and 60 milliliters of ethanol is added.Stirring is lower to add 0.93 gram of aniline
With 0.1 milliliter of glacial acetic acid, stirring reaction 1 hour at room temperature is warming up to 100 DEG C of back flow reactions 24 hours.Then remove molten
Agent, head product silicagel column separating-purifying, solvent is ethyl acetate/petroleum ether (1：30) 1.91 grams of product [2-, are obtained
(phenyl imido methyl) phenol], yield 96.9%.
1H-NMR (δ, ppm, TMS, CDCl3):8.63 (1H, s, CH=N), 7.86~7.66 (3H, m, ArH), 7.21~
7.60 (4H, m, ArH), 6.73~6.96 (2H, m, ArH), 3.71 (1H, s, OH)；Mass spectrum, FD-mass spectrometry:
197。
Embodiment 3：The synthesis of compound 2- (2,6- diisopropyls phenyl imido) methyl -4-TBP
In a there-necked flask, 1.78 grams of 3- tert-butyl groups salicylides and 70 milliliters of ethanol are added.Stirring is lower to add 1.77
Gram 2,6- diisopropyl anilines and 0.2 milliliter of glacial acetic acid, stirring reaction 1 hour, is warming up to 100 DEG C of back flow reactions at room temperature
24 hours.Then solvent is removed, head product is purified with silicagel column, solvent is ethyl acetate/petroleum ether (1：30) 2.85, are obtained
Gram product [2- (2,6- diisopropyl phenyl imido) methyl -4-TBP], yield 84.5%.
1H-NMR(δ,ppm,TMS,CDCl3):8.64 (1H, s, CH=N), 7.96~7.86 (3H, m, ArH), 7.63~
7.52 (3H, m, ArH), 3.73 (1H, s, OH), 2.62~2.48 (2H, m, CH), 1.35~1.50 (9H, m, CH3), 1.27~
1.08(12H,m, CH3)；Mass spectrum, FD-mass spectrometry:337.
Embodiment 4：The synthesis of compound 2- phenyl imido methyl-6-tert-butylphenols
In a there-necked flask, 1.78 grams of 5- tert-butyl groups salicylides and 70 milliliters of ethanol are added.Stirring is lower to add 0.93
Gram aniline and 0.2 milliliter of formic acid, stirring reaction 0.5 hour at room temperature is warming up to 100 DEG C of back flow reactions 10 hours.Then remove
Solvent is removed, head product is purified with silicagel column, solvent is ethyl acetate/petroleum ether (1：30), obtaining 3.51 grams of products, (2- benzene is sub-
Aminomethyl -6- tert-butyl phenols), yield 92%.
1H-NMR(δ,ppm,TMS,CDCl3):8.63 (1H, s, CH=N), 7.96~7.82 (3H, m, ArH), 7.73~
7.56(5H, m,ArH),3.73(1H,s,OH),1.35(9H,m,CH3)；Mass spectrum, FD-mass spectrometry:253.
Embodiment 5：The synthesis of compound 2- phenyl imido methyl -4,6- DI-tert-butylphenol compounds
In a there-necked flask, 2.34 grams of 3,5- di-tert-butyl salicylaldehydes and 80 milliliters of ethanol are added.Stirring is lower to be added
0.93 gram of aniline and 0.2 milliliter of glacial acetic acid, stirring reaction 1 hour at room temperature is warming up to 100 DEG C of back flow reactions 24 hours.So
After remove solvent, head product is purified with silica gel column chromatography, solvent be ethyl acetate/petroleum ether (1：30) 2.85 grams of productions, are obtained
Product (2- phenyl imido methyl -4,6- DI-tert-butylphenol compounds), yield 92%.
1H-NMR(δ,ppm,TMS,CDCl3):8.63 (1H, s, CH=N), 7.96 (1H, m, ArH), 7.83~7.56 (6H,
M, ArH), 3.73 (1H, s, OH), 1.53~1.26 (18H, m, CH3)；Mass spectrum, FD-mass spectrometry:309.
Embodiment 6：The synthesis of compound 2- (2,6- diisopropyls phenyl imido) methyl -4,6- DI-tert-butylphenol compounds
In a there-necked flask, 2.34 grams of 3,5- di-tert-butyl salicylaldehydes and 60 milliliters of isopropanol are added.Stirring is lower to be added
Enter 1.77 grams of 2,6-DIPAs and 0.2 milliliter of glacial acetic acid, at room temperature stirring reaction 1 hour, be warming up to 100 DEG C and return
Stream reaction 24 hours.Then solvent is removed, head product is purified with silica gel column chromatography, solvent is ethyl acetate/petroleum ether (1：
30) 3.48 grams of products [2- (2,6- diisopropyl phenyl imido) methyl -4,6- DI-tert-butylphenol compounds], yield 88.5%, are obtained.
1H-NMR(δ,ppm,TMS,CDCl3):8.63 (1H, s, CH=N), 7.96 (1H, m, ArH), 7.73~7.56 (4H,
M, ArH), 3.73 (1H, s, OH), 2.60~2.46 (2H, m, CH), 1.35~1.50 (18H, m, CH3), 1.28~1.12
(12H,m, CH3)；Mass spectrum, FD-mass spectrometry:393.
Embodiment 7：The synthesis of compound 2- (2,6- diisopropyls phenyl imido) methylphenol
In a there-necked flask, 1.22 grams of salicylide and 70 milliliters of ethanol is added.Stirring is lower to add 2.05 grams of 2,6- bis-
Isopropyl aniline and 0.2 milliliter of glacial acetic acid, stirring reaction 1 hour at room temperature is warming up to 100 DEG C of back flow reactions 24 hours.So
After remove solvent, head product is purified with silicagel column, solvent be ethyl acetate/petroleum ether (1：30) 2.67 grams of product [2-, are obtained
(2,6- diisopropyl phenyl imido) methylphenol], yield 95%.
1H-NMR(δ,ppm,TMS,CDCl3):8.63 (1H, s, CH=N), 7.96 (1H, m, ArH), 7.73~7.46 (6H,
M, ArH), 3.72 (1H, s, OH), 2.78~2.66 (2H, m, CH), 1.38~1.12 (12H, m, CH3)；Mass spectrum, FD-mass
spectrometry:281。
Embodiment 8：The synthesis of compound 2- (2,6- imino dimethyl benzenes) methyl-6-tert-butylphenol
In a reaction bulb, 1.78 grams of 5- tert-butyl groups salicylide and 70 milliliters of ethanol is added.Stirring is lower to add 1.21 grams
2,6- dimethylanilines and 0.1 milliliter of glacial acetic acid, stirring reaction 0.5 hour, is warming up to 100 DEG C of back flow reactions 24 at room temperature
Hour.Then solvent is removed, head product is purified with silicagel column, solvent is ethyl acetate/petroleum ether (1：30) 2.40 grams, are obtained
Product [2- (2,6- imino dimethyl benzene) methyl-6-tert-butylphenol], yield 85%.
1H-NMR(δ,ppm,TMS,CDCl3):8.63 (1H, s, CH=N), 7.86 (1H, m, ArH), 7.67~7.46 (5H,
M, ArH), 3.73 (1H, s, OH), 2.12~2.43 (6H, m, CH3), 1.38~1.12 (9H, s, CH3)；Mass spectrum, FD-mass
spectrometry:281。
Embodiment 9：The synthesis of compound 2- (2,6- imino dimethyl benzenes) methyl -4-TBP
In a reaction bulb, 1.78 grams of 3- tert-butyl groups salicylides and 70 milliliters of ethanol are added.Stirring is lower to add 1.21 grams
2,6- dimethylanilines and 0.1 milliliter of glacial acetic acid, stirring reaction 0.5 hour, is warming up to 100 DEG C of back flow reactions 24 at room temperature
Hour.Then solvent, head product silica gel column chromatography separating-purifying are removed, solvent is ethyl acetate/petroleum ether (1：30), obtain
To 2.30 grams of product [2- (2,6- imino dimethyl benzene) methyl -4-TBP], yield 82%.
1H-NMR(δ,ppm,TMS,CDCl3):8.65 (1H, s, CH=N), 7.96 (1H, m, ArH), 7.78~7.36 (5H,
M, ArH), 3.72 (1H, s, OH), 2.20~2.48 (6H, s, CH3), 1.35~1.13 (9H, s, CH3)；Mass spectrum, FD-mass
spectrometry:281。
Embodiment 10：The synthesis of compound 2- (4- quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds
In a reaction bulb, 2.34 grams of 3,5- di-tert-butyl salicylaldehydes and 70 milliliters of ethanol is added.Stirring is lower to be added
1.44 grams of 4- aminoquinolines and 0.1 milliliter of glacial acetic acid, stirring reaction 0.5 hour, is warming up to 100 DEG C of back flow reactions at room temperature
24 hours.Then solvent, head product silica gel column chromatography separating-purifying are removed, solvent is ethyl acetate/petroleum ether (1：30),
Obtain 2.50 grams of products [2- (4- quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds], yield 70%.
1H-NMR(δ,ppm,TMS,CDCl3):8.60~8.76 (2H, m, CH=N), 7.96~7.65 (4H, m, ArH),
7.60~7.36 (3H, m, ArH), 3.73 (1H, s, OH), 1.30~1.54 (18H, m, CH3)；Mass spectrum, FD-mass
spectrometry:360。
Embodiment 11：The synthesis of compound 2- (8- quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds
In a reaction bulb, 2.34 grams of 3,5- di-t-butyl water salicylides and 70 milliliters of ethanol are added.Stir lower 1.44 grams
8- aminoquinolines and 0.1 milliliter of glacial acetic acid are added, stirring reaction 1 hour, is warming up to 100 DEG C of back flow reactions 24 small at room temperature
When.Then solvent is removed, head product is purified with silicagel column, solvent is ethyl acetate/petroleum ether (1：30) 2.82 grams of productions, are obtained
Product [2- (8- quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds], yield 80%.
1H-NMR(δ,ppm,TMS,CDCl3):8.60~8.76 (2H, m, CH=N), 7.96~7.65 (4H, m, ArH),
7.60~7.36 (3H, m, ArH), 3.74 (1H, s, OH), 1.30~1.54 (18H, m, CH3)；Mass spectrum, FD-mass
spectrometry: 360。
Embodiment 12：The synthesis of compound 2- (2,3,4,5,6- phenyl-pentafluorides imido grpup) methyl -4,6- DI-tert-butylphenol compounds
In a reaction bulb, 2.34 grams of 3,5- di-tert-butyl salicylaldehydes and 70 milliliters of ethanol are added.Lower 1.83 grams are stirred to add
Enter 2,3,4,5,6- pentafluoroanilines and 0.1 milliliter of glacial acetic acid, at room temperature stirring reaction 0.5 hour, be warming up to 100 DEG C of backflows
Reaction 24 hours.Then solvent is removed, head product is purified with silicagel column, solvent is ethyl acetate/petroleum ether (1：30), obtain
To 2.70 grams of products [2- (2,3,4,5,6- phenyl-pentafluoride imido grpup) methyl -4,6- DI-tert-butylphenol compounds], yield 67.7%.
1H-NMR(δ,ppm,TMS,CDCl3):8.60~8.76 (1H, m, CH=N), 7.64~7.36 (2H, m, ArH),
3.74 (1H, s, OH), 1.30~1.54 (18H, m, CH3)；Mass spectrum, FD-mass spectrometry:399.
Embodiment 13：The synthesis of compound 2- (own imido grpup) methyl -4,6- DI-tert-butylphenol compounds
In a reaction bulb, 2.34 grams of 3,5- di-tert-butyl salicylaldehydes and 70 milliliters of isopropanols are added.Stirring is lower to add 1-
Hexyl amine (1.01 grams) and 0.1 milliliter of glacial acetic acid, stirring reaction 0.5 hour, is warming up to 100 DEG C of back flow reactions 20 small at room temperature
When.Then solvent is removed, head product is purified with silicagel column, solvent is ethyl acetate/petroleum ether (1：30) 2.70 grams of productions, are obtained
Product [2- (own imido grpup) methyl -4,6- DI-tert-butylphenol compounds], yield 67.7%.
1H-NMR(δ,ppm,TMS,CDCl3):8.60~8.76 (1H, m, CH=N), 7.64~7.36 (2H, m, ArH),
3.74 (1H, s, OH), 2.78 (2H, m ,=NCH2), 1.33~1.54 (18H, m, CH3), 1.25~1.31 (8H, m, CH2),
0.89~1.08 (3H, t, CH3)；Mass spectrum, FD-mass spectrometry:317.
Embodiment 14：The synthesis of compound N-(1- naphthals) -2,6- diisopropyl anilines
In a reaction bulb, 1.56 grams of 1- naphthaldehydes and 80 milliliters of isopropanols are added.Stirring is lower to add 2,6- diisopropyl benzenes
Imines (1.78 grams) and 0.1 milliliter of glacial acetic acid, stirring reaction 0.5 hour at room temperature, temperature rising reflux react 24 hours.Then
Solvent is removed, head product is purified with silicagel column, solvent is ethyl acetate/petroleum ether (1：30) product N- (1- naphthalene methylenes, are obtained
Base) -2,6-DIPA (2.14 grams, yield 68%).
1H-NMR(δ,ppm,TMS,CDCl3):8.60~8.76 (1H, m, CH=N), 7.86~8.02 (2H, m, ArH),
7.64~7.36 (5H, m, ArH), 7.08~7.28 (3H, m, ArH), 3.16~3.34 (2H, s, CH), 1.32~1.52 (6H,
M, CH3), 1.23~1.32 (6H, m, CH3)；Mass spectrum, FD-mass spectrometry:315.
It is the preparation embodiment of catalytic component below
Embodiment 15
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 under stirring, and maintain 2.5 hours, after solid is completely dissolved,
Phthalic anhydride 1.4g is added, is continued to 1 hour, solution is cooled in less than -25 DEG C, 1 hour TiCl is added dropwise4, delay
Slowly 80 DEG C are warming up to, gradually separate out solids, add the electron donor compound 2 of the formula (II), the benzoyloxies of 4- bis-
Pentane (0.006 mole), maintains temperature 1 hour, after heat filtering, adds toluene 150mL, washs secondary, obtains solid, adds first
Benzene 100mL, is warming up to 110 DEG C, carries out three washings, and the time is respectively 10 minutes, adds the electron donor of the formula (I)
Compound 2- (2,6- diisopropyl phenyl imido) methyl -4,6- DI-tert-butylphenol compounds (0.006 mole), hexane 60mL, stirring 30
Minute, add hexane 60mL and wash three times.Solids 7.4g (catalytic component) is obtained, containing Ti：3.8%th, Mg：24.2%th,
Cl：50.6%.
Embodiment 16
Be the same as Example 15, difference is the electron donor compound 2 of the formula (II) in embodiment 15,4- hexichol
Carboxyphenyl pentane replaces with the benzoyloxy heptane of 3,5- bis-, and other conditions are constant.
Embodiment 17
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, is continued to 1 hour, solution is cooled in less than -25 DEG C, 1 hour TiCl is added dropwise4, delay
Slowly 80 DEG C are warming up to, gradually separate out solids, add the electron donor compound 2 of the formula (II), the benzoyloxies of 4- bis-
Electron donor compound 2- (8- quinoline imido grpup) methyl -4,6- di-t-butyls of pentane (0.003 mole) and the formula (I)
Phenol (0.003 mole), maintains temperature 1 hour, after heat filtering, adds toluene 150mL, washs secondary, obtains solid, adds
Toluene 100mL, is stirred 30 minutes, is warming up to 110 DEG C, carries out three washings, and the time is respectively 10 minutes, adds hexane 60mL
Washing three times, obtains solids 6.9g (catalytic component), containing Ti：3.5%th, Mg：23.5%th, Cl：52.0%.
Embodiment 18
Be the same as Example 17, difference is the electron donor compound 2- (8- of the formula (I) in embodiment 17
Quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds replace with the tertiary fourths of 2- (2,6- diisopropyls phenyl imido) methyl -4,6- two
Base phenol, other conditions are constant.
Embodiment 19
Be the same as Example 17, difference is the electron donor compound 2- (8- of the formula (I) in embodiment 17
Quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds replace with 2- (2,6- diisopropyls phenyl imido) methyl -4- tert-butyl benzenes
Phenol, other conditions are constant.
Embodiment 20
Be the same as Example 17, difference is the electron donor compound 2- (8- of the formula (I) in embodiment 17
Quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds replace with 2- (2,6- imino dimethyl benzenes) methyl -4- tert-butyl benzenes
Phenol, other conditions are constant.
Embodiment 21
Be the same as Example 17, difference is the electron donor compound 2- (8- of the formula (I) in embodiment 17
Quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds replace with 2- (3- quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds,
Other conditions are constant.
Embodiment 22
Be the same as Example 17, difference is the electron donor compound 2- of the formula (II) in embodiment 17
(8- quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds are changed to 2- (4- quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds,
Other conditions are constant.Embodiment 23
Be the same as Example 17, difference is the electron donor compound 2- of the formula (II) in embodiment 17
(8- quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds are changed to 2- (to bromobenzene imido grpup) methyl -4,6- DI-tert-butylphenol compounds,
Other conditions are constant.
Embodiment 24
Be the same as Example 17, difference is the electron donor compound 2- (8- of the formula (I) in embodiment 17
Quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds replace with N- (1- naphthals) -2,6-DIPA, other
Part is constant.
Embodiment 25
In the reactor being sufficiently displaced from by high pure nitrogen, plus 300mLTiCl4, -20 DEG C are cooled to, magnesium chloride is added
Alcohol adduct carrier 7.0g (see patent CN1330086A), when being warming up to 40 DEG C stage by stage under stirring, adds the formula (II)
The benzoyloxy pentanes of electron donor compound 2,4- bis- (0.003 mole) and the formula (I) electron donor compound 2- (2,
6- diisopropyls phenyl imido) methyl -4,6- DI-tert-butylphenol compounds (0.003 mole), temperature is maintained 2 hours, after filtering.Again plus
Enter TiCl4100mL, is warming up to 110 DEG C, carries out three processing.Hexane 60mL is added, is stirred 30 minutes；Add hexane 60mL
Washing three times.Solids 6.7g (catalytic component) is obtained, containing Ti：3.7%th, Mg：26.6%th, Cl：51.6%.
It is olefinic polymerization embodiment below
Embodiment 26
Volume is 5L stainless steel cauldron, after being sufficiently displaced from through gaseous propylene, adds AlEt32.5mL, methylcyclohexyl
Dimethoxysilane 5ml makes Al/Si (mol)=25, add above-described embodiment 15 preparation catalytic component 10mg and
1.2NL hydrogen, is passed through liquid propene 2.5L, is warming up to 70 DEG C, maintains this temperature 1 hour, cooling, bleeds off pressure, discharge to obtain polypropylene
Resin (PP resins), active 43500g/gCat., the isotacticity 97.6% of resulting polymers.
Embodiment 27
Be the same as Example 26, difference be by embodiment 26 catalytic component replace with it is made in embodiment 16
Standby catalytic component, other conditions are constant.Concrete outcome is shown in Table 1.
Embodiment 28
Be the same as Example 26, difference be by embodiment 26 catalytic component replace with it is made in embodiment 17
Standby catalytic component, other conditions are constant.Concrete outcome is shown in Table 1.
Embodiment 29
Be the same as Example 26, difference be by embodiment 26 catalytic component replace with it is made in embodiment 18
Standby catalytic component, other conditions are constant.Concrete outcome is shown in Table 1.
Embodiment 30
Be the same as Example 26, difference be by embodiment 26 catalytic component replace with it is made in embodiment 19
Standby catalytic component, other conditions are constant.Concrete outcome is shown in Table 1.
Embodiment 31
Be the same as Example 26, difference be by embodiment 26 catalytic component replace with it is made in embodiment 20
Standby catalytic component, other conditions are constant.Concrete outcome is shown in Table 1.
Embodiment 32
Be the same as Example 26, difference be by embodiment 26 catalytic component replace with it is made in embodiment 21
Standby catalytic component, other conditions are constant.Concrete outcome is shown in Table 1.
Embodiment 33
Be the same as Example 26, difference be by embodiment 26 catalytic component replace with it is made in embodiment 22
Standby catalytic component, other conditions are constant.Concrete outcome is shown in Table 1.
Embodiment 34
Be the same as Example 26, difference be by embodiment 26 catalytic component replace with it is made in embodiment 23
Standby catalytic component, other conditions are constant.Concrete outcome is shown in Table 1.
Embodiment 35
Be the same as Example 26, difference be by embodiment 26 catalytic component replace with it is made in embodiment 24
Standby catalytic component, other conditions are constant.Concrete outcome is shown in Table 1.
Embodiment 36
Be the same as Example 26, difference be by embodiment 26 catalytic component replace with it is made in embodiment 25
Standby catalytic component, other conditions are constant.Concrete outcome is shown in Table 1.
Embodiment 37
Be the same as Example 26, difference is the polymerization reaction time in embodiment 26 being extended for 2 hours, other conditions
It is constant.Concrete outcome is shown in Table 1.
Embodiment 38
Be the same as Example 26, difference is the polymerization reaction time in embodiment 26 being extended for 3 hours, other conditions
It is constant.Concrete outcome is shown in Table 1.
Embodiment 39
Be the same as Example 32, difference is the polymerization reaction time in embodiment 32 being extended for 2 hours, other conditions
It is constant.Concrete outcome is shown in Table 1.
Embodiment 40
Be the same as Example 29, difference is the added hydrogen in embodiment 29 being changed into 7.2NL, and other conditions are not
Become.Concrete outcome is shown in Table 1.
Embodiment 41
Be the same as Example 29, difference is the polymerization reaction time in embodiment 29 being extended for 2 hours, other conditions
It is constant.Concrete outcome is shown in Table 1.
Embodiment 42
Be the same as Example 29, difference is the polymerization reaction time in embodiment 29 being extended for 3 hours, other conditions
It is constant.Concrete outcome is shown in Table 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 and tributyl phosphate 12.5mL, is warming up to 50 DEG C under stirring, and maintains 2.5 hours, after solid is completely dissolved, adds
Phthalic anhydride 1.4g, is continued to 1 hour, solution is cooled in less than -25 DEG C, 1 hour TiCl is added dropwise4, it is slow to rise
Temperature gradually separates out solids to 80 DEG C, adds the benzoyloxy pentanes of 2,4- bis- (0.003 mole), maintains temperature 1 hour, heat
After filtering, toluene 150mL is added, washs secondary, obtains solid, add toluene 100mL, be warming up to 110 DEG C, wash for three times
Wash, the time is respectively 10 minutes, and hexane 60mL is stirred 30 minutes, adds hexane 60mL and washs three times.Obtain solids 7.4g
(catalytic component), containing Ti：2.4%th, Mg：22.0%th, Cl：50.6%.
Volume is 5L stainless steel cauldron, after being sufficiently displaced from through gaseous propylene, adds AlEt32.5mL, methylcyclohexyl
Dimethoxysilane (CHMMS) 5ml makes Al/Si (mol)=25, add above-mentioned preparation catalytic component 10mg and
1.2NL hydrogen, is passed through liquid propene 2.5L, is warming up to 70 DEG C, maintains this temperature 1 hour, cooling, bleeds off pressure, discharge to obtain polypropylene
Resin, concrete outcome is shown in Table 1.
Comparative example 2
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 under stirring, and maintain 2.5 hours, after solid is completely dissolved,
Phthalic anhydride 1.4g is added, is continued to 1 hour, solution is cooled in less than -25 DEG C, 1 hour TiCl4 is added dropwise, is delayed
Slowly 80 DEG C are warming up to, gradually separate out solids, add the benzoyloxy pentanes of 2,4- bis- (0.003 mole), maintain temperature 1 small
When, after heat filtering, toluene 150mL is added, washs secondary, obtains solid, add toluene 100mL, be warming up to 110 DEG C, carry out three
Secondary washing, the time is respectively 10 minutes, and hexane 60mL is stirred 30 minutes, adds hexane 60mL and washs three times.Obtain solids
7.4g (catalytic component), containing Ti：2.4%th, Mg：22.0%th, Cl：50.6%.
Volume is 5L stainless steel cauldron, after being sufficiently displaced from through gaseous propylene, adds AlEt32.5mL, methylcyclohexyl
Dimethoxysilane (CHMMS) 5ml makes Al/Si (mol)=25, add above-mentioned preparation catalytic component 10mg and
7.2NL hydrogen, is passed through liquid propene 2.5L, is warming up to 70 DEG C, maintains this temperature 1 hour, cooling, bleeds off pressure, discharge to obtain polypropylene
Resin, concrete outcome sees attached list 1.
Table 1
Data comparison with comparative example 1 and 2 can be seen that embodiment 26~42 using comprising of the present invention at least one
Kind of virtue imine internal electron donor compound a and at least one diolate type internal electron donor compound b compounds urging of being formed
The catalyst of agent component, in propylene polymerization, the activity of one side catalyst is higher (can be reached 88.9%, see reality
Apply example 42), hydrogen response is good (visible embodiment 29 and 40), and catalyst activity decay is slow；Another aspect resulting polymers etc.
Normality height (99.1% can be reached, see embodiment 39), high melt index (32.5 can be reached, see embodiment 40) and molecule
Wider distribution is measured, the application of resulting polymers is more extensive.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein word 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 is related 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 (13)
1. a kind of catalytic component for olefinic polymerization, it includes following components：Magnesium, titanium, halogen and internal electron donor, it is described
Internal electron donor include at least one internal electron donor compound a and at least one internal electron donor compound b；Wherein,
Described at least one internal electron donor compound a is selected from the fragrant group with imine moiety shown in formula (I)：
In formula (I), R1Selected from C1~C20Alkyl, C6~C20Aromatic radical, C7~C20Aralkyl, C7~C20Alkaryl and C9~
C20Condensed ring alkyl；R2Selected from hydrogen and C1~C20Alkyl；R3-R7It is identical or different, independently selected from hydrogen, halogen atom, hydroxyl, C1
~C20Alkyl, C1~C20Alkoxy and C2~C12Alkylene, R3-R7Between optionally bonded cyclization；
Described at least one internal electron donor compound b is selected from the diolate compound shown in formula (II)：
In formula (II), R1' and R2' identical or different, independently selected from C1~C20Alkyl, C6~C20Aromatic radical, C7~C20Virtue
Alkyl and C7~C20Alkaryl；R3'~R6' identical or different, independently selected from hydrogen, C1~C20Alkyl, C6~C20Aromatic radical and
C2~C12Alkylene；RⅠAnd RⅡIt is identical or different, independently selected from hydrogen, C1~C20Alkyl, C1~C20Cycloalkyl, C6~C20
Aromatic radical, C7~C20Aralkyl, C9~C20Condensed ring alkyl and C2~C12Alkylene；R3'~R6’、RⅠAnd RⅡBetween it is optionally bonded
Cyclization；N is 0~10 integer.
2. catalytic component according to claim 1, it is characterised in that described internal electron donor compound a formula
(I) in, R1Selected from C1~C8Alkyl, phenyl, substituted-phenyl, benzyl, naphthyl and quinolyl；R2Selected from hydrogen and C1~C6Alkyl；R3-
R7It is identical or different, independently selected from hydrogen, halogen atom, hydroxyl, C1~C6Alkyl, C1~C6Alkoxy and C2~C6Alkylene,
R3-R7Between optionally bonded cyclization.
3. catalytic component according to claim 1, it is characterised in that described internal electron donor compound b formula
(II) in, R1' and R2' identical or different, independently selected from C1~C6Alkyl, phenyl, substituted-phenyl and cinnamyl；R3'~R6’
It is identical or different, independently selected from hydrogen, C1~C6Alkyl, phenyl, substituted-phenyl and C2~C6Alkylene；RⅠAnd RⅡIt is identical or not
Together, independently selected from hydrogen, C1~C6Alkyl, C1~C6Cycloalkyl, benzyl, phenyl, substituted-phenyl, naphthyl and C2~C6Alkylene；
R3'~R6’、RⅠAnd RⅡBetween optionally bonded cyclization；N is 0~2 integer.
4. catalytic component according to claim 2, it is characterised in that described internal electron donor compound a is selected from 2-
(phenyl imido) methyl -4-TBP, 2- (phenyl imido) methyl -4,6- DI-tert-butylphenol compounds, 2- (phenyl imido) first
Base -4- chlorophenols, 2- (phenyl imido) methyl -4- fluorophenols, 2- (phenyl imido) methyl -4,6- chlorophenesic acids, 2- (benzene imines
Base) methyl -4- methylphenols, 2- (phenyl imido) methyl -4- isopropyl-phenols, 2- (phenyl imido) methylphenol, (benzene is sub- by 2-
Amido) methyl 4-phenyl phenol, 2- (2,6- diisopropyls phenyl imido) methyl -4,6- xylenols, (2,6- bis- is different by 2-
Propyl group phenyl imido) methyl -6- phenylphenols, 2- (2,6- diisopropyls phenyl imido) methyl -4- isopropyl-phenols, 2- (fourths
Imido grpup) methyl -4-TBP, 2- (fourth imido grpup) methyl -4,6- DI-tert-butylphenol compounds, 2- (own imido grpup) methyl -
4-TBP, 2- (own imido grpup) methyl -4,6- DI-tert-butylphenol compounds], 2- (pungent imido grpup) methyl -4- tert-butyl benzenes
Phenol, 2- (pungent imido grpup) methyl -4,6- DI-tert-butylphenol compounds, 2- (2,6- diisopropyls phenyl imido) methyl -4- tert-butyl benzenes
Phenol, 2- (2,6- diisopropyls phenyl imido) methyl -4,6- DI-tert-butylphenol compounds, the tertiary fourths of 2- (phenyl imido) methyl -4,6- two
Base phenol, 2- (phenyl imido) methyl-6-tert-butylphenol, 2- (2,6- diisopropyls phenyl imido) methyl -4,6- dimethyl
Phenol, 2- (2,6- imino dimethyl benzenes) methyl -4- DI-tert-butylphenol compounds, 2- (2,6- imino dimethyl benzenes) methyl -4,
6- DI-tert-butylphenol compounds, N- (2- methoxyl group -5- tert-butyl benzenes methylene) -2,6- diisopropyl anilines, N- (2- methoxyl groups -5-
Tert-butyl benzene methylene) -2,6- dimethylanilines, 2- (2,6- imino dimethyl benzenes) methyl -4- methoxyl group -6- tert-butyl benzenes
Phenol, N- benzylidene -2,6- diisopropyl anilines, 2- (4- chlorobenzenes imido grpup) methyl -4,6- DI-tert-butylphenol compounds, N- are to chlorobenzene
Methylene -2,6- diisopropyl anilines, N- (4- tert-butyl benzenes methylene) -2,6- diisopropyl anilines, N- benzylidenes -2,6-
Dimethylaniline, N- (2,4 dichloro benzene methylene) -2,6- dimethylanilines, N- (3,5- di-t-butyls benzylidene) aniline,
N- (2,4,6- trifluoros benzylidene) -2,6- dimethylanilines, [2- (2,3,4,5,6- phenyl-pentafluorides imido grpup) methyl -4,6- two
Tert-butyl phenol, N- (2- methoxynaphthalenes methylene) -2,6- diisopropyl anilines, 2- (2,6- diisopropyls phenyl imido) methyl
Phenol, 2- (2,6- imino dimethyl benzenes) methyl -6- tert-butyl phenols, 2- (2,6- diisopropyls phenyl imido) methyl -6-
(3,5- di-tert-butyls are sub- by tert-butyl phenol, N- (2- methoxyl group -3- tert-butyl benzenes methylene) -2,6- diisopropyl anilines, N-
Methyl)-naphthalidine, N- (3,5- di-t-butyls benzylidene) -2- naphthylamines, 2- (2- naphthalenes imido grpup) methylphenol, 2- (4- quinoline
Imido grpup) methyl -4,6- DI-tert-butylphenol compounds, 2- (3- quinoline imido grpup) methyl -4,6- DI-tert-butylphenol compounds, 2- (8- quinoline
Imido grpup) methyl -4,6- DI-tert-butylphenol compounds, N- (2- naphthals) -2,6- diisopropyl anilines, N- (1- naphthals) -
2,6- diisopropyl anilines, N- (1- naphthals) -2,6- dimethylanilines, N- (2- anthracenes methylene) -2,6- diisopropyl benzenes
Amine, N- (1- anthracenes methylene) -2,6- dimethylanilines, 2- (2- benzyls imido grpup) -4,6- DI-tert-butylphenol compounds, the 2- (uncles of 3,5- bis-
The hydroxyl of butyl -2) one kind or many in benzyl imido grpup phenol and 2- (hydroxyl of 3,5- di-t-butyls -2) benzyl imido grpup -1- naphthols
Kind.
5. catalytic component according to claim 3, it is characterised in that described internal electron donor compound b is selected from 2-
The benzoyloxy propane of isopropyl -1,3- two, the benzoyloxy propane of 2- butyl -1,3- two, the benzoyloxies third of 2- cyclohexyl -1,3- two
Alkane, the benzoyloxy propane of 2- benzyls -1,3- two, the benzoyloxy propane of 2- phenyl -1,3- two, 2- (1- naphthyls) -1,3- hexichol first
Carboxyl propane, 2- isopropyl -1,3- diethyl carboxyls propane, the benzoyloxy propane of 2- isopropyl -2- isopentyl -1,3- two, 2- are different
The benzoyloxy propane of propyl group -2- isobutyl groups -1,3- two, (the 4- butyl benzoyloxies) third of 2- isopropyl -2- isopentyl -1,3- two
Alkane, 2- isopropyl -2- isopentyl -1,3- dipropyl carboxyls propane, the benzoyloxy propane of 2- isopropyl -2- butyl -1,3- two, 2- are different
Propyl group -2- isopentyl -1- benzoyloxy -3- fourth carboxyls propane, 2- isopropyl -2- isopentyl -1- benzoyloxy -3- Chinese cassia tree carboxyls
Propane, 2- isopropyl -2- isopentyl -1- benzoyloxy -3- second carboxyls propane, 2,2- bicyclopentyl -1,3- hexichol carboxyls propane,
2,2- dicyclohexyl -1,3- hexichol carboxyls propane, 2,2- dibutyl -1,3- hexichol carboxyls propane, 2,2- diisobutyls -1,3- two
Benzene carboxyl propane, 2,2- diisopropyl -1,3- hexichol carboxyls propane, 2,2- diethyl -1,3- hexichol carboxyls propane, 2- ethyls -
2- butyl -1,3- hexichol carboxyls propane, the benzoyloxy pentanes of 2,4- bis-, the benzoyloxy pentanes of 3- ethyls -2,4- two, 3- methyl -
The benzoyloxy pentanes of 2,4- bis-, the benzoyloxy pentanes of 3- propyl group -2,4- two, the benzoyloxy pentanes of 3- isopropyls -2,4- two, 2,4-
Two (2- propyl group benzoyloxy) pentanes, 2,4- bis- (4- propyl group benzoyloxy) pentane, 2,4- bis- (2,4- dimethyl benzenes carboxyphenyl)
Pentane, 2,4- bis- (2,4 dichloro benzene carboxyphenyl) pentane, 2,4- bis- (4- chlorobenzenes carboxyphenyl) pentane, (the 4- cumenes of 2,4- bis-
Carboxyphenyl) pentane, 2,4- bis- (4- butyl benzoyloxy) pentane, 2,4- bis- (4- isobutyl-benzenes carboxyphenyl) pentane, 3,5- hexichol
Carboxyphenyl heptane, the benzoyloxy heptane of 4- ethyls -3,5- two, the benzoyloxy heptane of 4- propyl group -3,5- two, 4- isopropyls -3,5-
Two benzoyloxy heptane, 3,5- bis- (4- propyl group benzoyloxy) heptane, 3,5- bis- (4- cumenes carboxyphenyl) heptane, 3,5- bis-
(4- isobutyl-benzenes carboxyphenyl) heptane, 3,5- bis- (4- butyl benzoyloxy) heptane, 2- benzoyloxies -4- (4- isobutyl-benzene first
Carboxyl) pentane, 2- benzoyloxies -4- (4- butyl benzoyloxy) pentane, 2- benzoyloxies -4- (4- propyl group benzoyloxy) penta
Alkane, 3- benzoyloxies -5- (4- isobutyl-benzenes carboxyphenyl) heptane, 3- benzoyloxies -5- (4- butyl benzoyloxy) heptane, 3- benzene
Carboxyphenyl -5- (4- propyl group benzoyloxy) heptane, the benzoyloxy methyl fluorenes of 9,9- bis-, 9,9- bis- (the third carboxymethyl group) fluorenes, 9,9-
Two (isobutyl carboxymethyl group) fluorenes, 9,9- bis- (fourth carboxymethyl group) fluorenes, the benzoyloxy methyl -4- tert-butyl groups fluorenes of 9,9- bis-, 9,9- bis-
Benzoyloxy methyl -4- propyl group fluorenes, the benzoyloxy methyl isophthalic acids of 9,9- bis-, 2,3,4- tetrahydrochysenes fluorenes, the benzoyloxy methyl isophthalic acids of 9,9- bis-,
2,3,4,5,6,7,8- octahydros fluorenes, the phenylpropyl alcohol indenes of bis- benzoyloxy methyl -2,3,6,7- of 9,9- two, the benzoyloxy methyl of 9,9- bis- -
1,8- dichloros fluorenes, the norbornadienes of bis- benzoyloxy methyl -2,5- of 7,7- two, the benzoyloxy butane of 1,4- bis-, 2,3- diisopropyls
The benzoyloxy butane of base -1,4- two, the benzoyloxy butane of 2,3- dibutyl -1,4- two, the benzoyloxy benzene of 1,2- bis-, 3- ethyls -
The benzoyloxy benzene of 1,2- bis-, the benzoyloxy benzene of 4- butyl -1,2- two, the benzoyloxy naphthalenes of 1,8- bis-, 2- ethyl -1,8- hexichol first carboxylics
Base naphthalene, the benzoyloxy naphthalenes of 2- propyl group -1,8- two, the benzoyloxy naphthalenes of 2- butyl -1,8- two, the benzoyloxy naphthalenes of 4- butyl -1,8- two,
The benzoyloxy naphthalenes of 4- isobutyl groups -1,8- two, the benzoyloxy naphthalenes of 4- isopropyls -1,8- two, the benzoyloxy naphthalenes of 2- propyl group -1,8- two and
One or more in the benzoyloxy naphthalenes of 4- propyl group -1,8- two.
6. the catalytic component according to any one in Claims 1 to 5, it is characterised in that in described catalyst group
In point, the weight percentage for leading to the internal electron donor compound a shown in formula (I) is 0.01~20%；Shown in formula (II)
Internal electron donor compound b weight percentage is 0.01~20%.
7. catalytic component according to claim 6, it is characterised in that the internal electron donor compound a shown in logical formula (I)
Weight percentage be 1~15%；The weight percentage of internal electron donor compound b shown in formula (II) be 1~
15%.
8. catalytic component according to claim 6, it is characterised in that the internal electron donor compound a shown in logical formula (I)
Weight percentage be 2~10%.
9. a kind of catalyst for olefinic polymerization, it includes following components：
A. the catalytic component in claim 1~6 described in any one；
B. as the organo-aluminum compound of co-catalyst；With
C. optionally, external electron donor component.
10. catalyst according to claim 9, it is characterised in that described external electron donor is organo-silicon compound.
11. catalyst according to claim 10, it is characterised in that the organo-aluminum compound B and catalytic component A's
Mol ratio is calculated as 10~800 with aluminium/titanium:1, and/or the organo-silicon compound C and catalytic component A mol ratio with silicon/titanium
It is calculated as 0~200:1.
12. a kind of pre-polymerized catalyst for olefinic polymerization, described pre-polymerized catalyst is included according to claim 1~8
Catalytic component described in middle any one carries out the prepolymer obtained by prepolymerization with alkene.
13. in the catalytic component or claim 9-11 according to any one in claim 1~8 described in any one
Catalyst or claim 12 described in application of the pre-polymerized catalyst in olefinic polyreaction.
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410168579.2A CN105085726B (en) | 2014-04-24 | 2014-04-24 | A kind of catalytic component and catalyst for olefinic polymerization |
| MYPI2016703902A MY177142A (en) | 2014-04-24 | 2015-04-24 | Catalyst component for propene polymerization, preparation method thereof, and catalyst containing the same |
| CA2947095A CA2947095C (en) | 2014-04-24 | 2015-04-24 | Catalyst component for propene polymerization, preparation method thereof, and catalyst containing the same |
| ES15782393T ES2882951T3 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for propylene polymerization, method of preparation thereof and catalyst having the same |
| SG11201608923UA SG11201608923UA (en) | 2014-04-24 | 2015-04-24 | Catalyst component for propylene polymerization, preparation method therefor and catalyst having same |
| EP15782393.1A EP3135699B1 (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 |
| KR1020167032803A KR102305567B1 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for propylene polymerization, preparation method therefor and catalyst having same |
| 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 |
| PCT/CN2015/077379 WO2015161825A1 (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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| CN112759675B (en) * | 2019-10-21 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst component for preparing polyolefin, catalyst and application thereof |
| CN112759672B (en) * | 2019-10-21 | 2023-04-11 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization, catalyst and application thereof |
| CN112759676B (en) * | 2019-10-21 | 2023-08-15 | 中国石油化工股份有限公司 | Solid catalyst component for preparing polyolefin, catalyst and application thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364818A (en) * | 2002-02-09 | 2002-08-21 | 中国科学院上海有机化学研究所 | New olefine polymerization catalyst |
| CN1436796A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Solid catalyst component for olefine polymerization, catalyst with the component and its application |
| CN1436766A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Polyester compound for preparing olefine polymerizing catalyst |
| CN1472230A (en) * | 2000-07-04 | 2004-02-04 | 三井化学株式会社 | Method for preparing polar olefin copolymer and polar olefin copolymer therefrom |
| CN1827660A (en) * | 2005-02-28 | 2006-09-06 | 中国石油化工股份有限公司 | Supported bimetal polyvinyl catalyst and preparation method thereof |
| CN1884311A (en) * | 2006-05-22 | 2006-12-27 | 中国科学院上海有机化学研究所 | Mono-active center Ziegler-Natta catalyst for olefinic polymerization |
| EP2151446A1 (en) * | 2008-08-01 | 2010-02-10 | Telene SAS | Process for the preparation of bidentate schiff base ruthenium catalysts containing a salicylaldimine-type ligand |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020091120A (en) * | 2000-03-10 | 2002-12-05 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Polymerization of Olefins |
-
2014
- 2014-04-24 CN CN201410168579.2A patent/CN105085726B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1472230A (en) * | 2000-07-04 | 2004-02-04 | 三井化学株式会社 | Method for preparing polar olefin copolymer and polar olefin copolymer therefrom |
| CN1436796A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Solid catalyst component for olefine polymerization, catalyst with the component and its application |
| CN1436766A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Polyester compound for preparing olefine polymerizing catalyst |
| CN1364818A (en) * | 2002-02-09 | 2002-08-21 | 中国科学院上海有机化学研究所 | New olefine polymerization catalyst |
| CN1827660A (en) * | 2005-02-28 | 2006-09-06 | 中国石油化工股份有限公司 | Supported bimetal polyvinyl catalyst and preparation method thereof |
| CN1884311A (en) * | 2006-05-22 | 2006-12-27 | 中国科学院上海有机化学研究所 | Mono-active center Ziegler-Natta catalyst for olefinic polymerization |
| EP2151446A1 (en) * | 2008-08-01 | 2010-02-10 | Telene SAS | Process for the preparation of bidentate schiff base ruthenium catalysts containing a salicylaldimine-type ligand |
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