CN108517022A

CN108517022A - For the ingredient of solid catalyst and its catalyst of olefinic polymerization and application

Info

Publication number: CN108517022A
Application number: CN201710144264.8A
Authority: CN
Inventors: 王志武; 李树行; 李华姝; 张军伟; 胡乐; 代金松; 马庆利; 高勇; 陈颢; 焦文杰
Original assignee: Beijing Li Hezhixin Science And Technology Ltd
Current assignee: Beijing Li Hezhixin Science And Technology Ltd
Priority date: 2017-03-10
Filing date: 2017-03-10
Publication date: 2018-09-11
Anticipated expiration: 2037-03-10
Also published as: CN108517022B

Abstract

The present invention provides a kind of ingredient of solid catalyst for olefinic polymerization, it includes Mg, Ti, halogen and at least two electron donors, a kind of electron donor is the 2 substituted-amino phenyl ester compound A in general formula (I), and another electron donor is selected from the Lewis alkali cpds B containing one or more electronegativity groups.The invention also discloses the applications containing the catalyst of the ingredient of solid catalyst and the catalyst in olefinic polyreaction, the application especially in propylene polymerization.The catalyst has high activity, high isotacticity and broad molecular weight distribution polypropylene can be obtained, external electron donor is not needed and also can be obtained high isotatic polypropylene, when polymerization reduces Al/Ti and Al/Si, extends polymerization time, high activity can be still kept, the low ash content polymer of production is suitble to.

Description

For the ingredient of solid catalyst and its catalyst of olefinic polymerization and application

Technical field

The present invention relates to one kind being used for CH₂The ingredient of solid catalyst of=CHR olefinic polymerizations, wherein R is hydrogen or contains 1-12 The hydrocarbyl group of a carbon atom, it is more particularly related to containing at least one 2- substituted-aminos-phenyl ester compound with The ingredient of solid catalyst of Lewis alkali cpds, it is poly- in alkene containing the catalyst of the ingredient of solid catalyst and the catalyst Close the application in reaction, the application especially in propylene polymerization.

Background technology

In propylene polymerization industry, the catalyst studied and be most widely used is Ziegler-Natta catalyst, this is urged Agent is prepared by internal electron donor is added during carrying out load titanium to active magnesium chloride support.Due to internal electron donor Catalyst performance can farthest be changed, therefore study and find ideal internal electron donor compound to become Z-N catalyst The focus and hot spot of research.The research of internal electron donor is focused primarily upon both at home and abroad at present：1) traditional aliphatic ester and Aromatic esters compound, main representative are phthalate compounds；2) diether compound (such as EP0361493, EP0728724)；3) succinate compound compound (such as WO9856834, WO0063261, WO03022894)；4) diol-lipid Close object (such as WO9856834, WO0063261, WO03022894)；5) other functional groups compound (CN1105671, CN1242780, US20060128558) etc..

But in practical applications, above compound all exists as the internal electron donor of catalyst for olefines polymerizing and centainly asks Topic, the catalyst activity for such as making internal electron donor using binary aromatic carboxylic acid's ester type compound is not high, made polypropylene (PP) Relative molecular mass distribution is also relatively narrow, and phthalate compound is as common plasticizer, to the healthy reproduction of people There is very big harm with environment；Using 1, although the catalyst activity that 3- diether compounds make internal electron donor is higher, and urge Agent hydrogen response, but the relative molecular mass distribution of made PP is narrow, is unfavorable for developing the PP of the different trades mark；Succinic acid Ester type compound makees internal electron donor, and advantage is that the PP relative molecular mass distributions of synthesis are wider, is disadvantageous in that PP's is vertical The hydrogen response of structure regularity and catalyst is to be improved；And the activity of diol-lipid catalyst system and catalyzing is whole not as good as two ethers System is ideal.

When the catalyst prepared using single internal electron donor cannot be satisfied the particular requirement of polypropylene product, for example want The features such as asking catalyst to be provided simultaneously with super-active, high stereoselectivity, low external electron donor demand, a variety of internal electron donors Be used in compounding be also solves the problems, such as this effective ways, i.e., when preparing Z-N catalyst, at the same use two kinds or two kinds with On internal electron donor, and improve the comprehensive of Z-N catalyst by adjusting content of the different internal electron donors in Z-N catalyst Close performance.

Invention content

The purpose of the present invention is to provide one kind being used for CH₂The ingredient of solid catalyst of=CHR olefinic polyreactions.

Another object of the present invention is to provide the preparation methods of the ingredient of solid catalyst.

It is still another object of the present invention to provide the ingredients of solid catalyst in CH₂It is prepared by=CHR olefin polymerization catalysis In application.

In order to achieve the object of the present invention, the present invention provides the ingredient of solid catalyst (CH for olefinic polymerization₂= CHR alkene, wherein R are hydrogen or the hydrocarbyl group containing 1-12 carbon atom), it includes Mg, Ti, halogen and at least two electrons Body, a kind of electron donor A are 2- substituted-aminos-phenyl ester compound in general formula (I)：

Wherein, R¹、R²、R³And R⁴It is identical or different, it is H；Halogen；C₁-C₂₀Alkyl, can contain be selected from N, O, S, P, Si With one or more hetero atoms of halogen, as carbon atom either hydrogen atom or the substituent group of the two；R¹、R²、R³And R⁴Wherein Two or more be mutually bonded cyclization；R⁵For C₁-C₂₀Alkyl, containing one selected from N, O, S, P, Si and halogen or Multiple hetero atoms, as carbon atom either hydrogen atom or the substituent group of the two；R^IAnd R^IIIt is identical or different, it is H；C₁-C₂₀'s Alkyl can contain unsaturated bond containing one or more hetero atoms selected from N, O, S, P, Si and halogen；R^IAnd R^IIIt is bonding Cyclization or unsaturated bond；

Another electron donor B is selected from the Lewis alkali cpds containing one or more electronegativity groups；

The molar ratio of electron donor A and B are 0.01~100, preferably 0.02~50, more preferable 0.5~20.

Preferably, R in general formula (I)¹、R²、R³And R⁴It is identical or different, it is H；Halogen；C₁-C₂₀Linear chain or branched chain alkane It is base, naphthenic base, alkenyl, ester group, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl, halogenated or by N, O, S, P, Si hetero atom Substituted alkyl, naphthenic base, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl；Or it is selected from heterocyclic aryl substituent group；R¹、 R²、R³And R⁴It is therein it is two or more be mutually bonded circlewise structure, be saturation or it is undersaturated；R⁵For C₁-C₂₀ The alkyl of linear chain or branched chain, naphthenic base, alkenyl, ester group, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl, it is halogenated or by N, alkyl, naphthenic base, phenyl, alkyl phenyl, phenylalkyl, indenyl, the benzyl of O, S, P, Si hetero atom substitution；Or selected from miscellaneous Ring aryl substituent；R^IAnd R^IIIt is identical or different, it is H；C₁-C₂₀Linear chain or branched chain alkyl, naphthenic base, alkenyl, ester group, benzene Base, alkyl phenyl, phenylalkyl, indenyl, benzyl, halogenated or the alkyl, naphthenic base, the benzene that are replaced by N, O, S, P, Si hetero atom Base, alkyl phenyl, phenylalkyl, indenyl, benzyl；Or it is selected from heterocyclic aryl substituent group；R^IAnd R^IIBonding cyclization or insatiable hunger And key.

In one embodiment, R¹-R⁴At least one of (or two or three or four) R group be selected from substitution The hydrocarbyl group comprising 1 to 20 carbon atom, it is unsubstituted include 1 to 20 carbon atom hydrocarbyl group, include 1 to 20 The alkoxy base of carbon atom, hetero atom, and combinations thereof.

In one embodiment, R¹-R⁴In any adjacent R group can connect to form knot in interannular structure or ring Structure.Structure can be or can not be aromatics in interannular/ring.In one embodiment, structure is C5 membered rings in interannular/ring Or C6 membered rings.

In compound described in above-mentioned general formula (I), one is preferably the compound of the following general formula (II)：

Wherein, group R¹-R⁴And R^IIThere is meaning identical with formula (I) is led to；R^5’And R⁵It is identical or different, it is C₁-C₂₀'s Alkyl, containing one or more hetero atoms selected from N, O, S, P, Si and halogen, as carbon atom either hydrogen atom or two The substituent group of person, preferably C₁-C₂₀Linear chain or branched chain alkyl, naphthenic base, alkenyl, ester group, phenyl, alkyl phenyl, phenyl Alkyl, indenyl, benzyl, halogenated or the alkyl, naphthenic base, phenyl, alkyl phenyl, the octadecyloxy phenyl that are replaced by N, O, S, P, Si hetero atom Base, indenyl, benzyl；Or it is selected from heterocyclic aryl substituent group.

Being included in the specific example of the compound in general formula (II) is：

2- acetamides-phenylacetate；2- propionamides-phenyl propionate；2- butanamides-n-butyric acie phenyl ester；2- isobutyramides- Isobutyl acid phenenyl ester；The positive valeric acid phenyl ester of 2- n-valeramides-；2- isovaleramide-isoamyl acid phenenyl ester；2- n-caproamides-n-caproic acid phenyl ester； 2- hexamethylenes formamide-cyclohexanecarboxylic acid phenyl ester；The positive enanthic acid phenyl ester of the positive heptamides-of 2-；The positive caprylamides of 2--caprylic acid phenyl ester；The positive nonyls of 2- Amide-pelargonic acid phenyl ester；The positive decyl amide of 2--n-capric acid phenyl ester；The positive undecanoic acid phenyl ester of the positive undecanoic amides-of 2-；The positive lauramides-of 2- Positive lauric acid/dodecanoic acid phenyl ester；The positive tridecanoic acid phenyl ester of the positive tridecanoyl amine-of 2-；The positive tetradecylic acid phenyl ester of the positive myristamides-of 2-；The positive pentadecanoyls of 2- The positive pentadecanoic acid phenyl ester of amine-；The positive palmitamides of 2--n-hexadecanoic phenyl ester；The positive heptadecanoyl amine-margaric acid phenyl esters of 2-；2- positive 18 Amide-n-octadecanoic acid phenyl ester；The positive nonadecanoic acid phenyl ester of positive 19 amides-of 2-；Positive 20 acid phenenyl ester of positive 20 amides-of 2-；

2- acetamides -4- methyl-phenylacetate；2- propionamide -4- rnethyl-propanoic acid phenyl esters；2- butanamide -4- methyl - N-butyric acie phenyl ester；2- isobutyramides-isobutyl acid phenenyl ester；The positive valeric acid phenyl ester of 2- n-valeramides-；2- isovaleramide-isoamyl acid phenenyl ester； 2- n-caproamides -4- methyl-n-caproic acid phenyl ester；2- hexamethylene formamide -4- methyl-cyclohexyl phenyl formates；Positive heptamide -4- the first of 2- The positive enanthic acid phenyl ester of base-；Positive caprylamide -4- methyl-caprylic acid the phenyl esters of 2-；Positive pelargonamide -4- methyl-pelargonic acid the phenyl esters of 2-；2- is just Decyl amide -4- methyl-n-capric acid phenyl ester；The positive undecanoic acid phenyl ester of the positive undecanoic amide -4- methyl-of 2-；Positive lauramide -4- the first of 2- The positive lauric acid/dodecanoic acid phenyl ester of base-；The positive tridecanoic acid phenyl ester of the positive tridecanoyl amine -4- methyl-of 2-；Positive myristamide -4- the methyl of 2--positive tetradecylic acid Phenyl ester；The positive pentadecanoic acid phenyl ester of the positive pentadecanoyl amine -4- methyl-of 2-；Positive palmitamide -4- methyl-n-hexadecanoic the phenyl esters of 2-；2- positive ten Seven amide -4- methyl-margaric acid phenyl ester；Positive stearamide -4- methyl-n-octadecanoic acid the phenyl esters of 2-；The positive 19 amide -4- first of 2- The positive nonadecanoic acid phenyl ester of base-；Positive 20 acid phenenyl ester of the positive 20 amide -4- methyl-of 2-；

2- acetamides -4- ethyls-phenylacetate；2- propionamides -4- ethyls-phenyl propionate；2- butanamide -4- ethyls - N-butyric acie phenyl ester；2- isobutyramides -4- ethyls-isobutyl acid phenenyl ester；The positive valeric acid phenyl ester of 2- n-valeramide -4- ethyls -；2- isovaleryls Amine -4- ethyls-isoamyl acid phenenyl ester；2- n-caproamides -4- ethyls-n-caproic acid phenyl ester；2- hexamethylene formamide -4- ethyls-hexamethylene first Acid phenenyl ester；The positive enanthic acid phenyl ester of the positive heptamide -4- ethyls-of 2-；Positive caprylamide -4- ethyls-caprylic acid the phenyl esters of 2-；The positive pelargonamides-of 2- 4- ethyls-pelargonic acid phenyl ester；Positive decyl amide -4- ethyls-n-capric acid the phenyl esters of 2-；

2- acetamides -4- tertiary butyls-phenylacetate；2- propionamides -4- tertiary butyls-phenyl propionate；2- butanamide -4- uncles Butyl-n-butyric acie phenyl ester；2- isobutyramides -4- tertiary butyls-isobutyl acid phenenyl ester；The positive valeric acid benzene of 2- n-valeramide -4- tertiary butyls - Ester；2- isovaleramide -4- tertiary butyls-isoamyl acid phenenyl ester；2- n-caproamides -4- tertiary butyls-n-caproic acid phenyl ester；2- hexamethylene formyls Amine -4- tert-Butyl-cyclohex phenyl formates；The positive enanthic acid phenyl ester of the positive heptamide -4- tertiary butyls-of 2-；Positive caprylamide -4- the tertiary butyls-of 2- Caprylic acid phenyl ester；Positive pelargonamide -4- tertiary butyls-pelargonic acid the phenyl esters of 2-；Positive decyl amide -4- tertiary butyls-n-capric acid the phenyl esters of 2-；2- is just The positive undecanoic acid phenyl ester of undecanoic amide -4- tertiary butyls -；The positive lauric acid/dodecanoic acid phenyl ester of the positive lauramide -4- tertiary butyls-of 2-；The positive tridecanoyls of 2- The positive tridecanoic acid phenyl ester of amine -4- tertiary butyls -；The positive tetradecylic acid phenyl ester of the positive myristamide -4- tertiary butyls-of 2-；The positive pentadecanoyl amine -4- uncles of 2- The positive pentadecanoic acid phenyl ester of butyl-；Positive palmitamide -4- tertiary butyls-n-hexadecanoic the phenyl esters of 2-；The positive heptadecanoyl amine -4- tertiary butyls-of 2- are just Heptadecanoic acid phenyl ester；Positive stearamide -4- tertiary butyls-n-octadecanoic acid the phenyl esters of 2-；The positive 19 amide -4- tertiary butyls of 2--positive nonadecanoic acid Phenyl ester；Positive 20 acid phenenyl ester of the positive 20 amide -4- tertiary butyls-of 2-；

2- acetamide -4- methyl -6- methyl-phenylacetate；2- propionamide -4- methyl -6- rnethyl-propanoic acid phenyl esters；2- is just Butyramide -4- methyl -6- methyl-n-butyric acie phenyl ester；2- isobutyramide -4- methyl -6- methyl-isobutyl acid phenenyl ester；The positive valeryls of 2- The positive valeric acid phenyl ester of amine -4- methyl -6- methyl -；2- isovaleramide -4- methyl -6- methyl-isoamyl acid phenenyl ester；2- n-caproamides -4- Methyl -6- methyl-n-caproic acid phenyl ester；2- hexamethylene formamide -4- methyl -6- methyl-cyclohexyl phenyl formates；Positive heptamide-the 4- of 2- The positive enanthic acid phenyl ester of methyl -6- methyl -；Positive caprylamide -4- methyl -6- methyl-caprylic acid the phenyl esters of 2-；Positive pelargonamide -4- the methyl-of 2- 6- methyl-pelargonic acid phenyl ester；Positive decyl amide -4- methyl -6- methyl-n-capric acid the phenyl esters of 2-；

The chloro- phenylacetates of 2- acetamides -4-；The chloro- phenyl propionates of 2- propionamides -4-；The chloro- n-butyric acies of 2- butanamides -4- Phenyl ester；The chloro- isobutyl acid phenenyl esters of 2- isobutyramides -4-；The chloro- positive valeric acid phenyl esters of 2- n-valeramides -4-；2- isovaleramide -4- is chloro- different Valeric acid phenyl ester；The chloro- n-caproic acid phenyl esters of 2- n-caproamides -4-；The chloro- cyclohexanecarboxylic acid phenyl esters of 2- hexamethylene formamides -4-；The positive butyryl of 1- Amine -2- n-butyric acie naphthalene esters；

2-benzamide-phenol benzoate；2- is to chlorobenzamide-parachlorobenzoic-acid phenyl ester；Brombenzamide-between 2- Bromobenzoic acid phenyl ester；2- neighbour's chlorobenzamide -0-chloro-benzoic acid phenyl ester；2- is to methoxy benzamide-P-methoxybenzoic acid Phenyl ester；2- is to methyl benzamide-p-methylbenzoic acid phenyl ester；2- benzene oxygen formamide-benzene oxygen phenyl formate；2- (1- naphthalene formyls Amine)-(1- naphthoic acids) phenyl ester；2- phenyl-pentafluorides formamide-pentafluoro benzoic acid phenyl ester；2- is to trifluoromethyl benzamide-to trifluoro Methyl benzoic acid phenyl ester；1- benzamide -2- naphthol benzoates；

2- [N- benzoyl amine-n -s tertiary butyl]-phenol benzoate；2- [N- benzoyl amine-n -s tertiary butyl] -4- tertiary butyls - Phenol benzoate；2- [N- benzoyl amine-n -s tertiary butyl] -4- methyl-benzoic acid phenyl esters；2- [N- benzoyl amine-n -s tertiary butyl]- 4- ethyl-benzoic acid phenyl esters；2- [N- benzoyl amine-n -s tertiary butyl] -4- methyl -6- methyl-benzoic acid phenyl esters；2- [N- benzene first Acyl amine-n-tertiary butyl] -4- tertiary butyls-isoamyl acid phenenyl ester；2- [N- benzoyl amine-n -s phenyl] -4- t-butyl-benzoic acid phenyl esters； 2- [N- benzoyl amine-n -s phenyl] -4- methyl-benzoic acid phenyl esters；2- [N- benzoyl amine-n -s phenyl] -4- ethyls base-benzoic acid Phenyl ester；2- [N- benzoyl amine-n -s phenyl] -4- methyl -6- methyl-benzoic acid phenyl esters；2- [N- benzoyl amine-n -s phenyl] -4- Tertiary butyl-n-butyric acie phenyl ester；2- [N- benzoyl amine-n -s methyl] -4- tertiary butyls-n-butyric acie phenyl ester；

2-benzamide -4- methyl-benzoic acid phenyl esters；2- is to chlorobenzamide -4- methyl-parachlorobenzoic-acid phenyl ester；2- Between brombenzamide -4- methyl-m-bromobenzoic acid phenyl ester；2- neighbour's chlorobenzamide -4- methyl -0-chloro-benzoic acid phenyl ester；2- pairs Methoxy benzamide -4- methyl-p-methoxy phenol benzoates；2- is to methyl benzamide -4- methyl-p-methylbenzoic acid Phenyl ester；2- benzene oxygen formamide -4- methyl-benzene oxygen phenyl formate；2- (1- naphthalenecarboxamides) -4- methyl-(1- naphthoic acids) phenyl ester；2- Phenyl-pentafluoride formamide -4- methyl-pentafluoro benzoic acid phenyl ester；2- is to trifluoromethyl benzamide -4- methyl-to trifluoromethylbenzene first Acid phenenyl ester；

2-benzamide -4- ethyl-benzoic acid phenyl esters；2- is to chlorobenzamide -4- ethyls-parachlorobenzoic-acid phenyl ester；2- Between brombenzamide -4- ethyls-m-bromobenzoic acid phenyl ester；2- neighbour's chlorobenzamide -4- ethyls -0-chloro-benzoic acid phenyl ester；2- pairs Methoxy benzamide -4- ethyls-P-methoxybenzoic acid phenyl ester；2- is to methyl benzamide -4- ethyl-p-menthan benzoic acid Phenyl ester；2- benzene oxygen formamide -4- ethyls-benzene oxygen phenyl formate；2- (1- naphthalenecarboxamides) -4- ethyls-(1- naphthoic acids) phenyl ester；2- Phenyl-pentafluoride formamide -4- ethyls-pentafluoro benzoic acid phenyl ester；2- is to trifluoromethyl benzamide -4- ethyls-to trifluoromethylbenzene first Acid phenenyl ester；

2-benzamide -4- t-butyl-benzoic acid phenyl esters；2- is to chlorobenzamide -4- tertiary butyls-parachlorobenzoic-acid benzene Ester；Brombenzamide -4- tertiary butyls-m-bromobenzoic acid phenyl ester between 2-；2- neighbour's chlorobenzamide -4- tertiary butyls -0-chloro-benzoic acid Phenyl ester；2- is to methoxy benzamide -4- tertiary butyls-P-methoxybenzoic acid phenyl ester；2- is to the tertiary fourths of methyl benzamide -4- Base-p-methylbenzoic acid phenyl ester；2- benzene oxygen formamide -4- tertiary butyls-benzene oxygen phenyl formate；The tertiary fourths of 2- (1- naphthalenecarboxamides) -4- Base-(1- naphthoic acids) phenyl ester；2- phenyl-pentafluoride formamide -4- tertiary butyls-pentafluoro benzoic acid phenyl ester；2- is to trifluoromethylbenzoyl Amine -4- tertiary butyls-are to trifluoromethylbenzoic acid phenyl ester；

2-benzamide -4- methyl -6- methyl-benzoic acid phenyl esters；2- is to chlorobenzamide -4- methyl -6- methyl-to chlorine Phenol benzoate；Brombenzamide -4- methyl -6- methyl-m-bromobenzoic acid phenyl ester between 2-；2- neighbour chlorobenzamide -4- methyl - 6- methyl -0-chloro-benzoic acid phenyl ester；2- is to methoxy benzamide -4- methyl -6- methyl-p-methoxy phenol benzoates；2- To methyl benzamide -4- methyl -6- methyl-p-methylbenzoic acid phenyl ester；2- benzene oxygen formamide -4- methyl -6- methyl-benzene oxygen Phenyl formate；2- (1- naphthalenecarboxamides) -4- methyl -6- methyl-(1- naphthoic acids) phenyl ester；2- phenyl-pentafluoride formamide -4- methyl -6- Methyl-pentafluoro benzoic acid phenyl ester；2- is to trifluoromethyl benzamide -4- methyl -6- methyl-to trifluoromethylbenzoic acid phenyl ester；

The chloro- phenol benzoates of 2-benzamide -4-；2- is to the chloro- parachlorobenzoic-acid phenyl esters of chlorobenzamide -4-；Bromine between 2- The chloro- m-bromobenzoic acid phenyl esters of benzamide -4-；The chloro- 0-chloro-benzoic acid phenyl esters of 2- neighbour's chlorobenzamide -4-；2- is to methoxybenzene The chloro- P-methoxybenzoic acid phenyl esters of formamide -4-；2- is to the chloro- p-methylbenzoic acid phenyl esters of methyl benzamide -4-；2- benzene oxygen The chloro- benzene oxygen phenyl formates of formamide -4-；Chloro- (1- naphthoic acids) phenyl esters of 2- (1- naphthalenecarboxamides) -4-；2- phenyl-pentafluoride formamides -4- Chloro- pentafluoro benzoic acid phenyl ester；2- is chloro- to trifluoromethyl benzamide -4- to trifluoromethylbenzoic acid phenyl ester.

2- benzene oxygen formamide-benzene oxygen phenyl formate；2- benzene oxygen formamide -4- methyl-benzene oxygen phenyl formate；2- benzene oxygen formyls Amine -4- ethyls-benzene oxygen phenyl formate；2- benzene oxygen formamide -4- tertiary butyls-benzene oxygen phenyl formate；2- benzene oxygen formamide -4- first Base -6- methyl-benzene oxygen phenyl formate；2- is to methoxybenzene oxygen formamide-to methoxybenzene oxygen phenyl formate；Chlorobenzene oxygen first between 2- Amide-chlorobenzene oxygen phenyl formate；2- is to chlorobenzene oxygen formamide-to chlorobenzene oxygen phenyl formate；2- neighbour's chlorobenzene oxygen formamide-neighbour's chlorine Benzene oxygen phenyl formate；2- normal-butyls oxygen formamide-fourth oxygen phenyl formate；2- normal-butyl oxygen formamide -4- methyl-fourth oxygen formic acid benzene Ester；2- normal-butyl oxygen formamide -4- ethyls-fourth oxygen phenyl formate；2- normal-butyl oxygen formamide -4- tertiary butyls-fourth oxygen formic acid benzene Ester；- 6 methyl of 2- normal-butyl oxygen formamide -4- methyl-fourth oxygen phenyl formate；The chloro- fourth oxygen formic acid benzene of 2- normal-butyl oxygen formamides 4- Ester；2- isobutyl groups oxygen formamide-isobutyl oxygen phenyl formate；2- isopentyl oxygen formamide-isoamyl phenyl formate；2- n-octyl oxygen first Amide-Ding Xin phenyl formates；2- methylamino ethoxies amide-ethoxy phenyl formate；2- methylamino ethoxy amide -4- methyl-ethoxy phenyl formate； 2- methylamino ethoxy amide -4- ethyls-ethoxy phenyl formate；2- methylamino ethoxy amide -4- tertiary butyls-ethoxy phenyl formate；2- methylamino ethoxies - 6 methyl of amide -4- methyl-ethoxy phenyl formate；The chloro- ethoxy phenyl formates of 2- methylamino ethoxy amides 4-；

Lead in the compound described in formula (II), preferably the compound of the following general formula (III)：

Wherein, group R¹-R⁵There is meaning identical with formula (I) is led to, R^5’There is meaning identical with formula (II) is led to, R⁶With R^6’It is identical or different, it is selected from H；C₁-C₂₀Alkyl, containing selected from N, O, S, P, Si and halogen one or more hetero atoms, As carbon atom either hydrogen atom or the substituent group of the two, preferably C₁-C₂₀Linear chain or branched chain alkyl, naphthenic base, alkene Base, ester group, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl, it is halogenated or replaced by N, O, S, P, Si hetero atom alkyl, Naphthenic base, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl；Or it is selected from heterocyclic aryl substituent group.

Being included in the specific example of the compound in logical formula (III) is：

2- [N- benzoyl-N- benzyls]-phenol benzoate；2- [N- is to chlorobenzoyl-N- benzyls]-parachlorobenzoic-acid benzene Ester；2- [Bromophenacyl-N- benzyls between N-]-m-bromobenzoic acid phenyl ester；2- [N- neighbour chlorobenzoyl-N- benzyls] -0-chloro-benzoic acid Phenyl ester；2- [N- is to methoxybenzoyl-N- benzyls]-P-methoxybenzoic acid phenyl ester；[N- is to toluyl-N- benzyls by 2- Base]-p-methylbenzoic acid phenyl ester；2- [N- benzene oxygen formyl-N- benzyls]-benzene oxygen phenyl formate；2- (1- naphthalene formyl-N- benzyls)- (1- naphthoic acids) phenyl ester；2- [N- phenyl-pentafluoride formyl-N- benzyls]-pentafluoro benzoic acid phenyl ester；[N- is to trifluoromethylbenzoyl-by 2- N- benzyls]-to trifluoromethylbenzoic acid phenyl ester；1- [N- benzoyl-N- benzyls] -2- naphthol benzoates；

2- [N- benzoyl-N- benzyls] -4- t-butyl-benzoic acid phenyl esters；2- [N- is to chlorobenzoyl-N- benzyls] -4- uncles Butyl-parachlorobenzoic-acid phenyl ester；2- [Bromophenacyl-N- benzyls between N-] -4- tertiary butyls-m-bromobenzoic acid phenyl ester；2- [N- neighbour's chlorine Benzoyl-N- benzyls] -4- tertiary butyls -0-chloro-benzoic acid phenyl ester；2- [N- is to methoxybenzoyl-N- benzyls] -4- tertiary butyls - P-methoxybenzoic acid phenyl ester；2- [N- is to toluyl-N- benzyls] -4- t-butyl-p-methyl phenol benzoates；2-[N- Benzene oxygen formyl-N- benzyls] -4- tertiary butyls-benzene oxygen phenyl formate；2- (1- naphthalene formyl-N- benzyls) -4- tertiary butyls-(1- naphthalene first Acid) phenyl ester；2- [N- phenyl-pentafluoride formyl-N- benzyls] -4- tertiary butyls-pentafluoro benzoic acid phenyl ester；[N- is to trifluoromethylbenzene first by 2- Acyl-N- benzyls] -4- tertiary butyls-are to trifluoromethylbenzoic acid phenyl ester；

2- [N- benzoyl-N- isopropyls] -4- t-butyl-benzoic acid phenyl esters；2- [N- is to chlorobenzoyl-N- isopropyls]- 4- tertiary butyls-parachlorobenzoic-acid phenyl ester；2- [Bromophenacyl-N- isopropyls between N-] -4- tertiary butyls-m-bromobenzoic acid phenyl ester；2- [N- neighbour chlorobenzoyl-N- isopropyls] -4- tertiary butyls -0-chloro-benzoic acid phenyl ester；[N- is to methoxybenzoyl-N- isopropyls by 2- Base] -4- tertiary butyls-P-methoxybenzoic acid phenyl ester；2- [N- is to toluyl-N- isopropyls] -4- t-butyl-p-methyl benzene Phenyl formate；2- [N- benzene oxygen formyl-N- isopropyls] -4- tertiary butyls-benzene oxygen phenyl formate；2- (1- naphthalene formyl-N- isopropyls)- 4- tertiary butyls-(1- naphthoic acids) phenyl ester；2- [N- phenyl-pentafluoride formyl-N- isopropyls] -4- tertiary butyls-pentafluoro benzoic acid phenyl ester；2- [N- is to trifluoromethylbenzoyl-N- isopropyls] -4- tertiary butyls-are to trifluoromethylbenzoic acid phenyl ester；

2- [N- benzoyl-N- benzyls] -4- methyl-benzoic acid phenyl esters；2- [N- is to chlorobenzoyl-N- benzyls] -4- methyl - 6- methyl parachlorobenzoic-acid phenyl esters；2- [Bromophenacyl-N- benzyls between N-] -4- methyl -6- methyl-m-bromobenzoic acid phenyl ester；2- [N- neighbour chlorobenzoyl-N- benzyls] -4- methyl -0-chloro-benzoic acid phenyl ester；2- [N- is to methoxybenzoyl-N- benzyls] -4- first Base -6- methyl-p-methoxy phenol benzoates；2- [N- is to toluyl-N- benzyls] -4- methyl -6- methyl-is to methylbenzene Phenyl formate；2- [N- benzene oxygen formyl-N- benzyls] -4- methyl-benzene oxygen phenyl formate；2- (1- naphthalene formyl-N- benzyls) -4- first Base-(1- naphthoic acids) phenyl ester；2- [N- phenyl-pentafluoride formyl-N- benzyls] -4- methyl-pentafluoro benzoic acid phenyl ester；[N- is to fluoroform by 2- Base benzoyl-N- benzyls] -4- methyl-is to trifluoromethylbenzoic acid phenyl ester；

2- [N- benzoyl-N- phenethyls] -4- t-butyl-benzoic acid phenyl esters；2- [N- is to chlorobenzoyl-N- n-pentyls]- 4- tertiary butyls-parachlorobenzoic-acid phenyl ester；2- [N- is to chlorobenzoyl-N- isopropyls] -4- tertiary butyls-parachlorobenzoic-acid phenyl ester；2- [Bromophenacyl-N- isobutyl groups between N-] -4- tertiary butyls-m-bromobenzoic acid phenyl ester；2- [N- neighbour's chlorobenzoyl-N- cyclohexyl first Base] -4- tertiary butyls -0-chloro-benzoic acid phenyl ester；2- [N- is to methoxybenzoyl-N- to chlorophenylmethyl] -4- tertiary butyls-are to methoxy Yl benzoic acid phenyl ester；2- [N- is to toluyl-N- to mehtoxybenzyl] -4- t-butyl-p-methyl phenol benzoates；2- [N- benzene oxygen formyl-N- benzhydryls] -4- tertiary butyls-benzene oxygen phenyl formate；2- (1- naphthalene formyl-N- decyls) -4- tertiary butyls - (1- naphthoic acids) phenyl ester；2- [N- phenyl-pentafluoride formyl-N- n-hexyls] -4- tertiary butyls-pentafluoro benzoic acid phenyl ester；[N- is to trifluoro by 2- Toluyl-N- n-heptyls] -4- tertiary butyls-are to trifluoromethylbenzoic acid phenyl ester；

2- [N- benzoyl-N- phenethyls] -4- methyl -6- methyl-benzoic acid phenyl esters；2- [N- positive to chlorobenzoyl-N- penta Base] -4- methyl -6- methyl-parachlorobenzoic-acid phenyl ester；2- [N- is to chlorobenzoyl-N- n-propyls] -4- methyl -6- methyl-is to chlorine Phenol benzoate；2- [Bromophenacyl-N- isobutyl groups between N-] -4- methyl -6- methyl-m-bromobenzoic acid phenyl ester；

2- [N- benzoyl-N- benzhydryls] -4- methyl -6- methyl-benzoic acid phenyl esters；[N- is to chlorobenzoyl-N- two by 2- Benzyl] -4- methyl -6- methyl-parachlorobenzoic-acid phenyl ester；2- [N- is to chlorobenzoyl-N- benzhydryls] -4- methyl -6- first Base-parachlorobenzoic-acid phenyl ester；2- [Bromophenacyl-N- benzhydryls between N-] -4- methyl -6- methyl-m-bromobenzoic acid phenyl ester；

2- [N- acetyl-N- benzyls]-phenylacetate；2- [N- propionyl-N- benzyls]-phenyl propionate；2- [positive butyryl-the N- of N- Benzyl]-n-butyric acie phenyl ester；2- [N- isobutyryl-N- benzyls]-isobutyl acid phenenyl ester；The positive valeric acid benzene of 2- [the positive valeryl-N- benzyls of N-]- Ester；2- [N- isovaleryl-N- benzyls]-isoamyl acid phenenyl ester；2- [the positive hexanoyl-N- benzyls of N-]-n-caproic acid phenyl ester；2- [N- hexamethylene first Acyl-N- benzyls]-cyclohexanecarboxylic acid phenyl ester；The positive enanthic acid phenyl esters of 2- [the positive oenanthyl-N- benzyls of N-]-；2- [the positive decoyl-N- benzyls of N-]-is just Sad phenyl ester；2- [the positive nonanoyl-N- benzyls of N-]-pelargonic acid phenyl ester；2- [the positive caprinoyl-N- benzyls of N-]-n-capric acid phenyl ester；2-[N- Positive undecanoyl-N- benzyls]-positive undecanoic acid phenyl ester；The positive lauric acid/dodecanoic acid phenyl esters of 2- [the positive lauroyl-N- benzyls of N-]-；2- [N- positive 13 Acyl-N- benzyls]-positive tridecanoic acid phenyl ester；The positive tetradecylic acid phenyl esters of 2- [the positive myristoyl-N- benzyls of N-]-；2- [positive pentadecanoyl-N- the benzyls of N- Base]-positive pentadecanoic acid phenyl ester；2- [the positive palmityl-N- benzyls of N-]-n-hexadecanoic phenyl ester；2- [the positive heptadecanoyl-N- benzyls of N-]-is just Heptadecanoic acid phenyl ester；2- [the positive 18 acyl-N- benzyls of N-]-n-octadecanoic acid phenyl ester；2- [the positive 19 acyl-N- benzyls of N-]-positive nonadecanoic acid Phenyl ester；2- [the positive 20 acyl-N- benzyls of N-]-positive 20 acid phenenyl ester；

2- [N- acetyl-N- benzyls] -4- tertiary butyls-phenylacetate；2- [N- propionyl-N- benzyls] -4- rnethyl-propanoic acid benzene Ester；2- [the positive butyryl-N- benzyls of N-] -4- methyl-n-butyric acie phenyl ester；2- [N- isobutyryl-N- benzyls] -4- tertiary butyls-isobutyric acid Phenyl ester；The positive valeric acid phenyl ester of 2- [the positive valeryl-N- benzyls of N-] -4- methyl -；2- [N- isovaleryl-N- benzyls] -4- methyl-isovaleric acid Phenyl ester；2- [the positive hexanoyl-N- benzyls of N-] -4- methyl -6- methyl-n-caproic acid phenyl ester；2- [N- hexamethylene formyl-N- benzyls] -4- uncles Butyl-cyclohexa phenyl formate；The positive enanthic acid phenyl ester of 2- [the positive oenanthyl-N- benzyls of N-] -4- tertiary butyls -；2- [positive decoyl-N- the benzyls of N- Base] -4- methyl-caprylic acid phenyl ester；2- [the positive nonanoyl-N- benzyls of N-] -4- methyl-pelargonic acid phenyl ester；2- [positive caprinoyl-N- the benzyls of N- Base] -4- tertiary butyls-n-capric acid phenyl ester；The positive undecanoic acid phenyl ester of 2- [the positive undecanoyl-N- benzyls of N-] -4- tertiary butyls -；2- [N- positive ten Two acyl-N- benzyls] the positive lauric acid/dodecanoic acid phenyl ester of -4- tertiary butyls -；The positive tridecanoic acid benzene of 2- [the positive tridecanoyl-N- benzyls of N-] -4- tertiary butyls - Ester；The positive tetradecylic acid phenyl ester of 2- [the positive myristoyl-N- benzyls of N-] -4- tertiary butyls -；

2- [N- acetyl-N- phenethyls] -4- tertiary butyls-phenylacetate；2- [N- propionyl-N- phenethyls] -4- rnethyl-propanoic acids Phenyl ester；2- [the positive butyryl-N- n-pentyls of N-] -4- methyl-n-butyric acie phenyl ester；2- [N- isobutyryl-N- isobutyl groups] -4- tertiary butyls - Isobutyl acid phenenyl ester；The positive valeric acid phenyl ester of 2- [the positive valeryl-N- n-hexyls of N-] -4- methyl -；2- [N- isovaleryl-N- cyclohexyl methyls]- 4- methyl-isoamyl acid phenenyl ester；2- [the positive hexanoyl-N- positive decyls of N-] -4- methyl -6- methyl-n-caproic acid phenyl ester；2- [N- hexamethylene first Acyl-N- is to mehtoxybenzyl] -4- tert-Butyl-cyclohex phenyl formates；2- [the positive oenanthyl-N- neighbours chlorophenylmethyls of N-] tertiary fourths of -4- The positive enanthic acid phenyl ester of base-；2- [the positive decoyl-N- of N- are to methylbenzyl] -4- methyl-caprylic acid phenyl ester；[the positive nonanoyl-N- of N- are just by 2- Propyl] -4- methyl-pelargonic acid phenyl ester；2- [the positive caprinoyl-N- isopentyl of N-] -4- tertiary butyls-n-capric acid phenyl ester；2- [N- positive 11 Acyl-N- isopentyl] the positive undecanoic acid phenyl ester of -4- tertiary butyls -；2- [the positive lauroyl-N- cyclopentyl-methyls of N-] -4- tertiary butyls-positive ten Two acid phenenyl esters；The positive tridecanoic acid phenyl ester of 2- [the positive tridecanoyl-N- of N- are to trifluoromethylbenzel] -4- tertiary butyls -；2- [N- positive 14 Chlorophenylmethyl between acyl-N-] the positive tetradecylic acid phenyl ester of -4- tertiary butyls -；

2- [N- benzene oxygen formyl-N- benzyls]-benzene oxygen phenyl formate；2- [N- is to methylenedioxy phenoxy formyl-N- benzyls]-is to methyl Benzene oxygen phenyl formate；2- [N- is to methoxybenzene oxygen formyl-N- benzyls]-is to methoxybenzene oxygen phenyl formate；2- [N- benzene oxygen first Acyl-N- benzyls] -4- tertiary butyls-benzene oxygen phenyl formate；2- [N- benzene oxygen formyl-N- benzyls] -4- methyl-benzene oxygen phenyl formate；2- [N- benzene oxygen formyl-N- benzyls] -4- ethyls-benzene oxygen phenyl formate；2- [N- benzene oxygen formyl-N- benzyls] -4- methyl -6- methyl - Benzene oxygen phenyl formate；The positive fourth oxygen phenyl formates of 2- [N- normal-butyl oxygen formyl-N- benzhydryls]-；2- [N- isopentyl oxygen formyls- N- benzhydryls]-isoamyl oxygen phenyl formate；The positive fourth oxygen of 2- [N- normal-butyl oxygen formyl-N- benzhydryls] -4- methyl -6- methyl - Phenyl formate；The positive fourth oxygen phenyl formate of 2- [N- normal-butyl oxygen formyl-N- benzhydryls] -4- methyl -；2- [N- normal-butyl oxygen first Acyl-N- benzhydryls] the positive fourth oxygen phenyl formate of -4- tertiary butyls -；2- methylamino ethoxies amide-ethoxy phenyl formate；2- ethoxycarbonyls Amine -4- methyl-ethoxy phenyl formate；2- methylamino ethoxy amide -4- ethyls-ethoxy phenyl formate；The tertiary fourths of 2- methylamino ethoxy amide -4- Base-ethoxy phenyl formate；2- methylamino ethoxy amides -4- methyl-methyl-ethoxy phenyl formates；The chloro- methylamino ethoxies of 2- methylamino ethoxy amide 4- Acid phenenyl ester；

In compound described in logical formula (I), the compound of another preferably the following general formula (IV)：

Wherein, group R¹-R⁵There is meaning identical with formula (I) is led to；R⁶And R^6’Meaning identical with logical formula (III).

Being included in the specific example of the compound in logical formula (IV) is：

2- benzimides-phenol benzoate；2- benzene ethyleneimine-phenol benzoate；Positive tetrahydroform-the phenol benzoates of 2-；2- Positive penta imines-phenol benzoate；2- isoamyls imines-phenol benzoate；The positive fourth imines-phenol benzoates of 2-；Positive imines in the heptan-benzene of 2- Phenyl formate；2- (2- furfuryls) imines-phenol benzoate；The just own imines-phenol benzoates of 2-；The positive last of the ten Heavenly stems imines-benzene first of 2- Acid phenenyl ester；2- cyclohexyl methyls imines-phenol benzoate；2- cyclopentyl-methyls imines-phenol benzoate；2- is sub- to chlorobenzene first Amine-phenol benzoate；2- m-chloros benzimide-phenol benzoate；2- neighbour's chlorobenzene azomethine-phenol benzoate；2- is to methoxyl group Benzimide-phenol benzoate；2- is to methyl benzimide-phenol benzoate；1- benzimide -2- naphthol benzoates；

2- benzimide -4- methyl-benzoic acid phenyl esters；2- benzene ethyleneimine -4- methyl-benzoic acid phenyl esters；Positive penta imines-of 2- 4- methyl-benzoic acid phenyl esters；2- isoamyl imines -4- methyl-benzoic acid phenyl esters；The positive fourth imines -4- methyl-benzoic acid phenyl esters of 2-； Positive imines in the heptan -4- methyl-benzoic acid phenyl esters of 2-；2- (2- furfuryls) imines -4- methyl-benzoic acid phenyl esters；The just own imines-of 2- 4- methyl-benzoic acid phenyl esters；The positive last of the ten Heavenly stems imines -4- methyl-benzoic acid phenyl esters of 2-；2- cyclohexyl methyl imines -4- methyl-benzoic acids Phenyl ester；2- cyclopentyl-methyl imines -4- methyl-benzoic acid phenyl esters；2- is to chlorobenzene azomethine -4- methyl-benzoic acid phenyl esters；Between 2- Chlorobenzene azomethine -4- methyl-benzoic acid phenyl esters；2- neighbour's chlorobenzene azomethine -4- methyl-benzoic acid phenyl esters；2- is to methoxybenzene first Imines -4- methyl-benzoic acid phenyl esters；2- is to methyl benzimide -4- methyl-benzoic acid phenyl esters；

2- NSC 334072s-phenol benzoate；2- NSC 334072-4- methyl-benzoic acid phenyl esters；2- NSC 334072s- 4- methyl -6- methyl-benzoic acid phenyl esters；2- NSC 334072-4- t-butyl-benzoic acid phenyl esters；2- NSC 334072s-isobutyric acid Phenyl ester；2- NSC 334072-4- methyl-6- methyl-isobutyl acid phenenyl ester；2- NSC 334072s -4- methyl-m-chlorobenzoic acid benzene Ester；2- NSC 334072-4- methyl-6- methyl-benzene oxygen phenyl formate；

2- benzimide -4- t-butyl-benzoic acid phenyl esters；2- benzene ethyleneimine -4- t-butyl-benzoic acid phenyl esters；2- positive penta Imines -4- t-butyl-benzoic acid phenyl esters；2- isoamyl imines -4- t-butyl-benzoic acid phenyl esters；The positive fourth imines -4- tertiary butyls-of 2- Phenol benzoate；Positive imines in the heptan -4- t-butyl-benzoic acid phenyl esters of 2-；2- (2- furfuryls) imines -4- t-butyl-benzoic acids Phenyl ester；The just own imines -4- t-butyl-benzoic acid phenyl esters of 2-；The positive last of the ten Heavenly stems imines -4- t-butyl-benzoic acid phenyl esters of 2-；2- cyclohexyl first Base imines -4- t-butyl-benzoic acid phenyl esters；2- cyclopentyl-methyl imines -4- t-butyl-benzoic acid phenyl esters；2- is sub- to chlorobenzene first Amine -4- t-butyl-benzoic acid phenyl esters；2- m-chloro benzimide -4- t-butyl-benzoic acid phenyl esters；2- neighbour chlorobenzene azomethine -4- uncles Butyl-benzene phenyl formate；2- is to methoxybenzene azomethine -4- t-butyl-benzoic acid phenyl esters；2- is to methyl benzimide -4- uncles Butyl-benzene phenyl formate；2- is to methyl benzimide -4- methyl -6- methyl-benzoic acid phenyl esters；

2- benzimides-isobutyl acid phenenyl ester；2- benzene ethyleneimine-cyclohexanecarboxylic acid phenyl ester；The positive lauric acid/dodecanoic acid benzene of positive penta imines-of 2- Ester；2- isoamyls imines -0-chloro-benzoic acid phenyl ester；The positive fourth imines of 2--benzene oxygen phenyl formate；Positive imines in the heptan-pentafluoro benzoic acid benzene of 2- Ester；The just own imines-of 2- is to trifluoromethylbenzoic acid phenyl ester；The positive last of the ten Heavenly stems imines-P-methoxybenzoic acid phenyl esters of 2-；2- cyclohexyl methyls Imines-cyclohexanecarboxylic acid phenyl ester phenyl ester；The positive enanthic acid phenyl ester of 2- cyclopentyl-methyls imines-；2- m-chloros benzimide-n-hexadecanoic benzene Ester；2- is to methoxybenzene azomethine -0-chloro-benzoic acid phenyl ester；2- is to the positive valeric acid phenyl ester of methyl benzimide-；1- benzimides- 2- P-methoxybenzoic acid naphthalene esters；

2- benzimides -4- tertiary butyls-isobutyl acid phenenyl ester；2- benzene ethyleneimine -4- tert-Butyl-cyclohex phenyl formates；2- is just The positive lauric acid/dodecanoic acid phenyl ester of penta imines -4- tertiary butyls -；2- isoamyl imines -4- tertiary butyls -0-chloro-benzoic acid phenyl ester；The positive fourth imines -4- of 2- Tertiary butyl-benzene oxygen phenyl formate；Positive imines in the heptan -4- tertiary butyls-pentafluoro benzoic acid phenyl esters of 2-；The just own imines -4- tertiary butyls-of 2- are right Trifluoromethylbenzoic acid phenyl ester；The positive last of the ten Heavenly stems imines -4- tertiary butyls-P-methoxybenzoic acid phenyl esters of 2-；2- cyclohexyl methyl imines -4- Tert-Butyl-cyclohex phenyl formate phenyl ester；The positive enanthic acid phenyl ester of 2- cyclopentyl-methyl imines -4- tertiary butyls -；2- m-chloros benzimide- 4- tertiary butyls-n-hexadecanoic phenyl ester；2- is to methoxybenzene azomethine -4- tertiary butyls -0-chloro-benzoic acid phenyl ester；2- is to methylbenzene first The positive valeric acid phenyl ester of imines -4- tertiary butyls -；

2- benzimide -4- methyl -6- methyl-isobutyl acid phenenyl ester；2- benzene ethyleneimine -4- methyl-cyclohexyl phenyl formates；2- The positive lauric acid/dodecanoic acid phenyl ester of positive penta imines -4- ethyls -；2- isoamyl imines -4- methyl -0-chloro-benzoic acid phenyl ester；The positive fourth imines -4- first of 2- Base -6- methyl-benzene oxygen phenyl formate；Positive imines in the heptan -4- methyl-pentafluoro benzoic acid phenyl esters of 2-；The just own imines -4- methyl-of 2- is right Trifluoromethylbenzoic acid phenyl ester.

The just own imines of 2--benzene oxygen phenyl formate；The just own imines -4- methyl-benzene oxygen phenyl formates of 2-；The just own imines -4- of 2- Ethyl-benzene oxygen phenyl formate；The just own imines -4- tertiary butyls-benzene oxygen phenyl formates of 2-；The just own imines -4- methyl -6- methyl-of 2- Benzene oxygen phenyl formate；The just own chloro- benzene oxygen phenyl formates of imines -4- of 2-；2- isoamyls imines-is to methylenedioxy phenoxy phenyl formate；2- is just Fourth imines-chlorobenzene oxygen phenyl formate；The just pungent imines-of 2- is to methoxybenzene oxygen phenyl formate；The just pungent oxygen formic acid of the positive fourth imines-of 2- Phenyl ester；The just pungent oxygen phenyl formate of the positive fourth imines -4- methyl-of 2-；The just pungent oxygen phenyl formate of the positive fourth imines -4- tertiary butyls-of 2-；2- is just The chloro- just pungent oxygen phenyl formates of fourth imines -4-；The just pungent oxygen phenyl formate of the positive fourth imines -4- methyl -6- methyl-of 2-；The positive fourths of 2- are sub- The positive fourth oxygen phenyl formate of amine-；The just own imines of 2--isoamyl oxygen phenyl formate；The positive fourth imines-ethoxy phenyl formates of 2-；The positive fourths of 2- are sub- Amine -4- methyl-ethoxy phenyl formate；The positive fourth imines -4- tertiary butyls-ethoxy phenyl formates of 2-；The positive chloro- ethoxies of fourth imines -4- of 2- Phenyl formate；The positive fourth imines -4- methyl -6- methyl-ethoxy phenyl formates of 2-；The positive fourth imines-ethoxy phenyl formates of 2-；2- just oneself Imines-ethoxy phenyl formate；2- isopropyls imines-ethoxy phenyl formate.

The present invention 2- substituted-aminos-phenyl ester can be synthesized by various reactions, in order to illustrate but be not intended to limit synthesis side Method, for example substituted or unsubstituted o-aminophenol is reacted with acyl chlorides or chloro-formate, it can obtain working as R^IIFor H when general formula (II) compound：

Work as R^IIThe compound of logical formula (II) when not being H can be obtained by method shown in following formula, i.e., first will be substituted or not The phenolic hydroxyl group protected silane of substituted o-aminophenol, afterwards and R^IIBromo-derivative or iodo object reaction, hydroxyl goes to protect again later Shield reaction, is finally obtained by the reaction with acyl chlorides or chloro-formate.This method, which is especially suitable for preparing, works as R^IIFor aryl, substituted aryl, miscellaneous The compound of the logical formula (II) of the groups such as ring, tertiary butyl：

As the R of the compound of logical formula (II)⁵And R^5’When being different, following method can also be used and prepare：

Logical formula (III) compound is preferred as lead to formula (II) compound one, can be by will be substituted or unsubstituted O-aminophenol is first reacted with aldehydes or ketones, is obtained by the reaction again with acyl chlorides or chloro-formate after reduction reaction：

Again or by substituted or unsubstituted o-aminophenol with first react with aldehydes or ketones, then with acyl chlorides or chloro-formate Reaction can obtain the compound of logical formula (IV)：

The present invention ingredient of solid catalyst remove containing the general formula (I) 2- substituted-aminos-phenyl ester compound A it Outside, also include at least another electron donor compound B, compound B, which is selected from, contains one or more electronegativity groups Lewis alkali, electron donor atom therein are selected from the group of N, O, S, P, As or Sn composition, preferably are selected from two ethers, esters, diones With the electron donor compound of Diamines.When 2- substituted-aminos-phenyl ester compound and other above-mentioned published internal electron donors When compound is used together, the catalyst that performance can be adjusted can be obtained.

Lewis alkali electron compounds B preferably, is selected from 1,3-, bis- ethers of logical formula (V)：

Wherein：R、R¹、R²、R³、R⁴And R⁵It may be the same or different, represent H or have the straight chain of 1-18 carbon atom or branched alkane Base, naphthenic base, aryl, alkaryl or aralkyl；R⁶And R⁷It may be the same or different, represent the straight chain or branch for having 1-20 carbon atom Change the alkaryl and aralkyl of alkyl, the naphthenic base of 3-20 carbon atom, the aryl of 5-20 carbon atom, 7-20 carbon atom；R To R⁷One or more of group can link to form cyclic structure, may include selected from halogen, one of N, O, S, P and Si or Multiple hetero atoms.

The specific example for the ethers that can be advantageously used includes：2- (2- ethylhexyls) 1,3- dimethoxy propanes, 2- isopropyl -1,3- dimethoxy propanes, 2- butyl -1,3- dimethoxy propanes, 2- sec-butyl -1,3- dimethoxy propanes, 2- cyclohexyl -1,3- dimethoxy propanes, 2- phenyl -1,3- dimethoxy propanes, 2- tertiary butyl -1,3- dimethoxy propanes, 2- cumyl -1,3- dimethoxy propanes, 2- (2- phenylethyls) -1,3- dimethoxy propanes, 2- (2- cyclohexyl-ethyls) -1,3- Dimethoxy propane, 2- (rubigan) -1,3- dimethoxy propanes, 2- (diphenyl methyl) -1,3- dimethoxy propanes, 2 (1- naphthalenes) -1,3- dimethoxy propanes, 2 (p-fluorophenyl) -1,3- dimethoxy propanes, 2 (1- decahydros naphthalene) -1,3- diformazans Oxygroup propane, 2 (to tert-butyl-phenyl) -1,3- dimethoxy propanes, 2,2- dicyclohexyl -1,3- dimethoxy propanes, 2,2- Diethyl -1,3- dimethoxy propane, 2,2- dipropyl -1,3- dimethoxy propanes, 2,2- dibutyl -1,3- dimethoxys third Alkane, 2,2- diethyl -1,3- di ethyl propyl ethers, 2,2- bicyclopentyl -1,3- dimethoxy propanes, 2,2- dipropyl -1,3- Di ethyl propyl ether, 2,2- dibutyl -1,3- di ethyl propyl ethers, 2- methyl -2- ethyl -1,3- dimethoxy propanes, 2- first Base -2- propyl -1,3- dimethoxy propanes, 2- methyl -2- benzyl -1,3- dimethoxy propanes, 2- methyl -2- phenyl -1,3- Dimethoxy propane, 2- methyl -2- cyclohexyl -1,3- dimethoxy propanes, 2- methyl -2- methylcyclohexyl -1,3- dimethoxies Base propane, 2,2- bis- (rubigan) -1,3- dimethoxy propanes, 2,2- bis- (2- phenylethyls) -1,3- dimethoxy propanes, 2,2- bis- (2- cyclohexyl-ethyls) -1,3- dimethoxy propanes, 2- methyl -2- isobutyl group -1,3- dimethoxy propanes, 2- first Base -2- (2- ethylhexyls) -1,3- dimethoxy propanes, 2,2- bis- (2- ethylhexyls) -1,3- dimethoxy propanes, 2,2- is bis- (p-methylphenyl) -1,3- dimethoxy propanes, 2- methyl -2- isopropyl -1,3- dimethoxy propanes, 2,2- diisobutyls - 1,3- dimethoxy propane, 2,2- diphenyl -1,3- dimethoxy propanes, 2,2- dibenzyl -1,3- dimethoxy propanes, 2- are different Propyl -2- cyclopenta -1,3- dimethoxy propanes, 2,2- bis- (cyclohexyl methyl) -1,3- dimethoxy propanes, 2,2- bis- isobutyls Base -1,3- di ethyl propyl ether, 2,2- diisobutyl -1,3- dibutoxy propane, 2- isobutyl group -2- isopropyl -1,3- diformazans Oxygroup propane, 2,2- di-sec-butyl -1,3- dimethoxy propanes, 2,2- di-t-butyl -s 1,3- dimethoxy propanes, 2,2- bis- Neopentyl -1,3- dimethoxy propane, 2- i-propyl -2- isopentyl -1,3- dimethoxy propanes, benzyl -1 2- phenyl -2-, 3- dimethoxies _ _ base propane, 2- cyclohexyl -2- cyclohexyl methyl -1,3- dimethoxy propanes.Bis- (the methoxy)-rings of 1,1- Pentadiene；Bis- (the methoxy) -2,3,4,5- tetramethyl-ring pentadienes of 1,1-；Bis- (the methoxy) -2,3,4,5- of 1,1- Tetraphenyl cyclopentadiene；Bis- (the methoxy) -2,3,4,5- tetrafluoro cyclopentadiene of 1,1-；Bis- (methoxy) -3 1,1-, 4- bicyclopentyl cyclopentadiene；Bis- (methoxy) indenes of 1,1-；Bis- (the methoxy) -2,3- dimethyl indenes of 1,1-；1,1- Bis- (methoxy) -4,5,6,7- tetrahydroindenes；Bis- (the methoxy) -2,3,6,7- tetrafluoro indenes of 1,1-；Bis- (the methoxyl groups of 1,1- Methyl) -4,7- dimethyl indenes；Bis- (the methoxy) -3,6- dimethyl indenes of 1,1-；Bis- (the methoxy) -4- phenyl of 1,1- Indenes；Bis- (the methoxy) -4- phenyl -2- methyl indenes of 1,1-；Bis- (the methoxy) -4- cyclohexyl indenes of 1,1-；Bis- (the first of 1,1- Oxygroup methyl) -7- (3,3,3- trifluoro propyls) indenes；Bis- (the methoxy) -7- trimethyl silyl indenes of 1,1-；1,1- is bis- (methoxy) -7- trifluoromethyl indenes；Bis- (the methoxy) -4,7- dimethyl -4,5,6,7- tetrahydroindenes of 1,1-；1,1- is bis- (methoxy) -7- methyl indenes；Bis- (the methoxy) -7- cyclopenta indenes of 1,1-；Bis- (the methoxy) -7- isopropyls of 1,1- Base indenes；Bis- (the methoxy) -7- cyclohexyl indenes of 1,1-；Bis- (the methoxy) -7- tertiary butyl indenes of 1,1-；Bis- (the methoxies of 1,1- Ylmethyl) -7- tertiary butyl -2- methyl indenes；Bis- (the methoxy) -7- phenylindans of 1,1-；Bis- (the methoxy) -2- benzene of 1,1- Base indenes；Bis- (methoxy) -1H- benzos [e] indenes of 1,1-；Bis- (methoxy) -1H-2- methyl benzo [e] indenes of 1,1-；9, Bis- (methoxy) fluorenes of 9-；Bis- (the methoxy) -2,3,6,7- tetramethyl fluorenes of 9,9-；Bis- (methoxy) -2 9,9-, 3,4,5,6,7- hexafluoro fluorenes；Bis- (the methoxy) -2,3- benzfluorenes of 9,9-；Bis- (the methoxy) -2,3,6,7- of 9,9- two Benzfluorene；Bis- (the methoxy) -2,7- diisopropyl fluorenes of 9,9-；Bis- (the methoxy) -1,8- dichloro fluorenes of 9,9-；9,9- is bis- (methoxy) -2,7- bicyclopentyl fluorenes；Bis- (the methoxy) -1,8- difluoro fluorenes of 9,9-；9,9- bis- (methoxies)- 1,2,3,4- tetrahydrochysene fluorenes；Bis- (the methoxy) -1,2,3,4,5,6,7,8- octahydro fluorenes of 9,9-；9,9- bis- (methoxies)- 4- tertiary butyl fluorenes.

Lewis alkali electron compounds B is preferably monocarboxylic esters or polybasic carboxylic acid esters compound, specific example are Aromatic binary carboxylic acid compound and aliphatic chain dicarboxylic acids esters compound：

The diester of aromatic binary carboxylic acid, such as ditridecyl phthalate or bis- terephthalate.Ditridecyl phthalate Including：Repefral, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, N-butyl phthalate, diisobutyl phthalate, Methyl Benzene-o-dicarboxylate ethyl ester, Methyl Benzene-o-dicarboxylate isopropyl Ester, Methyl Benzene-o-dicarboxylate n-propyl, ethyl phthalate N-butyl, ethyl phthalate isobutyl ester, phthalic acid Two n-pentyl esters, di-iso-amyl phthalate, dihexyl phthalate, heptyl phthalate ester, phthalic acid two N-octyl, diisooctyl phthalate, phthalic acid (2,2- dimethylhexanyl) diester, phthalic acid (2- ethyl hexyls Base) diester, 2-nonyl-phthalate ester, diisooctyl phthalate, phthalic acid (2,2- dimethyl heptyl) diester, N-butyl phthalate dissident's base ester, n-butyl phthalate (2- ethylhexyls) ester, phthalic acid n-pentyl ester just oneself The different nonyl ester of ester, phthalic acid n-pentyl ester, the positive last of the ten Heavenly stems ester of isoamyl phthalate, phthalic acid n-pentyl ester hendecane ester, neighbour The just own ester (2- methylhexyl esters) of phthalic acid isopentyl dissident base ester, phthalic acid, phthalic acid n-hexyl (2- ethyls Hexyl ester), the just own ester (different nonyl ester) of phthalic acid, phthalic acid n-hexyl (positive last of the ten Heavenly stems ester), the positive heptyl ester (2- of phthalic acid Ethylhexyl), the positive heptyl ester of phthalic acid (different nonyl ester), the new nonyl ester of the positive heptyl ester of phthalic acid and phthalic acid 2- ethyls Own ester (different nonyl ester).These esters can be independent or a variety of be used in mixed way.Bis- terephthalate includes：Terephthalic acid (TPA) diformazan Ester, diethyl terephthalate, terephthalic acid (TPA) di-n-propyl ester, terephthalic acid (TPA) diisopropyl ester, di-n-butyl terephthalate, Di-n-butyl terephthalate, isobutyl terephthalate, terephthalic acid (TPA) ethyl ester methyl ester, terephthalic acid (TPA) methyl esters isopropyl Ester, terephthaldehyde's acetoacetic ester (n-propyl), terephthaldehyde's acetoacetic ester (N-butyl), terephthaldehyde's acetoacetic ester (isobutyl ester), to benzene Two n-pentyl ester of dioctyl phthalate, terephthalic acid (TPA) diisoamyl ester, terephthalic acid (TPA) dihexyl, two positive heptyl ester of terephthalic acid (TPA), to benzene two Formic acid di-n-octyl, two different n-octyl of terephthalic acid (TPA), terephthalic acid (TPA) two (2,2- dimethylhexanyl) ester, terephthalic acid (TPA) two (2- ethylhexyls) ester, two positive nonyl ester of terephthalic acid (TPA), terephthalic acid (TPA) dinonyl, terephthalic acid (TPA) diisodecyl ester, to benzene Dioctyl phthalate two (2,2- dimethyl ethyl heptyl) ester, terephthalic acid (TPA) N-butyl dissident ester, terephthalic acid (TPA) N-butyl (2 ethyls Hexyl) ester, the just own ester of terephthalic acid (TPA) n-pentyl ester, terephthalic acid (TPA) n-pentyl ester dissident ester, terephthaldehyde's isoamyl valerate (heptyl ester), Terephthalic acid (TPA), terephthalic acid (TPA) n-pentyl ester (2- ethylhexyls) ester, terephthalic acid (TPA) n-pentyl ester (different nonyl ester), terephthalic acid (TPA) Isopentyl ester (positive last of the ten Heavenly stems ester), terephthalic acid (TPA) n-pentyl ester hendecane ester, terephthaldehyde isoamyl valerate dissident ester, terephthalic acid (TPA) just oneself The just own ester (positive last of the ten Heavenly stems ester) of base (2- ethylhexyls), terephthalic acid (TPA) n-hexyl (isononyl ester), terephthalic acid (TPA), terephthaldehyde Sour n-heptyl (2- ethylhexyls), terephthalic acid (TPA) n-heptyl (isononyl ester), terephthalic acid (TPA) n-heptyl (new last of the ten Heavenly stems ester) and Terephthalic acid (TPA) 2- ethylhexyls (isononyl ester).These esters can be independent or a variety of be used in mixed way.

Diethyl phthalate, dipropyl phthalic butyl ester, terephthalic acid (TPA) two are recommended in these diester Isopropyl ester, n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, phthalic acid two Different monooctyl ester, di-n-butyl terephthalate, isobutyl terephthalate, terephthalic acid (TPA) di-n-octyl, terephthalic acid (TPA) two One or more of different monooctyl ester, (2- ethylhexyls) ester of terephthalic acid (TPA) two or diisooctyl phthalate mix It closes.

It is particularly preferred that the succinate compound compound selected from logical formula (VI) in polybasic carboxylic acid esters compound：

Wherein, group R¹And R², it is same or different to each other, is C1-C20 line styles or branched-alkyl, alkenyl, naphthenic base, virtue Base, aralkyl or alkylaryl group optionally include hetero atom；R³-R⁶In at least two groups be different from hydrogen and be selected from C¹- C²⁰Line style or branched-alkyl, alkenyl, naphthenic base, aryl, aralkyl or alkylaryl group, optionally contain hetero atom, in addition, Group R³-R⁶It can be connected together and constitute a ring.R¹And R²Preferably C1-C8 alkyl, naphthenic base, aryl, aralkyl and alkane virtue Base group.Particularly preferably such compound, wherein R¹And R²Selected from primary alkyl, especially branched primary alkyl.Suitable R¹ And R²Example be methyl, ethyl, n-propyl, normal-butyl, isobutyl group, neopentyl, 2- ethylhexyls.Particularly preferably second Base, isobutyl group and neopentyl.

One of the preferred compounds category of logical formula (VI) description is such, wherein R³-R⁵It is hydrogen and R⁶It is with 3-10 Branched-alkyl, naphthenic base, aryl, aralkyl and the alkylaryl group of a carbon atom.Particularly preferably such compound, Middle R⁶It is the branched primary alkyl group or group of naphthene base with 3-10 carbon atom.Suitable monosubstituted succinate compound Specific example be sec-butyl diethyl succinate, hexyl diethyl succinate, cyclopropyl diethyl succinate, norborny amber Amber diethyl phthalate, perhydrogenating diethyl succinate, trimethyl-succinic acid diethylester, methoxyl group diethyl succinate, to methoxyl group Phenylsuccinic acid diethylester, rubigan diethyl succinate, phenylsuccinic acid diethylester, cyclohexyl diethyl succinate, benzyl Base diethyl succinate, cyclohexyl methyl diethyl succinate, tertiary butyl diethyl succinate, isobutyl group diethyl succinate, Isopropyl diethyl succinate, neopentyl diethyl succinate, isopentyl diethyl succinate, (1- trifluoromethyls ethyl) amber Diethyl phthalate, fluorenyl diethyl succinate, phenylsuccinic acid (1- ethyoxyl carbonyls diisobutyl ester) (1- (ethoxycarbo Diisobutyl phenylsuccinate), sec-butyl di-iso-octyl succinate, hexyl di-iso-octyl succinate, cyclopropyl amber Amber acid diisobutyl ester, norborny di-iso-octyl succinate, perhydrogenating di-iso-octyl succinate, trimethyl silyl succinic acid Diisobutyl ester, methoxyl group di-iso-octyl succinate, p-methoxyphenyl di-iso-octyl succinate, p-chlorophenyl succinic acid two are different Butyl ester, cyclohexyl di-iso-octyl succinate, benzyl di-iso-octyl succinate, cyclohexyl methyl di-iso-octyl succinate, tertiary butyl Di-iso-octyl succinate, isobutyl group di-iso-octyl succinate, isopropyl di-iso-octyl succinate, two isobutyl of neopentyl succinic acid It is ester, isopentyl di-iso-octyl succinate, (1- trifluoromethyls ethyl) di-iso-octyl succinate, fluorenyl di-iso-octyl succinate, secondary Two peopentyl ester of butyl succinic acid, two peopentyl ester of hexyl succinic acid, two peopentyl ester of cyclopropyl succinic acid, norborny succinic acid two are new Pentyl ester, two peopentyl ester of perhydrogenating succinic acid, two peopentyl ester of trimethyl silyl succinic acid, two peopentyl ester of methoxyl group succinic acid, Two peopentyl ester of p-methoxyphenyl succinic acid, two peopentyl ester of rubigan succinic acid, two peopentyl ester of phenylsuccinic acid, cyclohexyl amber Two peopentyl esters of amber acid, two peopentyl ester of benzyl succinic acid, two peopentyl ester of cyclohexyl methyl succinic acid, tertiary butyl succinic acid two new penta Ester, two peopentyl ester of isobutyl group succinic acid, two peopentyl ester of isopropyl succinic acid, two peopentyl ester of neopentyl succinic acid, isopentyl amber Sour two peopentyl esters, two peopentyl ester of (1- trifluoromethyls ethyl) succinic acid, two peopentyl ester of fluorenyl succinic acid.

Another kind of preferred compound is such, wherein R in compound in logical formula (VI)³-R⁶In at least two Group is different from hydrogen and is selected from C1-C20 line styles or branched-alkyl, alkenyl, naphthenic base, aryl, aralkyl or alkaryl base Group, optionally contains hetero atom.The group of particularly preferably such compound, two of which non-hydrogen is connected to the same carbon On atom.Suitable two replace the specific example of succinate to be：2,2- dimethylsuccinic diethyl phthalates, 2- Ethyl-2-Methyls Diethyl succinate, 2- benzyl -2- isopropyls diethyl succinate, 2- cyclohexyl methyl -2- isobutyl group succinic acids diethyl _ _ ester, 2- cyclopenta -2- normal-butyls diethyl succinate, 2,2- diisobutyls diethyl succinate, 2- cyclohexyl -2- ethylsuccinic acids Diethylester, 2- isopropyl -2- methyl succinics diethyl phthalate, 2- myristyl -2- ethylsuccinic acids diethylester, 2- isobutyl groups -2- Ethylsuccinic acid diethylester, 2- (1- trifluoromethyls ethyl) -2- methyl succinics diethyl phthalate, 2- isopentyl -2- isobutyl group ambers Diethyl phthalate, 2- phenyl -2- normal-butyls diethyl succinate, 2,2- dimethyl succinates diisobutyl ester, 2- Ethyl-2-Methyl ambers Amber acid diisobutyl ester, 2- benzyl -2- isopropyls di-iso-octyl succinate, two isobutyl of 2- cyclohexyl methyl -2- isobutyl groups succinic acid Ester, 2- cyclopenta -2- normal-butyls di-iso-octyl succinate, 2,2- diisobutyls di-iso-octyl succinate, 2- cyclohexyl -2- ethyls Di-iso-octyl succinate, 2- isopropyl -2- methylsuccinic acids diisobutyl ester, 2- myristyl -2- ethylsuccinic acids diisobutyl ester, 2- isobutyl group -2- ethylsuccinic acids diisobutyl ester, 2- (1- trifluoromethyls ethyl) -2- methylsuccinic acids diisobutyl ester, 2- isoamyls Base -2- isobutyl groups di-iso-octyl succinate, 2- phenyl -2- normal-butyls di-iso-octyl succinate, 2,2- dimethyl succinates two are new Pentyl ester, two peopentyl ester of 2- Ethyl-2-Methyls succinic acid, two peopentyl ester of 2- benzyl -2- isopropyls succinic acid, 2- cyclohexyl methyls - Two peopentyl ester of 2- isobutyl groups succinic acid, two peopentyl ester of 2- cyclopenta -2- normal-butyls succinic acid, 2,2- diisobutyls succinic acid two are new Pentyl ester, two peopentyl ester of 2- cyclohexyl -2- ethylsuccinic acids, two peopentyl ester of 2- isopropyl -2- methylsuccinic acids, 2- myristyls - Two peopentyl ester of 2- ethylsuccinic acids, two peopentyl ester of 2- isobutyl group -2- ethylsuccinic acids, 2- (1- trifluoromethyls ethyl) -2- methyl Two peopentyl ester of succinic acid, two peopentyl ester of 2- isopentyl -2- isobutyl groups succinic acid, two peopentyl ester of 2- phenyl -2- normal-butyls succinic acid.

In addition, also particularly preferably such compound, the group of wherein at least two non-hydrogen are connected to different carbon atoms, i.e., R³And R⁵Or R⁴And R⁶.The specific example of suitable compound is 2,3- bis- (trimethyl silyl) diethyl succinate, 2- Sec-butyl -3- methyl succinics diethyl phthalate, 2- (3,3,3- trifluoro propyl) -3- methyl succinics diethyl phthalate, (the 2- ethyls of 2,3- bis- Butyl) diethyl succinate, 2,3- diethyl -2- isopropyls diethyl succinate, 2,3- diisopropyl -2- methylsuccinic acids two Ethyl ester, 2,3- dicyclohexyl -2- methyl succinics diethyl phthalate, 2,3- dibenzyl diethyl succinate, 2,3- diisopropyl ambers Diethyl phthalate, 2,3- bis- (cyclohexyl methyl) diethyl succinate, 2,3- di-t-butyls diethyl succinate, 2,3- diisobutyls Diethyl succinate, 2,3- di neo-pentyls diethyl succinate, 2,3- diisoamyl diethyl succinate, (the 1- trifluoros of 2,3- bis- Methylethyl) diethyl succinate, 2,3- bis- (myristyl) diethyl succinate, 2,3-, bis- fluorenyl diethyl succinates, 2- Isopropyl -3- isobutyl groups diethyl succinate, 2- tertiary butyl -3- isopropyls diethyl succinate, 2- isopropyl -3- cyclohexyl ambers Amber diethyl phthalate, 2- isopentyl -3- cyclohexyl diethyl succinate, 2- myristyl -3- cyclohexyl diethyl succinate, 2- rings Hexyl -3- cyclopenta diethyl succinate, 2,2,3,3- tetramethyl diethyl succinates, 2,2,3,3- tetraethyl succinic acid diethyls Ester, 2,2,3,3- tetrapropyl diethyl succinates, 2,3- diethyl -2,3- diisopropyls diethyl succinate, 2,2,3,3- tetra- Fluorine diethyl succinate, 2,3- bis- (trimethyl silyl) di-iso-octyl succinate, 2- sec-butyl -3- methylsuccinic acids two are different Butyl ester, 2- (3,3,3- trifluoro propyl) -3- methylsuccinic acids diisobutyl ester, 2,3- bis- (2- ethyl-butyls) succinic acid, two isobutyl Ester, 2,3- diethyl -2- isopropyls di-iso-octyl succinate, 2,3- diisopropyl -2- methylsuccinic acids diisobutyl ester, 2,3- bis- Cyclohexyl -2- methylsuccinic acids diisobutyl ester, 2,3- dibenzyl di-iso-octyl succinate, 2,3- diisopropyls succinic acid, two isobutyl Ester, 2,3- bis- (cyclohexyl methyl) di-iso-octyl succinate, 2,3- di-t-butyls di-iso-octyl succinate, 2,3- diisobutyl ambers Amber acid diisobutyl ester, 2,3- di neo-pentyls di-iso-octyl succinate, 2,3- diisoamyl di-iso-octyl succinate, 2,3-, bis- (1- Trifluoromethyl ethyl) di-iso-octyl succinate, 2,3- bis- (myristyl) di-iso-octyl succinate, 2,3-, bis- fluorenyl succinic acids two Isobutyl ester, 2- isopropyl -3- isobutyl groups di-iso-octyl succinate, 2- tertiary butyl -3- isopropyls di-iso-octyl succinate, 2- isopropyls Base -3- cyclohexyl di-iso-octyl succinate, 2- isopentyl -3- cyclohexyl di-iso-octyl succinate, 2- myristyl -3- cyclohexyl Methylsuccinic acid diisobutyl ester, 2- cyclohexyl -3- cyclopenta di-iso-octyl succinate, 2,2,3,3- tetramethyl succinic acid, two isobutyl Ester, 2,2,3,3- tetraethyl di-iso-octyl succinates, 2,2,3,3- tetrapropyl di-iso-octyl succinates, 2,3- diethyl -2,3- Dipropyl di-iso-octyl succinate, 2,2,3,3- tetrafluoro di-iso-octyl succinates, 2,3- bis- (trimethyl silyl) succinic acid Two peopentyl esters, two peopentyl ester of 2- sec-butyl -3- methylsuccinic acids, 2- (3,3,3- trifluoro propyl) -3- methylsuccinic acids two new penta Ester, 2,3- bis- (2- ethyl-butyls) succinic acid, two peopentyl ester, 2,3- diethyl -2- isopropyls succinic acid, two peopentyl ester, 2,3- bis- Two peopentyl ester of isopropyl -2- methylsuccinic acids, 2,3- dicyclohexyl -2- methylsuccinic acids, two peopentyl ester, 2,3- dibenzyl ambers Sour two peopentyl esters, 2,3- diisopropyls succinic acid, two peopentyl ester, 2,3- bis- (cyclohexyl methyl) succinic acid, two peopentyl ester, 2,3- bis- Two peopentyl ester of tertiary butyl succinic acid, 2,3- diisobutyls succinic acid, two peopentyl ester, 2,3- di neo-pentyls succinic acid, two peopentyl ester, 2, Two peopentyl ester of 3- diisoamyl succinic acid, 2,3- (1- trifluoromethyls ethyl) succinic acid, two peopentyl ester, 2,3- bis- (myristyl) Two peopentyl ester of succinic acid, 2,3-, bis- fluorenyl succinic acids, two peopentyl ester, two peopentyl ester of 2- isopropyl -3- isobutyl groups succinic acid, uncle 2- Two peopentyl ester of butyl -3- isopropyls succinic acid, two peopentyl ester of 2- isopropyl -3- cyclohexyl succinic acid, 2- isopentyl -3- cyclohexyl Two peopentyl ester of succinic acid, two peopentyl ester of 2- myristyl -3- cyclohexyl methyls succinic acid, 2- cyclohexyl -3- cyclopenta succinic acids Two peopentyl esters, 2,2,3,3- tetramethyl succinic acid, two peopentyl ester, 2,2,3,3- tetraethyl succinic acid, two peopentyl ester 2,2,3,3- tetra- Two peopentyl ester of propyl succinic acid, 2,3- diethyl -2,3- diisopropyls succinic acid, two peopentyl ester, 2,2,3,3- tetrafluoro succinic acids two Peopentyl ester.

Such as group R mentioned above, being connected on same carbon atom³-R⁶In two or four compositions that link together The compound of the logical formula (VI) of one ring is also preferred.The specific example of suitable compound is 1- (carbethoxyl group) -1- (second Oxygroup acetyl) -2,6- dimethyl cyclohexanes, 1- (carbethoxyl group) -1- (Ethoxyacetyl) -2,5- dimethylcyclopentanes, 1- (second Oxygen carbonyl) -1- (Ethoxyacetylmethyl) -2- hexahydrotoluenes, 1- (carbethoxyl group) -1- (Ethoxyacetylcyclohexyl) Hexamethylene.

Compound above-mentioned can be or different with position in the form of pure isomer or with the form of mixtures of enantiomer The form of mixtures of structure body and enantiomer uses.When pure isomer to be used, common technology well known in the art is generally used It is separated.In particular, certain in succinate of the present invention can be used as pure racemic or meso-form, or alternatively Mixture in the form of both uses.

Lewis alkali electron compounds B is further preferably selected from the glycol ester compounds of logical formula (VII)：

R in formula¹-R⁶、R^1’-R^2’For identical or different hydrogen, the C1- of halogen or substituted or unsubstituted linear chain or branched chain C20 alkyl, C3-C20 naphthenic base, C6-C20 aryl, C7-C20 alkaryls, C7-C20 aralkyl, C2-C10 alkylenes or C10- C20 fused ring aryls；But R^1’And R^2’It is not hydrogen, R¹-R⁶One or more of it is optionally cyclic or not cyclic.

The diol-lipid compound specifically can be used：1,3-PD dibenzoate, 2- methyl-1s, 3-propanediol Dibenzoate, 2- ethyls -1,3-PD dibenzoate, 2- propyl -1,3-PD dibenzoate, butyl -1 2-, 3-propanediol dibenzoate, 2,2-dimethyl-1,3-propanediol dibenzoate, 2- ethyls -2- butyl -1,3-PD two Benzoic ether, 2,2- diethyl -1,3-PD dibenzoate, 2- methyl-2-propyls -1,3-PD dibenzoate, 2- isopropyls -2- isopentyl -1,3-PD dibenzoate, 2,4- glycol dibenzoates, 3- methyl -2,4- pentanediols Dibenzoate, 3- ethyls -2,4- glycol dibenzoate, 3- propyl -2,4- glycol dibenzoate, butyl -2 3-, 4- glycol dibenzoates, 3,3- dimethyl -2,4- glycol dibenzoate, 2- methyl-1s, 3- pentanediol dibenzoic acids Ester, 2,2- dimethyl -1,3- glycol dibenzoate, 2- ethyls -1,3- glycol dibenzoate, 2- butyl -1,3- penta Bisbenzoate, 2- methyl-1s, 3- glycol dibenzoates, 2- ethyls -1,3- glycol dibenzoate, 2- third Base -1,3- glycol dibenzoate, 2- butyl -1,3- glycol dibenzoate, 2,2- dimethyl -1,3- pentanediol hexichol Formic acid esters, 2- methyl-1s, 3- glycol dibenzoates, 2,2- dimethyl -1,3- glycol dibenzoate, ethyl -1 2-, 3- glycol dibenzoates, 2- butyl -1,3- glycol dibenzoate, 2,2,4- trimethyl -1,3- pentanediol hexichol first Acid esters, 3- methyl -3- butyl -2,4- glycol dibenzoate, 2,2- dimethyl -1,5-PD dibenzoate, 3,5- Heptandiol dibenzoate, 4- ethyl -3,5- heptandiol dibenzoates etc..It is preferred that pentadiol ester and heptandiol ester.

The present invention the ingredient of solid catalyst for olefinic polymerization, including titanium compound, magnesium compound, be selected among the above At least one 2- substituted-aminos-phenyl ester compound A and at least one ether, ester, ketone or amine simple function group or polyfunctional group give The precursor of Lewis alkali electron compound B, the magnesium compound are selected from least one：X_nMg(OR)_2-n, MgCl₂MROH, R_2- _nMgX_n, MgCl₂/SiO₂, MgCl₂/Al₂O₃Or the mixture of magnesium halide and alcohol titanium, m is the number of 0.1-6,0≤n≤2, X in formula For halogen, R is C₁-C₂₀Alkyl；The general formula of the titanium compound is TiX_N(OR)_4-N, it is 1-20's that R, which is carbon atom number, in formula Alkyl, X are halogen, N=1-4.

The magnesium compound of the present invention preferably uses magnesium hydrocarbyloxy compound.

Another alcohol adduct for preferably using magnesium dihalide of magnesium compound of the present invention.

The titanium compound of the present invention includes titanium tetrachloride, titanium tetrabromide, titanium tetra iodide or alkyl halide titanium, alkyl halide titanium Such as methoxytitanium trichloride, ethyoxyl titanium trichloride, propoxyl group titanium trichloride, nbutoxytitanium trichloride, dimethoxy dichloro Change titanium, diethoxy titanium chloride, dipropoxy titanium chloride, two n-butoxy titanium chloride, trimethoxy titanium chloride, three second Oxygroup titanium chloride, tripropoxy titanium chloride or three n-Butoxyl titanium-chlorides.It can be applied in these halogenated titaniums one or more mixed It closes and uses.Wherein preferably use titanium tetrachloride.

The preparation of the ingredient of solid catalyst of the present invention can be carried out according to several method.

According to one of which method, TiCl is used₄Or aromatic hydrocarbons (such as toluene, dimethylbenzene etc.) solution of titanium alkoxides can be with It is reacted with two magnesium hydrocarbyloxy compounds of such as dialkoxy magnesium or two aryloxy group magnesium etc at -25-0 DEG C, and at 80-130 DEG C Carry out halogenation.Use TiCl₄The processing that carries out of arene solution can be repeated one or more times, and one in repeatedly such processing It is secondary or above-mentioned 2- substituted-aminos-phenyl ester compound A and second of Lewis alkali electron donor compounds B is added portionwise.Such as it can It is prepared by the preparation method of the solids containing titanium catalytic component with reference to disclosed in US5077357：Sequentially add magnesium ethylate, Purity titanium tetraethoxide, o-cresol, ethyl alcohol and chlorobenzene, stirring；By TiCl₄/ chlorobenzene solution rapidly joins in aforesaid liquid, and heating has waited for After fully dissolved, it is continuously heating to specific temperature；Utilize N₂Bubbling continues to stir certain time after taking away ethanol synthesis object, then uses Hot chlorobenzene washed once, and isooctane washes twice, then N₂Drying can obtain carrier.Or according to another example：Successively by TiCl₄、 Purity titanium tetraethoxide, magnesium ethylate and o-cresol are added in chlorobenzene, stirring；Ethyl alcohol is added, waits for that magnesium ethylate dissolving is subsequent under high temperature Continuous stirring 3h；Then filtering while hot washed once using warm chlorobenzene, isooctane washed once, last N₂It is dry.

According to another method, the alcoholates or chlorohydrin of magnesium and in the solution contain above-mentioned 2- substituted-aminos- The excessive TiCl of phenyl ester compound A and second of Lewis alkali electron donor compounds B₄It is reacted at a temperature of 80-135 DEG C. Can be TiX by general formula according to preferred method_n(OR)_4-nTitanium compound, R is the alkyl that carbon atom number is 1-20 in formula, and X is Halogen, n=1-4；It is preferred that TiCl₄, with from general formula be MgCl₂The adduct of mROH reacts and prepares ingredient of solid catalyst, formula Middle m is the number of 0.1-6, preferably 2-3.5, and R is the alkyl for having 1-20 carbon atom.Adduct can fit by the following method It preferably is made spherical：In the presence of the not unreactive hydrocarbons miscible with adduct, alcohol and magnesium chloride are mixed, keep the lotion anxious rapidly It is cold, to make adduct cure in the form of spheric granules.The spherical MgCl prepared according to the process₂The example of mROH adducts Son description is found in US4399054 and US4469648.The obtained adduct can directly be reacted with titanium compound, or It can first pass through the dealcoholization (80-130 DEG C) of thermal control to obtain a kind of adduct to person in advance, and the molal quantity of wherein alcohol is general Less than 3, preferably between 0.1 and 2.5.It can be by the way that adduct (dealcoholysis or itself) be suspended in cold TiCl₄(general- 25-0 DEG C) in reacted with titanium compound；It heats the mixture to 80-130 DEG C and keeps 0.5-2 small at this temperature When.Use TiCl₄The processing of progress can carry out primary or multiple.With TiCl₄Above-mentioned 2- substitutions can be added during processing Amino-phenyl ester compound A and second of Lewis alkali electron donor compound B processing, this processing can be repeated once or Person is multiple.

Another method for preparing ingredient of solid catalyst of the present invention includes that anhydrous magnesium chloride and above-mentioned 2- are replaced ammonia Base-phenyl ester compound A and second of Lewis alkali electron donor compounds B are ground together under conditions of magnesium dichloride activates Mill.The obtained product can be at a temperature of 80-130 DEG C with excessive TiCl₄It handles one or many.Hydrocarbon is used after processing The washing of class solvent is until not chloride ion-containing.According to further method, magnesium dichloride, the titanium compound to anhydrous state will be passed through It is co-mulled and made into and is obtained with above-mentioned 2- substituted-aminos-phenyl ester compound A and second of Lewis alkali electron donor compounds B Product, handled using the halogenated hydrocarbons of such as 1,2- dichloroethanes, chlorobenzene, dichloromethane etc.The processing at 40 DEG C extremely 1-4 hour is carried out at a temperature of between halogenated hydrocarbons boiling point.Then it is usually washed with the inert hydrocarbon solvent of hexane etc To product.

According to another method, magnesium dichloride is subjected to pre-activate according to known methods, then at about 80-135 DEG C At a temperature of with excessive TiCl₄Processing, wherein containing above-mentioned 2- substituted-aminos-phenyl ester compound A and second in the solution Lewis alkali electron donor compounds B.Use TiCl₄Processing is multiple and is cleaned to solid with hexane any for reaction to remove TiCl₄。

Further method includes that may further reference the preparation of the solids containing titanium catalytic component disclosed in CN1208045 It is prepared by method：First make liquid in the presence of a kind of compound being selected from alcohol, phenol, ketone, aldehyde, ether, amine, pyridine and ester at low temperature Body magnesium compound and liquid titanium compound contact, are settled out solid, and temperature when contact is generally -70-200 DEG C, preferably - 30-130 DEG C, with above-mentioned 2- substituted-aminos-phenyl ester compound A and second of Lewis alkali electron donor chemical combination in contact process Object processing.

Another method of ingredient of solid catalyst of the present invention includes：Magnesium compound is dissolved in by organic epoxy compound Object, organic phosphine compound and inert diluent (inert diluent be pentane, hexane, heptane, octane, decane, benzene, toluene, The mixture of diformazan benzene and its derivative or any of the above kind compound arbitrary proportion, preferably toluene, heptane or hexane) composition It in dicyandiamide solution, is mixed with titanium compound after forming homogeneous solution, in the presence of precipitation additive, solids is precipitated；This solid Object above-mentioned 2- substituted-aminos-phenyl ester compound A and second of Lewis alkali electron donor compound B processing, make it be carried on On solids, when necessary, then is handled and obtained with titanium tetrahalide and inert diluent, wherein precipitation additive is organic acid anhydride, has One kind in machine acid, ether, ketone.For each component in terms of every mole of magnesium halide, organic epoxy compound object is 0.2-10 moles, organic Phosphine compound is 0.1-3 moles, and precipitation additive is 0-1.0 moles, and Ti compounds are 0.5-150 moles.

The ingredient of solid catalyst of the present invention can also be used in SiO₂, inorganic oxides or the porous resin such as aluminium oxide The magnesium compound of upper load is prepared as carrier, then is activated by well known method, then in about 80-135 DEG C of temperature Lower excessive TiCl₄Processing, being added in processing procedure has above-mentioned 2- substituted-aminos-phenyl ester compound A and second Lewis alkali electron donor compounds B.

Above-mentioned reaction results in the magnesium halide in activity morphology, and (general crystal magnesium halide compound with regular structure can load Ti it is seldom, thus catalytic activity is low, to prepare the supported catalyst of high activity, and magnesium halide has to pass through activation process.Activation Processing method includes being made into crystallite with method physically and/or chemically, so that activated centre is carried on halogenation magnesium surface, side Edge and fault location, which is " magnesium halide in active ").In addition to these reactions, Also there is known other methods to make by forming the halogenation in activity morphology different from the compound initial substance of magnesium halide in document Magnesium.

In any preparation method, above-mentioned electron donor compound can be directly added into itself or by optional Mode carries out, such as is made in situ by using appropriate precursor, before this is appropriate in the resonable electron donor compound thought of physical efficiency Such as it completes to convert by chemical reaction known to such as esterification, transesterification etc..In general, relative to MgCl₂For, with 0.01-5, the preferably molar ratio of 0.05-2.0 use above-mentioned electron donor compound.

In any preparation method, above-mentioned 2- substituted-aminos-phenyl ester compound A and second of Lewis alkali electron Body compound B can a batch or in batches, arbitrarily combined with random order and simultaneously or separately added in preparation process.

The ingredient of solid catalyst of the present invention with reacting for organo-aluminum compound by known method to be converted to by being used for The catalyst of olefinic polymerization.Particularly, it is an object of the present invention to provide one kind being used for alkene CH₂=CHR polymerizations are urged Agent, wherein R are hydrogen or the hydrocarbyl group containing 1-12 carbon atom, which includes the product of following substance reaction：

(a) ingredient of solid catalyst of the present invention, containing Mg, Ti and halogen, selected from least one of above-mentioned The simple function group or polyfunctional group electron donor compound B of 2- substituted-aminos-phenyl ester compound A and a kind of ether, ester, ketone or amine,

(b) at least one general formula is AlR_nX_(3-n)Organo-aluminum compound, R is the alkyl of hydrogen, carbon atom number 1-20 in formula； X is halogen, and n is the integer of 0≤n≤3；With, optionally,

(c) at least one external donor compound.

Preferably, alkyl aluminum compound (b) is selected from such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three normal-butyls The trialkyl compound of aluminium, tri-n-hexyl aluminum, trioctylaluminum etc.It is also possible to using trialkylaluminium and aluminum alkyl halide, Alkyl aluminum hydride or such as AlEt₂Cl and Al₂Et₃Cl₃Etc alkylaluminium sesquichloride mixture, can also use Alkylaluminoxane.

For needing the application of good isotacticity, external donor compound can be used.External donor compound selects Self-drifting is R_nSi(OR₁)_4-nSilicone compounds, R and R in formula₁For C₁-C₁₈Alkyl, optional also hetero atom；N be 0≤ The integer of n≤3.

The silicone compounds are concretely：Trimethylmethoxysilane, trimethylethoxysilane, three n-propyl first Oxysilane, three n-propyl Ethoxysilanes, three normal-butyl methoxy silanes, triisobutyl Ethoxysilane, thricyclohexyl first Base silane, thricyclohexyl Ethoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, diη-propyl diformazan Oxysilane, diisopropyl dimethoxy silane, diη-propyl diethoxy silane, diisopropyldiethoxysilane, two are just Butyl diethoxy silane, diisobutyl diethoxy silane, di-t-butyl dimethoxysilane, di-t-butyl dimethoxy silicon Alkane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, di-t-butyl diethoxy silane, di-n-butyl two Ethoxysilane, n-butylmethyldimethoxyforane, two (2- ethylhexyls) dimethoxysilanes, two (2- ethylhexyls) two Ethoxysilane, Dicyclohexyldimethoxysilane, dicyclohexyl diethoxy silane, dicyclopentyl dimethoxyl silane, two Cyclopenta diethoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl methyl diethoxy silane, cyclohexyl-ethyl two Methoxy silane, cyclohexyl isopropyl dimethoxysilane, cyclohexyl-ethyl diethoxy silane, cyclopentyl-methyl dimethoxy Silane, cyclopentyl ethyl diethoxy silane, cyclopenta isopropyl diethoxy silane, cyclopenta isobutyl group dimethoxy silicon Alkane, cyclohexyl n-propyl dimethoxysilane, cyclohexyl n-propyl diethoxy silane, cyclohexyl normal-butyl diethoxy silicon Alkane, phenyl-methyl dimethoxysilane, phenyl-methyl diethoxy silane, amyl ethyldimethoxysilane, amyl ethyl two Ethoxysilane, cyclohexyldimethyl methoxy silane, cyclohexyl diethylmethoxysilane, cyclohexyl diethyl ylmethoxy silicon Alkane, cyclohexyl diethylethoxysilane, 2- ethylhexyls trimethoxy silane, cyclohexyl dimethoxysilane, cyclohexyl two Ethoxysilane, 2- ethylhexyls triethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl three Methoxy silane, n-propyl triethoxysilane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, normal-butyl three Methoxy silane, trimethoxysilane, tert-butyl trimethoxy silane, ne-butyltriethoxysilaneand, cyclohexyl three Methoxy silane, cyclohexyltriethyloxysilane, cyclopentyl-trimethoxy-silane, cyclopenta triethoxysilane, vinyl three Methoxy silane, vinyltriethoxysilane, 2- ethylhexyls trimethoxy silane, 2- ethylhexyls triethoxysilane, Amyltrimethoxysilane, amyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane, cyclohexyl ring amyl diformazan Oxysilane, cyclohexyl ring amyl diethoxy silane, cyclohexyl ring amyl dipropoxy silane, 3- methyl cyclohexane cyclopentyls Dimethoxysilane, 4- methyl cyclohexane cyclopentyls dimethoxysilane, 3,5- dimethyleyelohexane cyclopentyl dimethoxy silicon Alkane, 3- methyl cyclohexane butylcyclohexyls dimethoxysilane, two (3- methylcyclohexyls) dimethoxysilanes, 4- methyl cyclohexane basic rings Hexyl dimethoxysilane, two (4- methylcyclohexyls) dimethoxysilanes, 3,5- dimethyleyelohexane butylcyclohexyl dimethoxys Silane, two (3,5- Dimethylcyclohexyl) dimethoxysilanes, tetrapropoxysilane, four butoxy silanes.In these organosilicons It is preferred in compound：Diη-propyl dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, Second, isobutyl dimethoxy silane, di-t-butyl dimethoxysilane, di-n-butyl diethoxy silane, tertiary butyl trimethoxy Silane, Dicyclohexyldimethoxysilane, dicyclohexyl diethoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl Ethyl diethoxy silane, cyclohexyl-ethyl dimethoxysilane, cyclohexyl-ethyl diethoxy silane, cyclopentyl-methyl diformazan Oxysilane, cyclopentyl-methyl diethoxy silane, cyclopentyl ethyl dimethoxysilane, cyclohexyl ring dicyclopentyldimetoxy silicon Alkane, cyclohexyl ring amyl diethoxy silane, 3- methyl cyclohexane cyclopentyls dimethoxysilane, 4- methyl cyclohexane cyclopentyls Dimethoxysilane and 3,5- dimethylcyclopentyl dimethoxysilanes etc..These compounds C, which can be used alone or mix, to be made With.

The example of preferred silicon compound has Cyclohexyl Methyl Dimethoxysilane；Diisopropyl dimethoxy silane；Two Normal-butyl dimethoxysilane；Second, isobutyl dimethoxy silane；Dimethoxydiphenylsilane；Phenyl triethoxysilane； Methyl-t-butyldimethoxysilane；Dicyclopentyl dimethoxyl silane；2- ethyl piperidine base -2- t-butyldimethoxysilanes (1,1,1- tri- fluoro- 2- propyl) -2- ethyl piperidine base dimethoxysilanes and (1,1,1- tri- fluoro- 2- propyl)-methyl and first Oxysilane, cyclohexyl trimethoxy silane；Tert-butyl trimethoxy silane and tertiary hexyl trimethoxysilane.

The catalyst of the present invention can be used for alkene CH₂In=CHR (co) polymerizations, the alkene is ethylene, propylene, 1- fourths Alkene, 4-methyl-1-pentene, 1- hexenes and 1- octenes.

In order to which the catalyst in the application present invention carries out olefinic polymerization, homopolymerization and copolymerization can be applied above by component A, the catalyst prepared by b or c.The molar ratio of the Ti in Al and component a in usual component b is 1-1000, preferably 50- 800；When containing component c, the molar ratio of component c and component b is 0.002-10, preferably 0.01-2, preferably 0.01-0.5.

Olefin polymerization catalysis of the present invention preferably includes the reaction product of following component or following component, that is, does not need Use external electron donor：

A) above-mentioned ingredient of solid catalyst；

B) at least one general formula is AlR_nX_(3-n)Organo-aluminum compound, R is the alkyl of hydrogen, carbon atom number 1-20 in formula；X For halogen, n is the integer of 0≤n≤3.

Olefinic polymerization, homopolymerization and copolymerization are preferably only applied above by the catalyst prepared by component a and b, in component b The molar ratio of Ti in Al and component a is 1-1000mol, preferably 50-800.

The charging sequence of each component is arbitrary, and is added in paradigmatic system at first with component b, and the rear component a that is added is preferred； When using component c, component c is added after component b, is eventually adding component a and is preferred.

Polymerization technique in the present invention can be carried out in the case where having solvent or without solvent.Olefinic monomer can be gas Phase or liquid phase.Hydrogen is further added and can be used as molecular weight regulator.Certainly polymerization can also be in not molecular weight regulator In the case of carry out.Polymerization temperature is not higher than 200 DEG C, preferably 20-100 DEG C, more preferable 40-80 DEG C of temperature.Polymerization pressure is not To be more than 10MPa, preferably 1-5MPa.Continuous polymerization or batch polymerization process can be applied.And polymerisation can divide one Step, two steps or multistep carry out.

The alkene that homopolymerization or copolymerization are carried out using catalyst of the present invention includes linear alkene：Ethylene, propylene, 1- fourths Alkene, 1- amylenes, 1- hexenes, 1- heptene, 1- nonenes, 1- decene；Branched-chain alkene is such as：3-methyl-1-butene and 4- methyl-1-pentenes Alkene；Alkadienes is such as：Butadiene, vinylcyclopentene and vinylcyclohexene.Catalyst of the present invention is preferably applied to gather In ethylene and polypropylene.These alkene can be independent or a variety of be used in mixed way.

Using the polymerization (herein referring to mass polymerization) of catalytic component a, b, c of the present invention alkene carried out, recommend to carry out Prepolymerization is come isotacticity, the particle properties etc. that increase the living polymer of catalyst.The prepolymerization technology can be equally used for benzene Ethylene homo.

The charging sequence of each component and monomer is arbitrary in prepolymerization technology.Preferably first component b is added to and is contained In having inertia or the alkene gas that will be polymerize, the one or more alkene to be polymerize then are added after component a is added. Using the alkene of organosilan it is prepolymerized during, it is proposed that the alkene that component b is added to inert gas or polymerize In the prepolymerization system of gas, component c is then added, component a is then added, finally adds alkene.

The present invention is using the 2- substituted-aminos-phenyl ester compound and another kind Lewis alkali cpds as interior electron Body, when especially being compounded with diether compound, the activity of the catalyst of gained, which is significantly higher than, uses individually 2- substitution ammonia Base-phenyl ester compound and diether compound, and the moderate molecular weight distribution of gained polyolefin can overcome two ethers catalyst to live Though the shortcomings that property height but polymer molecular weight narrowly distributing.Such catalytic component resulting polymers when without using external electron donor Still there is high isotactic, there is super-active, and as polymerization time extension still keeps high-level activity, gained polyolefin Ash content is relatively low.When using the 2- substituted-aminos-phenyl ester compound and succinate compound compounding as internal electron donor, The molecular weight distribution of gained polyolefin can be further widened, such catalyst is suitable for preparing broad molecular weight distribution polymers production Product.In addition, when using the 2- substituted-aminos-phenyl ester compound and other common electron donor compound compoundings, performance has not The isotacticity of polymer can be improved with the improvement of degree, and adjacent two ester type compound of benzene or glycol ester compounds compounding.

Specific implementation mode

The present invention is further described with embodiment below, is conducive to be better understood by the present invention and its advantage, effect, but The embodiment is merely to illustrate the present invention rather than the limitation present invention.

The compound enumerated in embodiment is only used as example to illustrate the present invention, does not limit the present invention, other belong to this Invention scope but the compound not referred in embodiment.

Term used herein is only to be illustrated to specific embodiment, is not intended to and limits the invention. Unless otherwise defined, all terms (including technical terms and scientific terms) used herein with it is of the art The understanding of those skilled in the art is identical.Must also it is clear that, it is usually fixed in such as dictionary in addition to having specific definition herein The term of justice should be construed in the context of this specification and the relevant technologies can have the consistent meaning, without what should be explained Idealization or excessively formalization.

The measurement of polymer isotacticity

It is measured (heptane boiling extracting 6 hours) using heptane extraction process.Two grams of dry polymer samples, are placed on extractor It is middle with boiling heptane extract 6 hours after, by residue dry to obtained by constant weight polymer weight (g) with 2 ratio be etc. Normality.

The measurement of polymer molecular weight distribution

Using PL-220 type gel permeation chromatographies, (standard specimen is measured at 150 DEG C by solvent of trichloro-benzenes：Polystyrene, stream Fast 1.0mL/min, pillar：3xPlgel 10um M1Xed-B 300x7.5nm).

The measurement of polymer ash content

It is measured according to GB/T 9345.1-2008.

Table 1

Table 2

Table 3

Polymerization 1

Component using solid catalyst as olefin polymerization catalysis carries out polymerization evaluation：

In 5L stainless steel cauldrons after nitrogen is sufficiently displaced from, the triethyl aluminum hexane of a concentration of 0.5mol/L of 5mL is added Solution and Cyclohexylmethyldimethoxysilane (CMMS) hexane solution of a concentration of 0.1mol/L of 1mL and the catalyst of preparation Then 10mg is added 10mL hexanes and rinses charge line, add 2L (under standard state) hydrogen and 2.5L refines propylene, control System reaction was warming up to 70 DEG C, at this temperature polymerisation 1 hour in 20 DEG C of pre-polymerizations 5 minutes.After reaction, by reaction kettle Cool down and stop stirring discharge reaction product, through being dried to obtain polymer.

Embodiment 1

In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, 10g diethoxies magnesium and 80mL first is added Benzene prepares suspension, -10 DEG C of dropwise addition titanium tetrachloride 20mL is maintained at, after system is to slowly warm up to 10 DEG C after being added dropwise Titanium tetrachloride 60mL is added dropwise, is to slowly warm up to 90 DEG C again later, 3g 2-benzamides-phenol benzoate and 1g 9 is added, 9- is bis- Methoxyl methyl fluorenes, then proceedes to be warming up to 120 DEG C of constant temperature 2 hours, is then filtered dry only liquid pressure, filters off liquid, gained is consolidated Body is washed 3 times with 120mL titanium tetrachlorides at 125 DEG C.The solid of gained is washed 2 times with 150mL hexanes at 60 DEG C, room temperature washing 2 It is secondary, liquid and drying are filtered off, it is ingredient of solid catalyst to obtain solid powder.The Ti content of ingredient of solid catalyst interior is given Electron content and aggregated data are shown in Table 4.

Embodiment 2-8

Ingredient of solid catalyst preparation method such as embodiment 1, difference are to distinguish 2-benzamide-phenol benzoate The compound in table 1- tables 3 is replaced in order.

Embodiment 9

Ingredient of solid catalyst preparation method such as embodiment 7, difference are that the bis- methoxyl methyl fluorenes of 9,9- are replaced with neighbour Phthalic acid di-n-butyl.

Embodiment 10

Ingredient of solid catalyst preparation method such as embodiment 7, difference are that the bis- methoxyl methyl fluorenes of 9,9- are replaced with 2- Isopropyl -2- isopentyl-malonic ester.

Embodiment 11

Ingredient of solid catalyst preparation method such as embodiment 7, difference are that the bis- methoxyl methyl fluorenes of 9,9- are replaced with 2, 3- diisopropyl diethyl succinates.

Embodiment 12

Ingredient of solid catalyst preparation method such as embodiment 7, difference are that the bis- methoxyl methyl fluorenes of 9,9- are replaced with 2, 4- glycol dibenzoates.

Embodiment 13

Ingredient of solid catalyst preparation method such as embodiment 7, difference are by 3g 2- [N- benzoyl-N- benzyls] -4- T-butyl-benzoic acid phenyl ester and the bis- methoxyl methyl fluorenes of 1g 9,9- are changed to 3g 2- [N- benzoyl-N- benzyls] -4- tertiary butyls-benzene Phenyl formate and the bis- methoxyl methyl fluorenes of 1.5g 9,9-.

Embodiment 14

Ingredient of solid catalyst preparation method such as embodiment 7, difference are by 3g 2- [N- benzoyl-N- benzyls] -4- T-butyl-benzoic acid phenyl ester and the bis- methoxyl methyl fluorenes of 1g 9,9- are changed to 1.5g 2- [N- benzoyl-N- benzyls] -4- tertiary butyls - Phenol benzoate and the bis- methoxyl methyl fluorenes of 1.5g 9,9-.

Embodiment 15

Ingredient of solid catalyst preparation method such as embodiment 7, difference are by 3g 2- [N- benzoyl-N- benzyls] -4- T-butyl-benzoic acid phenyl ester and the bis- methoxyl methyl fluorenes of 1g 9,9- are changed to 2g 2- [N- benzoyl-N- benzyls] -4- tertiary butyls-benzene Phenyl formate and the bis- methoxyl methyl fluorenes of 1.5g 9,9-.

Embodiment 16

Ingredient of solid catalyst preparation method such as embodiment 7, difference are by 3g 2- [N- benzoyl-N- benzyls] -4- T-butyl-benzoic acid phenyl ester and the bis- methoxyl methyl fluorenes of 1g 9,9- are changed to 3g 2- [N- benzoyl-N- benzyls] -4- tertiary butyls-benzene Phenyl formate and the bis- methoxyl methyl fluorenes of 0.5g 9,9-.

Embodiment 17

Ingredient of solid catalyst preparation method such as embodiment 7, difference are by 3g 2- [N- benzoyl-N- benzyls] -4- T-butyl-benzoic acid phenyl ester and the bis- methoxyl methyl fluorenes of 1g 9,9- are changed to 2g 2- [N- benzoyl-N- benzyls] -4- tertiary butyls-benzene Phenyl formate and the bis- methoxyl methyl fluorenes of 2g 9,9-.

Embodiment 18

Ingredient of solid catalyst preparation method such as embodiment 1, difference are that 2-benzamide-phenol benzoate is changed to 2- [N- benzoyl-N- tertiary butyls]-phenol benzoate.

Embodiment 19

Ingredient of solid catalyst preparation method such as embodiment 1, difference are that 2-benzamide-phenol benzoate is changed to 2- [N- benzoyl-N- phenyl] -4- t-butyl-benzoic acid phenyl esters.

Embodiment 20

In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, 10gMgCl is added at -15 DEG C₂· 3C₂H₅OH microballoons and 150mL titanium tetrachlorides prepare suspension, are maintained at -15 DEG C 1 hour, are slowly warming up to 80 DEG C, are added 3g 2- [N- benzoyl-N- benzhydryls] -4- t-butyl-benzoic acids phenyl esters and the bis- methoxyl methyl fluorenes of 1g 9,9-, then proceed to It is warming up to 110 DEG C of constant temperature 1 hour, then liquid pressure is filtered dry only, filters off liquid, the solid of gained is existed with 120mL titanium tetrachlorides 125 DEG C are washed 3 times.The solid of gained is washed 4 times with 150mL hexanes at 60 DEG C, filters off liquid and dry to get to solid catalysis Agent component.

Embodiment 21

The 2-Ethylhexyl Alcohol of anhydrous magnesium chloride 8g, 38mL decane and 35mL reacted at 130 DEG C 2 hours with formed uniformly it is molten Liquid.1.7g phthalic anhydrides are added in solution, mixture stirs 1 hour at 130 DEG C, so that phthalic anhydride is completely molten Solution is in homogeneous solution.Obtained homogeneous solution is cooled to room temperature, and is added drop-wise in 1 hour and is maintained at -20 DEG C of 200mL tetra- In titanium chloride；It drips rear mixed solution and is heated to 110 DEG C in 4 hours, 3g 2- [N- benzene is added when temperature reaches 110 DEG C Formyl-N- benzhydryls] -4- t-butyl-benzoic acids phenyl ester and the bis- methoxyl methyl fluorenes of 1g 9,9-, mixture is at the temperature disclosed above Stirring 2 hours.After reaction 2 hours, solid portion is collected by heat filtering.Solid portion is suspended in 275mL titanium tetrachlorides, It is reacted 2 hours under the conditions of 110 DEG C.After reaction, solids portion is collected by heat filtering, at 110 DEG C with decane and hexane into Row fully washing, obtains ingredient of solid catalyst after draining.

Embodiment 22

In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, room temperature addition 10g anhydrous magnesium chlorides, 150mL toluene, 17mL epoxychloropropane and 16mL tributyl phosphates are warming up to 50 DEG C, and maintain 2 hours under stirring, solid is complete Then fully dissolved is added 2.40g phthalic anhydrides, then maintains 1 hour.Solution is cooled to -25 DEG C, is added dropwise in 1 hour Titanium tetrachloride 110mL is to slowly warm up to 80 DEG C, in temperature-rise period, gradually washes out solids.3g 2- [N- benzoyls-are added N- benzhydryls] -4- t-butyl-benzoic acids phenyl ester and the bis- methoxyl methyl fluorenes of 1g 9,9-, it is maintained 1 hour at 80 DEG C.After filtering 200mL toluene washes twice, and 120mL toluene and 80mL titanium tetrachlorides is then added, and continues to be warming up to 110 DEG C, constant temperature 2 hours, Then liquid pressure is filtered dry only, it is primary repeats processing.Liquid is filtered off, the solid of gained is washed 1 time with 100mL dichloroethanes, Hexane washs 4 times, and ingredient of solid catalyst is obtained after dry.

Embodiment 23

Ingredient of solid catalyst preparation method such as embodiment 20, difference are that the bis- methoxyl methyl fluorenes of 9,9- are changed to 2,4- Glycol dibenzoate.

Embodiment 24

Ingredient of solid catalyst preparation method such as embodiment 21, difference are that the bis- methoxyl methyl fluorenes of 9,9- are changed to 2,4- Glycol dibenzoate.

Embodiment 25

Ingredient of solid catalyst preparation method such as embodiment 22, difference are that the bis- methoxyl methyl fluorenes of 9,9- are changed to 2,4- Glycol dibenzoate.

Embodiment 26

Ingredient of solid catalyst preparation method such as embodiment 20, difference are that the bis- methoxyl methyl fluorenes of 9,9- are changed to 2,3- Diisopropyl diethyl succinate.

Embodiment 27

Ingredient of solid catalyst preparation method such as embodiment 21, difference are that the bis- methoxyl methyl fluorenes of 9,9- are changed to 2,3- Diisopropyl diethyl succinate.

Embodiment 28

Ingredient of solid catalyst preparation method such as embodiment 22, difference are that the bis- methoxyl methyl fluorenes of 9,9- are changed to 2,3- Diisopropyl diethyl succinate.

Comparative example 1

Ingredient of solid catalyst preparation method such as embodiment 1, difference are by 3g 2-benzamides-phenol benzoate With 1g 9, the bis- methoxyl methyl fluorenes of 9- are changed to 4g 2-benzamides-phenol benzoate.

Comparative example 2

Ingredient of solid catalyst preparation method such as embodiment 1, difference are by 3g 2-benzamides-phenol benzoate With 1g 9, the bis- methoxyl methyl fluorenes of 9- are changed to 4g 2-benzamide 4- t-butyl-benzoic acid phenyl esters.

Comparative example 3

Ingredient of solid catalyst preparation method such as embodiment 1, difference are by 3g 2-benzamides-phenol benzoate With 1g 9, the bis- methoxyl methyl fluorenes of 9- are changed to 4g 2- benzimides-phenol benzoate.

Comparative example 4

Ingredient of solid catalyst preparation method such as embodiment 1, difference are by 3g 2-benzamides-phenol benzoate With 1g 9, the bis- methoxyl methyl fluorenes of 9- are changed to 4g 2- benzimide -4- methyl-benzoic acid phenyl esters.

Comparative example 5

Ingredient of solid catalyst preparation method such as embodiment 1, difference are by 3g 2-benzamides-phenol benzoate With 1g 9, the bis- methoxyl methyl fluorenes of 9- are changed to 4g 2- (1- naphthalenecarboxamide-N- benzyls) -4- methyl-(1- naphthoic acids) phenyl ester.

Comparative example 6

Ingredient of solid catalyst preparation method such as embodiment 1, difference are by 3g 2-benzamides-phenol benzoate With 1g 9, the bis- methoxyl methyl fluorenes of 9- are changed to 4g 2- (decoyl amine-n-n-hexyl) -4- methyl-octanoic phenyl esters.

Comparative example 7

Ingredient of solid catalyst preparation method such as embodiment 1, difference are by 3g 2-benzamides-phenol benzoate With 1g 9, the bis- methoxyl methyl fluorenes of 9- are changed to 4g 2- [N- benzoyl-N- benzyls] -4- t-butyl-benzoic acid phenyl esters.

Comparative example 8

Ingredient of solid catalyst preparation method such as embodiment 1, difference are by 3g 2-benzamides-phenol benzoate With 1g 9, the bis- methoxyl methyl fluorenes of 9- are changed to 4g 2- [N- benzoyl-N- benzyls] -4- methyl -6- methyl-benzoic acid phenyl esters.

Comparative example 9

It is by 3g 2-benzamides-phenylamino benzoic acid that ingredient of solid catalyst preparation method such as embodiment 1, which is difference, Ester and the bis- methoxyl methyl fluorenes of 1g 9,9- are changed to 4g n-butyl phthalates.

Comparative example 10

Ingredient of solid catalyst preparation method such as embodiment 1, difference are by 3g 2-benzamides-phenol benzoate With 1g 9, the bis- methoxyl methyl fluorenes of 9- are changed to 4g 9,9- methoxyl methyl fluorenes.

Comparative example 11

Ingredient of solid catalyst preparation method such as embodiment 1, difference are by 3g 2-benzamides-phenol benzoate With 1g 9, the bis- methoxyl methyl fluorenes of 9- are changed to 4g 2- isopropyls -2- isopentyl-malonic ester.

Comparative example 12

Ingredient of solid catalyst preparation method such as embodiment 1, difference are by 3g 2-benzamides-phenol benzoate With 1g 9, the bis- methoxyl methyl fluorenes of 9- are changed to 4g 2,3- diisopropyl diethyl succinates.

Comparative example 13

Ingredient of solid catalyst preparation method such as embodiment 1, difference are by 3g 2-benzamides-phenol benzoate With 1g 9, the bis- methoxyl methyl fluorenes of 9- are changed to 4g 2,4- glycol dibenzoates.

Table 4

DNBP：N-butyl phthalate, FLU：9,9- methoxyl methyl fluorenes

DIE：2- isopropyls -2- isopentyl-malonic ester, SUC：2,3- diisopropyl diethyl succinates

BRD：2,4- glycol dibenzoates, "-" indicate that this does not have

8 kinds of 2- substituted-aminos-phenyl ester compounds and 9, the bis- methoxyl methyl fluorenes of 9- are respectively adopted it can be seen from 4 data of table When compounding the internal electron donor as catalytic component (embodiment 1-8, embodiment 13-19), the activity of catalyst is significantly high In exclusive use 2- substituted-aminos-phenyl ester compound (comparative example 1-8) and the bis- methoxyl methyl fluorenes (comparative examples of 9,9- are used alone 10) it is the activity of the catalyst of internal electron donor, the molecular weight distribution of resulting polymers is between 2- substituted-aminos-phenyl ester compound Between the bis- methoxyl methyl fluorenes of 9,9-.When other conditions fix only 2- substituted-aminos-phenyl ester compound and 9, the bis- methoxyl methyls of 9- When the ratio difference of fluorenes compounding (embodiment 7,13~17), the activity of catalyst and the molecular weight distribution of resulting polymers are significantly not Together, highest can be improved to 93.2KgPP/gCat, and polymer molecular weight distribution is moderate.

When being compounded using 2- substituted-aminos-phenyl ester compound and succinate (embodiment 11), resulting polymers molecule It is wider when amount distribution is than using individually 2- substituted-aminos-phenyl ester compound (comparative example 7) and succinate (comparative example 12).

When being compounded using 2- substituted-aminos-phenyl ester compound and n-butyl phthalate (embodiment 9), compared to When using individually 2- substituted-aminos-phenyl ester compound (comparative example 7) and n-butyl phthalate (comparative example 9), institute Obtaining the isotacticity of polymer can further improve.(embodiment when 2- substituted-aminos-phenyl ester compound and glycol ester compounds compound 12) polymer isotacticity, can be improved (compared to comparative example 7 and comparative example 13).

Polymerizing condition 2

Component using solid catalyst as olefin polymerization catalysis carries out polymerization evaluation according to following condition：

In 5L stainless steel cauldrons after nitrogen is sufficiently displaced from, the triethyl aluminum hexane solution of a concentration of 0.5mol/L is added Then (amount of triethyl aluminum is shown in Table the Al/Ti in 4) and the 3-5mg catalyst prepared is added 10mL hexanes and rinses charge line, It adding 2L (under standard state) hydrogen and 2.5L and refines propylene, control reaction was warming up to 70 DEG C in 20 DEG C of pre-polymerizations 5 minutes, The polymerisation corresponding time (being shown in Table 5) at a temperature of this.After reaction, reaction kettle is cooled down and stops stirring and reaction product is discharged, Through being dried to obtain polymer.Acquired results are shown in Table 5.

Embodiment 29- embodiments 34

It is polymerize according to condition described in polymerizing condition 2 and table 5 using catalyst CAT-13, polymerization result is shown in Table 5.

Embodiment 35- embodiments 40

It is polymerize according to condition described in polymerizing condition 2 and table 5 using catalyst CAT-17, polymerization result is shown in Table 5.

Comparing embodiment 14

It is polymerize according to condition described in polymerizing condition 2 and table 5 using catalyst REF-7, polymerization result is shown in Table 5.

Comparing embodiment 15- comparing embodiments 19

Catalyst REF-9~REF-13 is respectively adopted according to condition described in polymerizing condition 2 and table 5 to be polymerize, polymerize It the results are shown in Table 5.

Table 5

It can be seen from 5 data of table 2- substituted-aminos-phenyl ester compound and 9, the bis- first of 9- are used using magnesium ethylate carrier The catalyst CAT-13 and CAT-17 of oxygen methyl fluorenes compounding, without using external donor compound, can be obtained super in polymerization High activity far above the catalyst (comparative example 14- comparative examples 19) of non-compounding under same polymerizing condition, and still maintains 98.0% or more high isotactic.90 minutes and 120 minutes were extended between upon polymerization from 60 minutes, catalyst can keep superelevation Activity is unattenuated.It is relatively low using gained polypropylene ash content when low Al/Ti, it is minimum to be down to 25ppm.

Although above the present invention is described in detail with a general description of the specific embodiments, On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.

Claims

1. for the ingredient of solid catalyst of olefinic polymerization, it includes Mg, Ti, halogen and at least two electron donors, one kind to give Electron A is 2- substituted-aminos-phenyl ester compound in general formula (I)：

Wherein, R¹、R²、R³And R⁴It is identical or different, it is H；Halogen；C₁-C₂₀Alkyl, can contain be selected from N, O, S, P, Si and halogen One or more hetero atoms；R¹、R²、R³And R⁴It is therein two or more to be mutually bonded cyclization；R⁵For C₁-C₂₀Alkyl, Containing one or more hetero atoms selected from N, O, S, P, Si and halogen, as carbon atom, either hydrogen atom or the two take Dai Ji；R^IAnd R^IIIt is identical or different, it is H；C₁-C₂₀Alkyl, containing selected from N, O, S, P, Si and halogen one or more Hetero atom can contain unsaturated bond；R^IAnd R^IIBonding cyclization or unsaturated bond；

The molar ratio of electron donor A and B are 0.01~100.

2. ingredient of solid catalyst according to claim 1, which is characterized in that in general formula (I), R¹、R²、R³And R⁴It is identical or Difference is H；Halogen；C₁-C₂₀Linear chain or branched chain alkyl, naphthenic base, alkenyl, ester group, phenyl, alkyl phenyl, octadecyloxy phenyl Base, indenyl, benzyl, halogenated or the alkyl, naphthenic base, phenyl, alkyl phenyl, the octadecyloxy phenyl that are replaced by N, O, S, P, Si hetero atom Base, indenyl, benzyl；Or it is selected from heterocyclic aryl substituent group；R¹、R²、R³And R⁴It is therein two or more to be mutually bonded cyclization Shape structure is saturation or undersaturated；R⁵For C₁-C₂₀Linear chain or branched chain alkyl, naphthenic base, alkenyl, ester group, benzene Base, alkyl phenyl, phenylalkyl, indenyl, benzyl, halogenated or the alkyl, naphthenic base, the benzene that are replaced by N, O, S, P, Si hetero atom Base, alkyl phenyl, phenylalkyl, indenyl, benzyl；Or it is selected from heterocyclic aryl substituent group；R^IAnd R^IIIt is identical or different, it is H； C₁-C₂₀Linear chain or branched chain alkyl, naphthenic base, alkenyl, ester group, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl, halogen Generation or alkyl, naphthenic base, phenyl, alkyl phenyl, phenylalkyl, indenyl, the benzyl replaced by N, O, S, P, Si hetero atom；Or Selected from heterocyclic aryl substituent group；R^IAnd R^IIBonding cyclization or unsaturated bond.

3. ingredient of solid catalyst according to claim 1, which is characterized in that the electron donor is selected from logical formula (II) Compound：

Wherein, group R¹-R⁴And R^IIThere is meaning identical with formula (I) is led to；R^5’And R⁵It is identical or different, it is C₁-C₂₀Alkyl, Containing one or more hetero atoms selected from N, O, S, P, Si and halogen, as carbon atom, either hydrogen atom or the two take Dai Ji, preferably C₁-C₂₀Linear chain or branched chain alkyl, naphthenic base, alkenyl, ester group, phenyl, alkyl phenyl, phenylalkyl, indenes Base, benzyl, halogenated or the alkyl, naphthenic base, phenyl, alkyl phenyl, phenylalkyl, the indenes that are replaced by N, O, S, P, Si hetero atom Base, benzyl；Or it is selected from heterocyclic aryl substituent group.

4. ingredient of solid catalyst according to claim 3, which is characterized in that the electron donor is selected from logical formula (III) Compound：

Wherein, group R¹-R⁵There is meaning identical with formula (I) is led to, R^5’There is meaning identical with formula (II) is led to, R⁶And R^6’Phase It is same or different, it is selected from H；C₁-C₂₀Alkyl, containing selected from N, O, S, P, Si and halogen one or more hetero atoms, as Carbon atom either hydrogen atom or the substituent group of the two, preferably C₁-C₂₀Linear chain or branched chain alkyl, naphthenic base, alkenyl, ester Base, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl, halogenated or the alkyl, the cycloalkanes that are replaced by N, O, S, P, Si hetero atom Base, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl；Or it is selected from heterocyclic aryl substituent group.

5. ingredient of solid catalyst according to claim 1, which is characterized in that the electron donor is selected from logical formula (IV) Compound：

6. ingredient of solid catalyst according to any one of claims 1-5, which is characterized in that another electron donor Close object B and be selected from the Lewis alkali containing one or more electronegativity groups, electron donor atom therein be selected from N, O, S, P, As or The group of Sn compositions, such as the electron donor compound selected from two ethers, esters, diones and Diamines.

7. ingredient of solid catalyst according to claim 6, which is characterized in that the diether compound is selected from general formula (V) 1,3-, bis- ethers：

Wherein：R、R¹、R²、R³、R⁴And R⁵It may be the same or different, represent H or have the straight chain or branched-alkyl, ring of 1-18 carbon atom Alkyl, aryl, alkaryl or aralkyl；R⁶And R⁷It may be the same or different, represent the straight chain for having 1-20 carbon atom or branched alkane The alkaryl and aralkyl of base, the naphthenic base of 3-20 carbon atom, the aryl of 5-20 carbon atom, 7-20 carbon atom；R to R⁷ One or more of group can link to form cyclic structure, may include selected from halogen, N, O, S, P and Si one or more Hetero atom.

8. ingredient of solid catalyst according to claim 6, which is characterized in that the ester type compound is monocarboxylic esters Or polybasic carboxylic acid esters compound, the diester of optimization aromatic dicarboxylic acids, such as ditridecyl phthalate or terephthalic acid (TPA) two Ester.

9. ingredient of solid catalyst according to claim 8, which is characterized in that the ester type compound is selected from logical formula (VI) Succinate compound compound：

Wherein, group R¹And R², it is same or different to each other, is C₁-C₂₀Line style or branched-alkyl, alkenyl, naphthenic base, aryl, virtue Alkyl or alkylaryl group optionally include hetero atom；R³-R⁶In at least two groups be different from hydrogen and be selected from C₁-C₂₀Line style Or branched-alkyl, alkenyl, naphthenic base, aryl, aralkyl or alkylaryl group, optionally contain hetero atom, in addition, group R³-R⁶It can be connected together and constitute a ring.

10. ingredient of solid catalyst according to claim 6, which is characterized in that the ester type compound is selected from general formula (VII) glycol ester compounds：

In formula, R¹-R⁶、R^1’-R^2’For the C1-C20 alkane of identical or different hydrogen, halogen or substituted or unsubstituted linear chain or branched chain Base, C3-C20 naphthenic base, C6-C20 aryl, C7-C20 alkaryls, C7-C20 aralkyl, C2-C10 alkylenes or C10-C20 are thick Cyclophane base；But R^1’And R^2’It is not hydrogen, R¹-R⁶One or more of it is optionally cyclic or not cyclic.

11. ingredient of solid catalyst according to claim 1, which is characterized in that the 2- substituted-aminos-of the general formula (I) The molar ratio of phenyl ester compound A and Lewis alkali cpd B is preferred 0.02-50, more preferable 0.05-20.

12. according to the ingredient of solid catalyst described in any one of claim 1-11, including titanium compound, magnesium compound and choosing From the reaction product of the 2- substituted-aminos-phenyl ester compound A and Lewis alkali cpd B, the precursor of the magnesium compound selects From at least one：X_nMg(OR)_2-n, MgCl₂MROH, R_2-nMgX_n, MgCl₂/SiO₂, MgCl₂/Al₂O₃Or magnesium halide and alcohol titanium Mixture, m is the number of 0.1-6 in formula, and 0≤n≤2, X are halogen, and R is hydrogen or C₁-C₂₀Alkyl；The titanium compound leads to Formula is TiX_N(OR)_4-N, R is the alkyl that carbon atom number is 1-20 in formula, and X is halogen, N=1-4.

13. a kind of method preparing the ingredient of solid catalyst described in any one of claim 1-12 for olefinic polymerization, It is characterized in that, including：Make magnesium compound and titanium compound and is selected from the 2- substituted-aminos-phenyl ester internal electron donor compound A and Lewis alkali cpds B contacts, to obtain ingredient of solid catalyst.

14. one kind being used for alkene CH₂=CHR polymerization catalyst, wherein R be hydrogen or the hydrocarbyl group containing 1-12 carbon atom, It is characterized in that, includes the product of following substance reaction：

(a) ingredient of solid catalyst described in any one of claim 1-12；

(b) at least one general formula is AlR_nX_(3-n)Organo-aluminum compound, R is the alkyl of hydrogen, carbon atom number 1-20 in formula；X is Halogen, n are the integer of 0≤n≤3；With, optionally,

(c) at least one general formula that is selected from is R_nSi(OR₁)_4-nSilicone compounds as external donor compound, in formula R and R₁For C₁-C₁₈Alkyl, optional also hetero atom；N is the integer of 0≤n≤3.

15. one kind being used for alkene CH₂=CHR polymerization catalyst, wherein R be hydrogen or the hydrocarbyl group containing 1-12 carbon atom, It is characterized in that, includes the product of following substance reaction：

(a) ingredient of solid catalyst described in any one of claim 1-12；

(b) at least one general formula is AlR_nX_(3-n)Organo-aluminum compound, R is the alkyl of hydrogen, carbon atom number 1-20 in formula；X is Halogen, n are the integer of 0≤n≤3.

16. being used for alkene CH₂The method of=CHR polymerizations, including homopolymerization, pre-polymerization and copolymerization, wherein R are former for hydrogen or containing 1-12 carbon The hydrocarbyl group of son, catalyst described in claims 14 or 15 in the presence of, carry out.