CN108517022B

CN108517022B - Solid catalyst component for olefin polymerization, catalyst and application thereof

Info

Publication number: CN108517022B
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 LIHE TECHNOLOGY Ltd
Current assignee: BEIJING LIHE TECHNOLOGY Ltd
Priority date: 2017-03-10
Filing date: 2017-03-10
Publication date: 2020-10-27
Anticipated expiration: 2037-03-10
Also published as: CN108517022A

Abstract

The invention provides a solid catalyst component for olefin polymerization, which comprises Mg, Ti, halogen and at least two electron donors, wherein one electron donor is a 2-substituted amino-phenyl ester compound A selected from a general formula (I), and the other electron donor is a Lewis base compound B containing one or more electronegative groups. The invention also discloses a catalyst containing the solid catalyst component and application of the catalyst in olefin polymerization reaction, in particular application in propylene polymerization reaction. The catalyst has high activity, can obtain polypropylene with high isotacticity and wide molecular weight distribution, can also obtain polypropylene with high isotacticity without an external electron donor, reduces Al/Ti and Al/Si during polymerization, prolongs the polymerization time, can still maintain high activity, and is suitable for producing low-ash polymers.

Description

Solid catalyst component for olefin polymerization, catalyst and application thereof

Technical Field

The invention relates to a method for CH₂The present invention relates to a solid catalyst component for the polymerization of olefins, wherein R is hydrogen or a hydrocarbyl group containing from 1 to 12 carbon atoms, more particularly to a solid catalyst component comprising at least one 2-substituted amino-phenyl ester compound and a Lewis base compound, to a catalyst comprising the solid catalyst component and to the use of the catalyst in the polymerization of olefins, in particular in the polymerization of propylene.

Background

In the propylene polymerization industry, the most widely studied and used catalyst is the Ziegler-Natta catalyst, which is prepared by adding an internal electron donor during the titanium loading of an active magnesium chloride support. Since the internal electron donor can change the catalyst performance to the greatest extent, research and search of an ideal internal electron donor compound become a focus and hot spot of research on Z-N catalysts. At present, the research on internal electron donors at home and abroad mainly focuses on: 1) traditional fatty acid ester and aromatic acid ester compounds, mainly represented by phthalate ester compounds; 2) diethers (e.g. EP0361493, EP 0728724); 3) succinate compounds (e.g. WO9856834, WO0063261, WO 03022894); 4) diol ester compounds (e.g., WO9856834, WO0063261, WO 03022894); 5) other functional group compounds (CN1105671, CN1242780, US20060128558) and the like.

However, in practical applications, the above compounds have certain problems as internal electron donors of catalysts for olefin polymerization, such as low activity of catalysts using binary aromatic carboxylic acid ester compounds as internal electron donors, narrow relative molecular mass distribution of the Prepared Polypropylene (PP), and great harm to human reproductive health and environment due to the use of phthalate compounds as common plasticizers; although the catalyst using the 1, 3-diether compound as the internal electron donor has high activity and good hydrogen regulation sensitivity, the prepared PP has narrow relative molecular mass distribution and is not beneficial to developing PP with different brands; the succinate compound is used as an internal electron donor, has the advantages that the synthesized PP has wider relative molecular mass distribution, and has the defects that the stereoregularity of the PP and the hydrogen regulation sensitivity of the catalyst need to be improved; the activity of the glycol ester catalytic system is not as good as that of the diether system.

When the catalyst prepared by adopting a single internal electron donor cannot meet the specific requirements of a polypropylene product, for example, the catalyst is required to have the characteristics of ultrahigh activity, high stereospecificity, low external electron donor demand and the like, the compound use of multiple internal electron donors is also an effective method for solving the problem, namely when the Z-N catalyst is prepared, two or more than two internal electron donors are used simultaneously, and the comprehensive performance of the Z-N catalyst is improved by adjusting the content of different internal electron donors in the Z-N catalyst.

Disclosure of Invention

The invention aims to provide a method for CH₂Solid catalyst component for CHR olefin polymerization.

It is another object of the present invention to provide a method for preparing the solid catalyst component.

It is a further object of the present invention to provide the solid catalyst component in CH₂Use in the preparation of a CHR olefin polymerisation catalyst.

In order to achieve the object of the present invention, the present invention provides a solid catalyst Component (CH) for olefin polymerization₂CHR olefins, where R is hydrogen or a hydrocarbyl group containing 1 to 12 carbon atoms), comprising Mg, Ti, halogen and at least two electron donors, one electron donor a being a 2-substituted amino-phenyl ester compound selected from formula (i):

wherein R is¹、R²、R³And R⁴Identical or different, is H; halogen; c₁-C₂₀May contain one or more heteroatoms selected from N, O, S, P, Si and halogen as substituents of carbon atoms or hydrogen atoms or both; r¹、R²、R³And R⁴Two or more of which may be bonded to each other to form a ring; r⁵Is C₁-C₂₀May contain one or more heteroatoms selected from N, O, S, P, Si and halogen as substituents of carbon atoms or hydrogen atoms or both; r^IAnd R^IIIdentical or different, is H; c₁-C₂₀May contain one or more heteroatoms selected from N, O, S, P, Si and halogen, may contain unsaturated bonds; r^IAnd R^IICan be bonded to form a ring or an unsaturated bond;

the other electron donor B is selected from Lewis base compounds containing one or more electronegative groups;

the molar ratio of the electron donors A and B is 0.01-100, preferably 0.02-50, and more preferably 0.5-20.

Preferably, R in the formula (I)¹、R²、R³And R⁴Identical or different, is H; halogen; c₁-C₂₀Linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, alkyl which is halogenated or substituted with the N, O, S, P, Si heteroatom, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or is selected from heterocyclic aryl substituents; r¹、R²、R³And R⁴Two or more of which may be bonded to each other to form a cyclic structure, which may be saturated or unsaturated; r⁵Is C₁-C₂₀Linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, alkyl which is halogenated or substituted with the N, O, S, P, Si heteroatom, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or is selected from heterocyclic aryl substituents; r^IAnd R^IIIdentical or different, is H; c₁-C₂₀Linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, alkyl which is halogenated or substituted with the N, O, S, P, Si heteroatom, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or is selected from heterocyclic aryl substituents; r^IAnd R^IIMay be bonded to form a ring or an unsaturated bond.

In one embodiment, R¹-R⁴At least one (or two, or three, or four) R group(s) in (a) is selected from the group consisting of substituted hydrocarbyl groups containing 1 to 20 carbon atoms, unsubstituted hydrocarbyl groups containing 1 to 20 carbon atoms, alkoxy groups containing 1 to 20 carbon atoms, heteroatoms, and combinations thereof.

In one embodiment, R¹-R⁴Any adjacent R groups in (a) may be linked to form an inter-ring structure or an intra-ring structure. The inter/intra ring structures may or may not be aromatic. In one embodiment, an inter/intra ring junctionThe structure is a C5 membered ring or a C6 membered ring.

Among the compounds represented by the above general formula (I), a compound represented by the following general formula (II) is preferable:

wherein the radical R¹-R⁴And R^IIHas the same meaning as in the general formula (I); r^5’And R⁵Same or different is C₁-C₂₀May contain one or more heteroatoms selected from N, O, S, P, Si and halogen as substituents of carbon atoms or hydrogen atoms or both, preferably C₁-C₂₀Linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, alkyl which is halogenated or substituted with the N, O, S, P, Si heteroatom, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or is selected from heterocyclic aryl substituents.

Specific examples of the compounds included in the general formula (II) are:

2-acetamide-phenyl acetate; 2-propionamide-phenyl propionate; 2-n-butylamide-phenyl n-butyrate; 2-isobutyramide-phenyl isobutyrate; 2-n-valeramide-n-pentanoic acid phenyl ester; 2-isovaleramide-phenyl isovalerate; 2-hexanamide-phenyl hexanoate; 2-cyclohexanecarboxamide-phenyl cyclohexanecarboxylate; 2-n-heptanoamide-n-heptanoic acid phenyl ester; 2-n-octanoyl amide-n-octanoyl phenyl ester; 2-n-nonanamide-phenyl n-nonanoate; 2-n-decanamide-phenyl n-decanoate; 2-n-undecanamide-n-undecanoic acid phenyl ester; 2-n-dodecanoamide-phenyl n-dodecanoate; 2-n-tridecylamide-n-tridecanoic acid phenyl ester; 2-n-tetradecanamide-n-tetradecanoic acid phenyl ester; 2-n-pentadecanamide-n-pentadecanoic acid phenyl ester; 2-n-hexadecanamide-n-hexadecanoic acid phenyl ester; 2-n-heptadecanamide-n-heptadecanoic acid phenyl ester; 2-n-octadecanamide-n-octadecanoic acid phenyl ester; 2-n-nonadecanamide-n-nonadecanoic acid phenyl ester; 2-n-eicosamide-n-eicosanoic acid phenyl ester;

2-acetamide-4-methyl-phenyl acetate; 2-propionamide-4-methyl-propionic acid phenyl ester; 2-n-butylamide-4-methyl-n-butyric acid phenyl ester; 2-isobutyramide-phenyl isobutyrate; 2-n-valeramide-n-pentanoic acid phenyl ester; 2-isovaleramide-phenyl isovalerate; 2-hexanamide-4-methyl-phenyl hexanoate; 2-cyclohexanecarboxamide-4-methyl-cyclohexanecarboxylic acid phenyl ester; 2-n-heptanoamide-4-methyl-n-heptanoic acid phenyl ester; 2-n-octanoyl amide-4-methyl-n-octanoic acid phenyl ester; 2-n-nonanamide-4-methyl-n-nonanoic acid phenyl ester; 2-n-decanamide-4-methyl-phenyl n-decanoate; 2-n-undecanamide-4-methyl-n-undecanoic acid phenyl ester; 2-n-dodecanoamide-4-methyl-n-dodecanoic acid phenyl ester; 2-n-tridecanoic acid phenyl ester-4-methyl-n-tridecanoic acid; 2-n-tetradecanamide-4-methyl-n-tetradecanoic acid phenyl ester; 2-n-pentadecanamide-4-methyl-n-pentadecanoic acid phenyl ester; 2-n-hexadecanamide-4-methyl-n-hexadecanoic acid phenyl ester; 2-n-heptadecanamide-4-methyl-n-heptadecanoic acid phenyl ester; 2-n-octadecanamide-4-methyl-n-octadecanoic acid phenyl ester; 2-n-nonadecamide-4-methyl-n-nonadecanoic acid phenyl ester; 2-n-eicosanamide-4-methyl-n-eicosanoic acid phenyl ester;

2-acetamide-4-ethyl-phenyl acetate; 2-propionamide-4-ethyl-propionic acid phenyl ester; 2-n-butylamide-4-ethyl-n-butyric acid phenyl ester; 2-isobutyramide-4-ethyl-isobutyric acid phenyl ester; 2-n-valeramide-4-ethyl-n-pentanoic acid phenyl ester; 2-isovaleramide-4-ethyl-isovalerate phenyl ester; 2-hexanamide-4-ethyl-hexanoic acid phenyl ester; 2-cyclohexanecarboxamide-4-ethyl-cyclohexanecarboxylic acid phenyl ester; 2-n-heptanoamide-4-ethyl-n-heptanoic acid phenyl ester; 2-n-octanoyl amide-4-ethyl-n-octanoic acid phenyl ester; 2-n-nonanamide-4-ethyl-n-nonanoic acid phenyl ester; 2-n-decanamide-4-ethyl-n-decanoic acid phenyl ester;

2-acetamide-4-tert-butyl-phenyl acetate; 2-propionamide-4-tert-butyl-propionic acid phenyl ester; 2-n-butylamide-4-tert-butyl-n-butyric acid phenyl ester; 2-isobutyramide-4-tert-butyl-phenyl isobutyrate; 2-n-valeramide-4-tert-butyl-n-pentanoic acid phenyl ester; 2-isovaleramide-4-tert-butyl-phenyl isovalerate; 2-n-hexanamide-4-tert-butyl-n-hexanoic acid phenyl ester; 2-cyclohexanecarboxamide-4-tert-butyl-cyclohexanecarboxylic acid phenyl ester; 2-n-heptanoamide-4-tert-butyl-n-heptanoic acid phenyl ester; 2-n-octanoyl amide-4-tert-butyl-n-octanoic acid phenyl ester; 2-n-nonanamide-4-tert-butyl-n-nonanoic acid phenyl ester; 2-n-decanamide-4-tert-butyl-phenyl n-decanoate; 2-n-undecanamide-4-tert-butyl-n-undecanoic acid phenyl ester; 2-n-dodecanoamide-4-tert-butyl-n-dodecanoic acid phenyl ester; 2-n-tridecyl-4-tert-butyl-n-tridecyl ester; 2-n-tetradecanamide-4-tert-butyl-n-tetradecanoic acid phenyl ester; 2-n-pentadecanamide-4-tert-butyl-n-pentadecanoic acid phenyl ester; 2-n-hexadecanamide-4-tert-butyl-n-hexadecanoic acid phenyl ester; 2-n-heptadecanamide-4-tert-butyl-n-heptadecanoic acid phenyl ester; 2-n-octadecanamide-4-tert-butyl-n-octadecyl ester; 2-n-nonadecamide-4-tert-butyl-n-nonadecanoic acid phenyl ester; 2-n-eicosanamide-4-tert-butyl-n-eicosanoic acid phenyl ester;

2-acetamide-4-methyl-6-methyl-phenyl acetate; 2-propionamide-4-methyl-6-methyl-propionic acid phenyl ester; 2-n-butylamide-4-methyl-6-methyl-phenyl n-butyrate; 2-isobutyramide-4-methyl-6-methyl-phenyl isobutyrate; 2-n-valeramide-4-methyl-6-methyl-phenyl n-valerate; 2-isovaleramide-4-methyl-6-methyl-phenyl isovalerate; 2-n-hexanamide-4-methyl-6-methyl-phenyl hexanoate; 2-cyclohexanecarboxamide-4-methyl-6-methyl-cyclohexanecarboxylic acid phenyl ester; 2-n-heptanoamide-4-methyl-6-methyl-n-heptanoic acid phenyl ester; 2-n-octanoyl amide-4-methyl-6-methyl-n-octanoic acid phenyl ester; 2-n-nonanamide-4-methyl-6-methyl-n-nonanoic acid phenyl ester; 2-n-decanamide-4-methyl-6-methyl-phenyl n-decanoate;

2-acetamide-4-chloro-phenyl acetate; 2-propionamide-4-chloro-propionic acid phenyl ester; 2-n-butylamide-4-chloro-n-butyric acid phenyl ester; 2-isobutyramide-4-chloro-phenyl isobutyrate; 2-n-valeramide-4-chloro-n-pentanoic acid phenyl ester; 2-isovaleramide-4-chloro-isovaleric acid phenyl ester; 2-n-hexanamide-4-chloro-n-hexanoic acid phenyl ester; 2-cyclohexanecarboxamide-4-chloro-cyclohexanecarboxylic acid phenyl ester; 1-n-butylamide-2-naphthyl n-butyrate;

2-benzamide-phenyl benzoate; 2-p-chlorobenzamide-p-chlorobenzoic acid phenyl ester; 2-m-bromobenzamide-m-phenyl bromobenzoate; 2-o-chlorobenzamide-phenyl o-chlorobenzoate; 2-p-methoxybenzamide-p-methoxybenzoic acid phenyl ester; 2-p-methylbenzamide-p-methylbenzoate; 2-phenoxyformamide-phenylphenoxyformate; phenyl 2- (1-naphthamide) - (1-naphthoate); 2-pentafluorobenzamide-phenyl pentafluorobenzoate; 2-p-trifluoromethylbenzamide-p-trifluoromethylphenyl benzoate; 1-benzamide-2-naphthyl benzoate;

2- [ N-benzamide-N-tert-butyl ] -benzoic acid phenyl ester; 2- [ N-benzamide-N-tert-butyl ] -4-tert-butyl-benzoic acid phenyl ester; 2- [ N-benzamide-N-tert-butyl ] -4-methyl-benzoic acid phenyl ester; 2- [ N-benzamide-N-tert-butyl ] -4-ethyl-benzoic acid phenyl ester; 2- [ N-benzamide-N-tert-butyl ] -4-methyl-6-methyl-benzoic acid phenyl ester; 2- [ N-benzamide-N-tert-butyl ] -4-tert-butyl-phenyl isovalerate; 2- [ N-benzamide-N-phenyl ] -4-tert-butyl-benzoic acid phenyl ester; 2- [ N-benzamide-N-phenyl ] -4-methyl-benzoic acid phenyl ester; 2- [ N-benzamide-N-phenyl ] -4-ethyl-benzoic acid phenyl ester; 2- [ N-benzamide-N-phenyl ] -4-methyl-6-methyl-benzoic acid phenyl ester; 2- [ N-benzamide-N-phenyl ] -4-tert-butyl-phenyl N-butyrate; 2- [ N-benzamide-N-methyl ] -4-tert-butyl-phenyl N-butyrate;

2-benzamide-4-methyl-benzoic acid phenyl ester; 2-p-chlorobenzamide-4-methyl-p-chlorobenzoic acid phenyl ester; 2-m-bromobenzamide-4-methyl-m-bromobenzoic acid phenyl ester; 2-o-chlorobenzamide-4-methyl-phenyl-o-chlorobenzoate; 2-p-methoxybenzamide-4-methyl-p-methoxybenzoic acid phenyl ester; 2-p-methylbenzamide-4-methyl-p-methylbenzoic acid phenyl ester; 2-phenoxyformamide-4-methyl-phenylphenoxyformate; 2- (1-naphthamide) -4-methyl- (1-naphthoic acid) phenyl ester; 2-pentafluorobenzamide-4-methyl-phenyl pentafluorobenzoate; 2-p-trifluoromethylbenzamide-4-methyl-p-trifluoromethylphenyl benzoate;

2-benzamide-4-ethyl-benzoic acid phenyl ester; 2-p-chlorobenzamide-4-ethyl-p-chlorobenzoic acid phenyl ester; 2-m-bromobenzamide-4-ethyl-m-bromobenzoate phenyl ester; 2-o-chlorobenzamide-4-ethyl-o-chlorobenzoic acid phenyl ester; 2-p-methoxybenzamide-4-ethyl-p-methoxybenzoic acid phenyl ester; 2-p-methylbenzamide-4-ethyl-p-methylbenzoate; 2-phenoxyformamide-4-ethyl-phenoxybenzoic acid phenyl ester; 2- (1-naphthamide) -4-ethyl- (1-naphthoic acid) phenyl ester; 2-pentafluorobenzamide-4-ethyl-pentafluorobenzoic acid phenyl ester; 2-p-trifluoromethylbenzamide-4-ethyl-p-trifluoromethylphenyl benzoate;

2-benzamide-4-tert-butyl-benzoic acid phenyl ester; 2-p-chlorobenzamide-4-tert-butyl-p-chlorobenzoic acid phenyl ester; 2-m-bromobenzamide-4-tert-butyl-m-bromobenzoate phenyl ester; 2-o-chlorobenzamide-4-tert-butyl-phenyl o-chlorobenzoate; 2-p-methoxybenzamide-4-tert-butyl-p-methoxybenzoic acid phenyl ester; 2-p-methylbenzamide-4-tert-butyl-p-methylbenzoate; 2-phenoxyformamide-4-tert-butyl-phenylphenoxyformate; 2- (1-naphthamide) -4-tert-butyl- (1-naphthoic acid) phenyl ester; 2-pentafluorobenzamide-4-tert-butyl-phenyl pentafluorobenzoate; 2-p-trifluoromethylbenzamide-4-tert-butyl-p-trifluoromethylphenyl benzoate;

2-benzamide-4-methyl-6-methyl-benzoic acid phenyl ester; 2-p-chlorobenzamide-4-methyl-6-methyl-p-chlorobenzoic acid phenyl ester; 2-m-bromobenzamide-4-methyl-6-methyl-m-bromobenzoic acid phenyl ester; 2-o-chlorobenzamide-4-methyl-6-methyl-o-chlorobenzoic acid phenyl ester; 2-p-methoxybenzamide-4-methyl-6-methyl-p-methoxybenzoic acid phenyl ester; 2-p-methylbenzamide-4-methyl-6-methyl-p-methylbenzoic acid phenyl ester; 2-phenoxyformamide-4-methyl-6-methyl-phenylphenoxyformate; 2- (1-naphthamide) -4-methyl-6-methyl- (1-naphthoic acid) phenyl ester; 2-pentafluorobenzamide-4-methyl-6-methyl-phenyl pentafluorobenzoate; 2-p-trifluoromethylbenzamide-4-methyl-6-methyl-p-trifluoromethylphenyl benzoate;

2-benzamide-4-chloro-benzoic acid phenyl ester; 2-p-chlorobenzamide-4-chloro-p-chlorobenzoic acid phenyl ester; 2-m-bromobenzamide-4-chloro-m-bromobenzoic acid phenyl ester; 2-o-chlorobenzamide-4-chloro-o-chlorobenzoic acid phenyl ester; 2-p-methoxybenzamide-4-chloro-p-methoxybenzoic acid phenyl ester; 2-p-methylbenzamide-4-chloro-p-methylbenzoate; 2-phenoxyformamide-4-chloro-phenyloxy formate; 2- (1-naphthamide) -4-chloro- (1-naphthoic acid) phenyl ester; 2-pentafluorobenzamide-4-chloro-pentafluorobenzoic acid phenyl ester; 2-p-trifluoromethylbenzamide-4-chloro-p-trifluoromethylphenyl benzoate.

2-phenoxyformamide-phenylphenoxyformate; 2-phenoxyformamide-4-methyl-phenylphenoxyformate; 2-phenoxyformamide-4-ethyl-phenoxybenzoic acid phenyl ester; 2-phenoxyformamide-4-tert-butyl-phenylphenoxyformate; 2-phenoxyformamide-4-methyl-6-methyl-phenylphenoxyformate; 2-p-methoxyphenoxyformamide-p-methoxyphenoxybenzoic acid phenyl ester; 2-m-chlorophenoxyformamide-m-chlorophenoxybenzoic acid phenyl ester; 2-p-chlorophenoxyformamide-p-chlorophenoxybenzoic acid phenyl ester; 2-o-chlorophenoxyformamide-o-chlorophenoxybenzoic acid phenyl ester; 2-n-butyloxycarboxamide-phenyl butoxide; 2-n-butyloxycarboxamide-4-methyl-benzoic acid phenyl ester; 2-n-butyloxycarboxamide-4-ethyl-benzoic acid phenyl ester; 2-n-butyloxycarboxamide-4-tert-butyl-benzoic acid phenyl ester; 2-n-butyloxycarboxamide-4-methyl-6 methyl-phenyl butoxide; 2-n-butyloxycarboxamide 4-chloro-benzoic acid phenyl ester; 2-isobutyloxycarboxamide-isobutyloxycarboxylic acid phenyl ester; 2-isopentyloxyformamide-phenyl isovalerate; 2-n-octyloxycarboxamide-phenylcaprylate; 2-ethoxyformamide-ethoxybenzoic acid phenyl ester; 2-ethoxyformamide-4-methyl-ethoxybenzoic acid phenyl ester; 2-ethoxyformamide-4-ethyl-ethoxybenzoic acid phenyl ester; 2-ethoxyformamide-4-tert-butyl-ethoxybenzoic acid phenyl ester; 2-ethoxyformamide-4-methyl-6-methyl-ethoxybenzoic acid phenyl ester; 2-ethoxyformamide 4-chloro-ethoxybenzoic acid phenyl ester;

among the compounds of the general formula (II), preferred are compounds of the following general formula (III):

wherein the radical R¹-R⁵Has the same meaning as in the general formula (I), R^5’Has the same meaning as in the general formula (II), R⁶And R^6’Identical or different, selected from H; c₁-C₂₀May contain one or more heteroatoms selected from N, O, S, P, Si and halogen as substituents of carbon atoms or hydrogen atoms or both, preferably C₁-C₂₀Linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, alkyl which is halogenated or substituted with the N, O, S, P, Si heteroatom, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or is selected from heterocyclic aryl substituents.

Specific examples of the compounds included in the general formula (III) are:

2- [ N-benzoyl-N-benzyl ] -benzoic acid phenyl ester; 2- [ N-p-chlorobenzoyl-N-benzyl ] -p-chlorobenzoic acid phenyl ester; 2- [ N-m-bromobenzoyl-N-benzyl ] -m-bromobenzoate phenyl ester; 2- [ N-o-chlorobenzoyl-N-benzyl ] -o-chlorobenzoic acid phenyl ester; 2- [ N-p-methoxybenzoyl-N-benzyl ] -p-methoxybenzoic acid phenyl ester; 2- [ N-p-methylbenzoyl-N-benzyl ] -p-methylbenzoic acid phenyl ester; 2- [ N-benzoyl-N-benzyl ] -phenyloxy-formate; 2- (1-naphthoyl-N-benzyl) - (1-naphthoic acid) phenyl ester; 2- [ N-pentafluorobenzoyl-N-benzyl ] -phenyl pentafluorobenzoate; 2- [ N-p-trifluoromethylbenzoyl-N-benzyl ] -p-trifluoromethylphenyl benzoate; 1- [ N-benzoyl-N-benzyl ] -2-naphthyl benzoate;

2- [ N-benzoyl-N-benzyl ] -4-tert-butyl-benzoic acid phenyl ester; 2- [ N-p-chlorobenzoyl-N-benzyl ] -4-tert-butyl-p-chlorobenzoic acid phenyl ester; 2- [ N-m-bromobenzoyl-N-benzyl ] -4-tert-butyl-m-bromobenzoate phenyl ester; 2- [ N-o-chlorobenzoyl-N-benzyl ] -4-tert-butyl-o-chlorobenzoic acid phenyl ester; 2- [ N-p-methoxybenzoyl-N-benzyl ] -4-tert-butyl-p-methoxybenzoic acid phenyl ester; 2- [ N-p-methylbenzoyl-N-benzyl ] -4-tert-butyl-p-methylbenzoic acid phenyl ester; 2- [ N-benzoyl-N-benzyl ] -4-tert-butyl-phenyloxy-formate; 2- (1-naphthoyl-N-benzyl) -4-tert-butyl- (1-naphthoic acid) phenyl ester; 2- [ N-pentafluorobenzoyl-N-benzyl ] -4-tert-butyl-phenyl pentafluorobenzoate; 2- [ N-p-trifluoromethylbenzoyl-N-benzyl ] -4-tert-butyl-p-trifluoromethylbenzoic acid phenyl ester;

2- [ N-benzoyl-N-isopropyl ] -4-tert-butyl-benzoic acid phenyl ester; 2- [ N-p-chlorobenzoyl-N-isopropyl ] -4-tert-butyl-p-chlorobenzoic acid phenyl ester; 2- [ N-m-bromobenzoyl-N-isopropyl ] -4-tert-butyl-m-bromobenzoate phenyl ester; 2- [ N-o-chlorobenzoyl-N-isopropyl ] -4-tert-butyl-o-chlorobenzoic acid phenyl ester; 2- [ N-p-methoxybenzoyl-N-isopropyl ] -4-tert-butyl-p-methoxybenzoic acid phenyl ester; 2- [ N-p-methylbenzoyl-N-isopropyl ] -4-tert-butyl-p-methylbenzoic acid phenyl ester; 2- [ N-benzoyl-N-isopropyl ] -4-tert-butyl-phenyloxy-formate; 2- (1-naphthoyl-N-isopropyl) -4-tert-butyl- (1-naphthoic acid) phenyl ester; 2- [ N-pentafluorobenzoyl-N-isopropyl ] -4-tert-butyl-phenyl pentafluorobenzoate; 2- [ N-p-trifluoromethylbenzoyl-N-isopropyl ] -4-tert-butyl-p-trifluoromethylbenzoic acid phenyl ester;

2- [ N-benzoyl-N-benzyl ] -4-methyl-benzoic acid phenyl ester; 2- [ N-p-chlorobenzoyl-N-benzyl ] -4-methyl-6-methyl-p-chlorobenzoic acid phenyl ester; 2- [ N-m-bromobenzoyl-N-benzyl ] -4-methyl-6-methyl-m-bromobenzoate phenyl ester; 2- [ N-o-chlorobenzoyl-N-benzyl ] -4-methyl-o-chlorobenzoic acid phenyl ester; 2- [ N-p-methoxybenzoyl-N-benzyl ] -4-methyl-6-methyl-p-methoxybenzoic acid phenyl ester; 2- [ N-p-methylbenzoyl-N-benzyl ] -4-methyl-6-methyl-p-methylbenzoic acid phenyl ester; 2- [ N-benzoyl-N-benzyl ] -4-methyl-phenyloxy-formate; 2- (1-naphthoyl-N-benzyl) -4-methyl- (1-naphthoic acid) phenyl ester; 2- [ N-pentafluorobenzoyl-N-benzyl ] -4-methyl-pentafluorobenzoic acid phenyl ester; 2- [ N-p-trifluoromethylbenzoyl-N-benzyl ] -4-methyl-p-trifluoromethylbenzoic acid phenyl ester;

2- [ N-benzoyl-N-phenylethyl ] -4-tert-butyl-benzoic acid phenyl ester; 2- [ N-p-chlorobenzoyl-N-pentyl ] -4-tert-butyl-p-chlorobenzoic acid phenyl ester; 2- [ N-p-chlorobenzoyl-N-isopropyl ] -4-tert-butyl-p-chlorobenzoic acid phenyl ester; 2- [ N-m-bromobenzoyl-N-isobutyl ] -4-tert-butyl-m-bromobenzoate phenyl ester; 2- [ N-o-chlorobenzoyl-N-cyclohexylmethyl ] -4-tert-butyl-o-chlorobenzoic acid phenyl ester; 2- [ N-p-methoxybenzoyl-N-p-chlorobenzyl ] -4-tert-butyl-p-methoxybenzoic acid phenyl ester; 2- [ N-p-methylbenzoyl-N-p-methoxybenzyl ] -4-tert-butyl-p-methylbenzoic acid phenyl ester; 2- [ N-benzoyl-N-benzhydryl ] -4-tert-butyl-phenyloxy-formate; 2- (1-naphthoyl-N-decyl) -4-tert-butyl- (1-naphthoic acid) phenyl ester; 2- [ N-pentafluorobenzoyl-N-hexyl ] -4-tert-butyl-phenyl pentafluorobenzoate; 2- [ N-p-trifluoromethylbenzoyl-N-heptyl ] -4-tert-butyl-p-trifluoromethylbenzoic acid phenyl ester;

2- [ N-benzoyl-N-phenylethyl ] -4-methyl-6-methyl-benzoic acid phenyl ester; 2- [ N-p-chlorobenzoyl-N-pentyl ] -4-methyl-6-methyl-p-chlorobenzoic acid phenyl ester; 2- [ N-p-chlorobenzoyl-N-propyl ] -4-methyl-6-methyl-p-chlorobenzoic acid phenyl ester; 2- [ N-m-bromobenzoyl-N-isobutyl ] -4-methyl-6-methyl-m-bromobenzoate phenyl ester;

2- [ N-benzoyl-N-benzhydryl ] -4-methyl-6-methyl-benzoic acid phenyl ester; 2- [ N-p-chlorobenzoyl-N-benzhydryl ] -4-methyl-6-methyl-p-chlorobenzoic acid phenyl ester; 2- [ N-p-chlorobenzoyl-N-benzhydryl ] -4-methyl-6-methyl-p-chlorobenzoic acid phenyl ester; 2- [ N-m-bromobenzoyl-N-benzhydryl ] -4-methyl-6-methyl-m-bromobenzoate phenyl ester;

2- [ N-acetyl-N-benzyl ] -phenyl acetate; 2- [ N-propionyl-N-benzyl ] -propionic acid phenyl ester; 2- [ N-butyryl-N-benzyl ] -N-butyric acid phenyl ester; 2- [ N-isobutyryl-N-benzyl ] -phenyl isobutyrate; 2- [ N-pentanoyl-N-benzyl ] -N-pentanoic acid phenyl ester; 2- [ N-isovaleryl-N-benzyl ] -isovaleric acid phenyl ester; 2- [ N-hexanoyl-N-benzyl ] -N-hexanoic acid phenyl ester; 2- [ N-cyclohexanecarboxyl-N-benzyl ] -cyclohexanecarboxylic acid phenyl ester; 2- [ N-heptanoyl-N-benzyl ] -N-heptanoic acid phenyl ester; 2- [ N-octanoyl-N-benzyl ] -N-octanoic acid phenyl ester; 2- [ N-nonanoyl-N-benzyl ] -N-nonanoic acid phenyl ester; 2- [ N-decanoyl-N-benzyl ] -N-decanoic acid phenyl ester; 2- [ N-undecanoyl-N-benzyl ] -N-undecanoic acid phenyl ester; 2- [ N-dodecanoyl-N-benzyl ] -N-dodecanoic acid phenyl ester; 2- [ N-tridecyl-N-benzyl ] -N-tridecanoic acid phenyl ester; 2- [ N-tetradecanoyl-N-benzyl ] -N-tetradecanoic acid phenyl ester; 2- [ N-pentadecyl-N-benzyl ] -N-pentadecyl phenyl ester; 2- [ N-hexadecanoyl-N-benzyl ] -N-hexadecanoic acid phenyl ester; 2- [ N-heptadecanoyl-N-benzyl ] -N-heptadecanoic acid phenyl ester; 2- [ N-octadecanoyl-N-benzyl ] -N-octadecanoic acid phenyl ester; 2- [ N-nonadecanoyl-N-benzyl ] -N-nonadecanoic acid phenyl ester; 2- [ N-eicosyl-N-benzyl ] -N-eicosanoic acid phenyl ester;

2- [ N-acetyl-N-benzyl ] -4-tert-butyl-phenyl acetate; 2- [ N-propionyl-N-benzyl ] -4-methyl-propionic acid phenyl ester; 2- [ N-butyryl-N-benzyl ] -4-methyl-phenyl N-butyrate; 2- [ N-isobutyryl-N-benzyl ] -4-tert-butyl-phenyl isobutyrate; 2- [ N-pentanoyl-N-benzyl ] -4-methyl-N-pentanoic acid phenyl ester; 2- [ N-isovaleryl-N-benzyl ] -4-methyl-phenyl isovalerate; 2- [ N-hexanoyl-N-benzyl ] -4-methyl-6-methyl-phenyl hexanoate; 2- [ N-cyclohexanecarboxyl-N-benzyl ] -4-tert-butyl-cyclohexanecarboxylic acid phenyl ester; 2- [ N-heptanoyl-N-benzyl ] -4-tert-butyl-N-heptanoic acid phenyl ester; 2- [ N-octanoyl-N-benzyl ] -4-methyl-phenyl N-octanoate; 2- [ N-nonanoyl-N-benzyl ] -4-methyl-N-nonanoic acid phenyl ester; 2- [ N-decanoyl-N-benzyl ] -4-tert-butyl-phenyl N-decanoate; 2- [ N-undecanoyl-N-benzyl ] -4-tert-butyl-N-undecanoic acid phenyl ester; 2- [ N-dodecanoyl-N-benzyl ] -4-tert-butyl-N-dodecanoic acid phenyl ester; 2- [ N-tridecyl-N-benzyl ] -4-tert-butyl-N-tridecyl acid phenyl ester; 2- [ N-tetradecanoyl-N-benzyl ] -4-tert-butyl-N-tetradecanoic acid phenyl ester;

2- [ N-acetyl-N-phenethyl ] -4-tert-butyl-phenyl acetate; 2- [ N-propionyl-N-phenylethyl ] -4-methyl-propionic acid phenyl ester; 2- [ N-butyryl-N-pentyl ] -4-methyl-phenyl N-butyrate; 2- [ N-isobutyryl-N-isobutyl ] -4-tert-butyl-phenyl isobutyrate; 2- [ N-pentanoyl-N-hexyl ] -4-methyl-N-pentanoic acid phenyl ester; 2- [ N-isovaleryl-N-cyclohexylmethyl ] -4-methyl-phenyl isovalerate; 2- [ N-hexanoyl-N-decyl ] -4-methyl-6-methyl-phenyl hexanoate; 2- [ N-cyclohexanoyl-N-p-methoxybenzyl ] -4-tert-butyl-cyclohexanecarboxylic acid phenyl ester; 2- [ N-heptanoyl-N-o-chlorobenzyl ] -4-tert-butyl-N-heptanoic acid phenyl ester; 2- [ N-octanoyl-N-p-methylbenzyl ] -4-methyl-phenyl N-octanoate; 2- [ N-nonanoyl-N-propyl ] -4-methyl-N-nonanoic acid phenyl ester; 2- [ N-decanoyl-N-isopentyl ] -4-tert-butyl-phenyl N-decanoate; 2- [ N-undecanoyl-N-isopentyl ] -4-tert-butyl-N-undecanoic acid phenyl ester; 2- [ N-lauroyl-N-cyclopentylmethyl ] -4-tert-butyl-N-dodecanoic acid phenyl ester; 2- [ N-tridecyl-N-p-trifluoromethylbenzyl ] -4-tert-butyl-N-tridecanoic acid phenyl ester; 2- [ N-tetradecanoyl-N-chlorobenzyl ] -4-tert-butyl-N-tetradecanoic acid phenyl ester;

2- [ N-benzoyl-N-benzyl ] -phenyloxy-formate; 2- [ N-p-methylphenoxybenzoyl-N-benzyl ] -p-methylphenoxybenzoic acid phenyl ester; 2- [ N-p-methoxyphenoxyformyl-N-benzyl ] -p-methoxyphenoxybenzoic acid phenyl ester; 2- [ N-benzoyl-N-benzyl ] -4-tert-butyl-phenyloxy-formate; 2- [ N-benzoyl-N-benzyl ] -4-methyl-phenyloxy-formate; 2- [ N-benzoyl-N-benzyl ] -4-ethyl-phenyloxy-formate; 2- [ N-benzoyl-N-benzyl ] -4-methyl-6-methyl-phenyloxy-formate; 2- [ N-N-butyloxycarbonyl-N-benzhydryl ] -phenyl N-butoxide; 2- [ N-isopentyloxyformyl-N-benzhydryl ] -phenyl isopentyloxyformate; 2- [ N-butyloxycarbonyl-N-benzhydryl ] -4-methyl-6-methyl-phenyl N-butoxide; phenyl 2- [ N-butyloxycarbonyl-N-benzhydryl ] -4-methyl-N-butoxide; phenyl 2- [ N-butyloxycarbonyl-N-benzhydryl ] -4-tert-butyl-N-butoxide; 2-ethoxyformamide-ethoxybenzoic acid phenyl ester; 2-ethoxyformamide-4-methyl-ethoxybenzoic acid phenyl ester; 2-ethoxyformamide-4-ethyl-ethoxybenzoic acid phenyl ester; 2-ethoxyformamide-4-tert-butyl-ethoxybenzoic acid phenyl ester; 2-ethoxyformamide-4-methyl-phenyl ethoxyformate; 2-ethoxyformamide 4-chloro-ethoxybenzoic acid phenyl ester;

among the compounds represented by the general formula (I), another preferred compound is a compound represented by the following general formula (IV):

wherein the radical R¹-R⁵Has the same meaning as in the general formula (I); r⁶And R^6’The same as in the general formula (III).

Specific examples of the compounds included in the general formula (IV) are:

2-benzimide-benzoate; 2-phenylethylimine-phenyl benzoate; 2-n-propyleneimine-phenyl benzoate; 2-n-pentylimine-phenyl benzoate; 2-isoamylimine-phenyl benzoate; 2-n-butylimine-phenyl benzoate; 2-n-heptylimine-phenyl benzoate; 2- (2-furylmethyl) imine-benzoic acid phenyl ester; 2-n-hexylimine-phenyl benzoate; 2-n-decylimide-phenyl benzoate; 2-cyclohexylmethylimine-phenyl benzoate; 2-cyclopentylmethyl imine-phenyl benzoate; 2-p-chlorobenzeneimine-phenyl benzoate; 2-m-chlorobenzeneimine-benzoic acid phenyl ester; 2-o-chlorobenzeneimine-benzoic acid phenyl ester; 2-p-methoxybenzeneimine-benzoic acid phenyl ester; 2-p-methylbenzylidene-benzoic acid phenyl ester; 1-benzimide-2-naphthyl benzoate;

2-benzimide-4-methyl-benzoic acid phenyl ester; 2-phenethylimine-4-methyl-benzoic acid phenyl ester; 2-n-pentamine-4-methyl-benzoic acid phenyl ester; 2-isopentylimine-4-methyl-benzoic acid phenyl ester; 2-n-butylimine-4-methyl-benzoic acid phenyl ester; 2-n-heptimine-4-methyl-benzoic acid phenyl ester; 2- (2-furylmethyl) imine-4-methyl-benzoic acid phenyl ester; 2-hexylimine-4-methyl-benzoic acid phenyl ester; 2-n-decylimide-4-methyl-benzoic acid phenyl ester; 2-cyclohexylmethylimine-4-methyl-benzoic acid phenyl ester; 2-cyclopentylmethyl imine-4-methyl-benzoic acid phenyl ester; 2-p-chlorobenzeneimine-4-methyl-benzoic acid phenyl ester; 2-m-chlorobenzeneimine-4-methyl-benzoic acid phenyl ester; 2-o-chlorobenzeneimine-4-methyl-benzoic acid phenyl ester; 2-p-methoxybenzeneimine-4-methyl-benzoic acid phenyl ester; 2-p-methylbenzylidene imine-4-methyl-benzoic acid phenyl ester;

2-dibenzylimine-phenyl benzoate; 2-dibenzylimine-4-methyl-benzoic acid phenyl ester; 2-dibenzylimine-4-methyl-6-methyl-benzoic acid phenyl ester; 2-dibenzylimine-4-tert-butyl-benzoic acid phenyl ester; 2-diphenylmethanimine-phenyl isobutyrate; 2-diphenylmethanimine-4-methyl-6-methyl-phenyl isobutyrate; 2-dibenzylimine-4-methyl-m-chlorobenzoic acid phenyl ester; 2-diphenylimid-4-methyl-6-methyl-phenyloxy-formate;

2-benzimide-4-tert-butyl-benzoic acid phenyl ester; 2-phenethylimine-4-tert-butyl-benzoic acid phenyl ester; 2-n-pentamine-4-tert-butyl-benzoic acid phenyl ester; 2-isopentylimine-4-tert-butyl-phenyl benzoate; 2-n-butylimine-4-tert-butyl-benzoic acid phenyl ester; 2-n-heptylimine-4-tert-butyl-benzoic acid phenyl ester; 2- (2-furylmethyl) imine-4-tert-butyl-benzoic acid phenyl ester; 2-n-hexylimine-4-tert-butyl-benzoic acid phenyl ester; 2-n-decylimide-4-tert-butyl-benzoic acid phenyl ester; 2-cyclohexylmethylimine-4-tert-butyl-benzoic acid phenyl ester; 2-cyclopentylmethyl imine-4-tert-butyl-benzoic acid phenyl ester; 2-p-chlorobenzeneimine-4-tert-butyl-benzoic acid phenyl ester; 2-m-chlorobenzeneimine-4-tert-butyl-benzoic acid phenyl ester; 2-o-chlorobenzeneimine-4-tert-butyl-benzoic acid phenyl ester; 2-p-methoxybenzeneimine-4-tert-butyl-benzoic acid phenyl ester; 2-p-methylbenzylidene imine-4-tert-butyl-benzoic acid phenyl ester; 2-p-methylbenzylidene imine-4-methyl-6-methyl-benzoic acid phenyl ester;

2-benzimide-phenyl isobutyrate; 2-phenylethylimine-phenylcyclohexanecarboxylic acid; 2-n-pentamine-phenyl n-dodecanoate; 2-isoamylimine-phenyl o-chlorobenzoate; 2-n-butylimine-phenyloxy formate; 2-n-heptylimine-phenyl pentafluorobenzoate; 2-n-hexylimine-p-trifluoromethylbenzoic acid phenyl ester; 2-n-decylimide-p-methoxybenzoic acid phenyl ester; 2-cyclohexylmethylimine-phenylcyclohexanecarboxylic acid ester; 2-cyclopentylmethyl imine-n-heptanoic acid phenyl ester; 2-m-chlorobenzeneimine-n-hexadecanoic acid phenyl ester; 2-p-methoxybenzylidene-o-chlorobenzoic acid phenyl ester; 2-p-methylbenzylidene-n-pentanoic acid phenyl ester; 1-benzimide-2-p-methoxybenzoic acid naphthyl ester;

2-benzimide-4-tert-butyl-phenyl isobutyrate; 2-phenethylimine-4-tert-butyl-phenylcyclohexanecarboxylic acid; 2-n-pentamine-4-tert-butyl-n-dodecanoic acid phenyl ester; 2-isoamylimine-4-tert-butyl-phenyl o-chlorobenzoate; 2-n-butylimine-4-tert-butyl-phenyloxy formate; 2-n-heptylimine-4-tert-butyl-phenyl pentafluorobenzoate; 2-n-hexylimine-4-tert-butyl-p-trifluoromethylbenzoic acid phenyl ester; 2-n-decylimide-4-tert-butyl-p-methoxybenzoic acid phenyl ester; 2-cyclohexylmethylimine-4-tert-butyl-phenylcyclohexanecarboxylic acid ester; 2-cyclopentylmethyl imine-4-tert-butyl-n-heptanoic acid phenyl ester; 2-m-chlorobenzeneimine-4-tert-butyl-n-hexadecanoic acid phenyl ester; 2-p-methoxybenzylidene imine-4-tert-butyl-phenyl o-chlorobenzoate; 2-p-methylbenzylidene imine-4-tert-butyl-n-pentanoic acid phenyl ester;

2-benzimide-4-methyl-6-methyl-phenyl isobutyrate; 2-phenethylimine-4-methyl-phenylcyclohexanecarboxylic acid; 2-n-pentamine-4-ethyl-n-dodecanoic acid phenyl ester; 2-isoamylimine-4-methyl-phenyl o-chlorobenzoate; 2-n-butylimine-4-methyl-6-methyl-phenyloxy-benzoate; 2-n-heptylimine-4-methyl-phenyl pentafluorobenzoate; 2-n-hexylimine-4-methyl-p-trifluoromethylbenzoic acid phenyl ester.

2-n-hexylimine-phenyloxy formate; 2-n-hexylimine-4-methyl-phenyloxy-formate; 2-n-hexylimine-4-ethyl-phenyloxy formate; 2-n-hexylimine-4-tert-butyl-phenyloxy formate; 2-n-hexylimine-4-methyl-6-methyl-phenyloxy-formate; 2-n-hexylimine-4-chloro-phenyloxy formate; 2-isopentylimine-p-methylphenoxy benzoate; 2-n-butylimine-m-chlorophenoxybenzoic acid phenyl ester; 2-n-octylimine-p-methoxyphenoxybenzoic acid phenyl ester; 2-n-butylimine-n-octyloxy benzoic acid phenyl ester; 2-n-butylimine-4-methyl-n-octyloxy benzoic acid phenyl ester; 2-n-butylimine-4-tert-butyl-n-octyloxy benzoic acid phenyl ester; 2-n-butylimine-4-chloro-n-octyloxy benzoic acid phenyl ester; 2-n-butylimine-4-methyl-6-methyl-n-octyloxy benzoic acid phenyl ester; 2-n-butylimine-phenyl n-butoxide; 2-n-hexylimine-phenyl isopentyloxyformate; 2-n-butylimine-ethoxybenzoic acid phenyl ester; 2-n-butylimine-4-methyl-ethoxybenzoic acid phenyl ester; 2-n-butylimine-4-tert-butyl-ethoxybenzoic acid phenyl ester; 2-n-butylimine-4-chloro-ethoxybenzoic acid phenyl ester; 2-n-butylimine-4-methyl-6-methyl-ethoxybenzoic acid phenyl ester; 2-n-butylimine-ethoxybenzoic acid phenyl ester; 2-n-hexylimine-ethoxybenzoic acid phenyl ester; 2-isopropylamine-phenyl ethoxyformate.

The 2-substituted amino-phenyl esters of the present invention may be synthesized by a variety of reactions, such as, for illustrative purposes and not by way of limitation, reacting a substituted or unsubstituted ortho-aminophenol with an acid chloride or chloroformate to yield R^IIA compound of formula (II) when H:

when R is^IIThe compound of formula (II) other than H can be obtained by protecting the phenolic hydroxyl group of a substituted or unsubstituted ortho-aminophenol with a silane and then reacting with R^IIThe bromide or iodide is reacted, then hydroxyl group is removed for protection reaction, and finally the product is reacted with acyl chloride or chloroformate. The process is particularly suitable for the preparation of^IIA compound of the general formula (II) which is an aryl, substituted aryl, heterocycle, t-butyl, etc. group:

when R of the compound of formula (II)⁵And R^5’The following method can also be adopted for preparation of different products:

the compound of formula (III) as a preferred compound of formula (II) can be obtained by reacting a substituted or unsubstituted ortho-aminophenol with an aldehyde or ketone, followed by a reduction reaction and then with an acid chloride or chloroformate:

or reacting the substituted or unsubstituted ortho-aminophenol with an aldehyde or ketone and then with an acid chloride or chloroformate to obtain a compound of the general formula (IV):

the solid catalyst component of the invention comprises at least another electron donor compound B besides the 2-substituted amino-phenyl ester compound A with the general formula (I), wherein the electron donor compound B is selected from Lewis base containing one or more electronegative groups, and the electron donor atom is selected from N, O, S, P, As or Sn, preferably from the electron donor compounds of diethers, esters, diketones and diamines. When the 2-substituted amino-phenyl ester compound is used together with other internal electron donor compounds as disclosed above, a catalyst with adjustable properties can be obtained.

The Lewis base electron-donor compound B is preferably chosen from 1, 3-diethers of general formula (V):

wherein: r, R¹、R²、R³、R⁴And R⁵Which may be identical or different, represent H or a linear or branched alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl radical having from 1 to 18 carbon atoms; r⁶And R⁷And may be the same or different and represent a straight-chain or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms and an arylalkyl group; r to R⁷One or more of the groups may be linked to form a cyclic structure, and may each comprise one or more heteroatoms selected from halogen, N, O, S, P, and Si.

Specific examples of ethers that can be advantageously used include: 2- (2-ethylhexyl) 1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2-tert-butyl-1, 3-dimethoxypropane, 2-cumyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2 (1-naphthyl) -1, 3-dimethoxypropane, 2 (p-fluorophenyl) -1, 3-dimethoxypropane, 2 (1-decahydronaphthyl) -1, 3-dimethoxypropane, 2 (p-tert-butylphenyl) -1, 3-dimethoxypropane, 2, 2-dicyclohexyl-1, 3-dimethoxypropane, 2, 2-diethyl-1, 3-dimethoxypropane, 2, 2-dipropyl-1, 3-dimethoxypropane, 2, 2-dibutyl-1, 3-dimethoxypropane, 2, 2-diethyl-1, 3-diethoxypropane, 2, 2-dicyclopentyl-1, 3-dimethoxypropane, 2, 2-dipropyl-1, 3-diethoxypropane, 2, 2-dibutyl-1, 3-diethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-methyl-2-methylcyclohexyl-1, 3-dimethoxypropane, 2, 2-bis (p-chlorophenyl) -1, 3-dimethoxypropane, 2, 2-bis (2-phenylethyl) -1, 3-dimethoxypropane, 2, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2, 2-bis (p-methylphenyl) -1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2, 2-diisobutyl-1, 3-dimethoxypropane, 2, 2-diphenyl-1, 3-dimethoxypropane, 2, 2-dibenzyl-1, 3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1, 3-dimethoxypropane, 2, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2, 2-diisobutyl-1, 3-diethoxypropane, 2, 2-diisobutyl-1, 3-dibutoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2, 2-di-sec-butyl-1, 3-dimethoxypropane, 2, 2-di-tert-butyl-1, 3-dimethoxypropane, 2, 2-dineopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-phenyl-2-benzyl-1, 3-dimethoxy __ -ylpropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane. 1, 1-bis (methoxymethyl) -cyclopentadiene; 1, 1-bis (methoxymethyl) -2,3,4, 5-tetramethylcyclopentadiene; 1, 1-bis (methoxymethyl) -2,3,4, 5-tetraphenylcyclopentadiene; 1, 1-bis (methoxymethyl) -2,3,4, 5-tetrafluorocyclopentadiene; 1, 1-bis (methoxymethyl) -3, 4-dicyclopentylcyclopentadiene; 1, 1-bis (methoxymethyl) indene; 1, 1-bis (methoxymethyl) -2, 3-dimethylindene; 1, 1-bis (methoxymethyl) -4,5,6, 7-tetrahydroindene; 1, 1-bis (methoxymethyl) -2,3,6, 7-tetrafluoroindene; 1, 1-bis (methoxymethyl) -4, 7-dimethylindene; 1, 1-bis (methoxymethyl) -3, 6-dimethylindene; 1, 1-bis (methoxymethyl) -4-phenylindene; 1, 1-bis (methoxymethyl) -4-phenyl-2-methylindene; 1, 1-bis (methoxymethyl) -4-cyclohexylindene; 1, 1-bis (methoxymethyl) -7- (3,3, 3-trifluoropropyl) indene; 1, 1-bis (methoxymethyl) -7-trimethylsilylindole; 1, 1-bis (methoxymethyl) -7-trifluoromethylindene; 1, 1-bis (methoxymethyl) -4, 7-dimethyl-4, 5,6, 7-tetrahydroindene; 1, 1-bis (methoxymethyl) -7-methylindene; 1, 1-bis (methoxymethyl) -7-cyclopentylindole; 1, 1-bis (methoxymethyl) -7-isopropylindene; 1, 1-bis (methoxymethyl) -7-cyclohexylindene; 1, 1-bis (methoxymethyl) -7-tert-butylindene; 1, 1-bis (methoxymethyl) -7-tert-butyl-2-methylindene; 1, 1-bis (methoxymethyl) -7-phenylindene; 1, 1-bis (methoxymethyl) -2-phenylindene; 1, 1-bis (methoxymethyl) -1H-benzo [ e ] indene; 1, 1-bis (methoxymethyl) -1H-2-methylbenzo [ e ] indene; 9, 9-bis (methoxymethyl) fluorene; 9, 9-bis (methoxymethyl) -2,3,6, 7-tetramethylfluorene; 9, 9-bis (methoxymethyl) -2,3,4,5,6, 7-hexafluorofluorene; 9, 9-bis (methoxymethyl) -2, 3-benzofluorene; 9, 9-bis (methoxymethyl) -2,3,6, 7-dibenzofluorene; 9, 9-bis (methoxymethyl) -2, 7-diisopropylfluorene; 9, 9-bis (methoxymethyl) -1, 8-dichlorofluorene; 9, 9-bis (methoxymethyl) -2, 7-dicyclopentylfluorene; 9, 9-bis (methoxymethyl) -1, 8-difluorofluorene; 9, 9-bis (methoxymethyl) -1,2,3, 4-tetrahydrofluorene; 9, 9-bis (methoxymethyl) -1,2,3,4,5,6,7, 8-octahydrofluorene; 9, 9-bis (methoxymethyl) -4-tert-butylfluorene.

The Lewis alkali electron compound B is preferably monocarboxylic ester or polycarboxylic ester compounds, and specific examples are aromatic dicarboxylic acid compounds and aliphatic chain dicarboxylic ester compounds:

diesters of aromatic dicarboxylic acids, such as phthalic diesters or terephthalic diesters. The phthalic diesters include: dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl isopropyl phthalate, methyl n-propyl phthalate, ethyl n-butyl phthalate, ethyl isobutyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, 2-dimethylhexyl phthalate, 2-ethylhexyl phthalate, di-n-nonyl phthalate, diisodecyl phthalate, 2-dimethylheptyl phthalate, n-hexyl phthalate, n-butyl (2-ethylhexyl) phthalate, n-hexyl phthalate, n-nonyl isononyl phthalate, isopentyl n-decyl phthalate, n-undecyl phthalate, isopentyl isohexyl phthalate, n-hexyl phthalate (2-methylhexyl phthalate), n-hexyl (2-ethylhexyl) phthalate, n-hexyl (isononyl) phthalate, n-hexyl (n-decyl) phthalate, n-heptyl (2-ethylhexyl) phthalate, n-heptyl (isononyl) phthalate, n-heptyl (nonyl) phthalate, and 2-ethylhexyl (isononyl) phthalate. These esters may be used alone or in combination of two or more. The terephthalic acid diester includes: dimethyl terephthalate, diethyl terephthalate, di-n-propyl terephthalate, diisopropyl terephthalate, di-n-butyl terephthalate, diisobutyl terephthalate, ethyl methyl terephthalate, methyl isopropyl terephthalate, ethyl (n-propyl) terephthalate, ethyl (n-butyl) terephthalate, ethyl (isobutyl) terephthalate, di-n-pentyl terephthalate, diisopentyl terephthalate, dihexyl terephthalate, di-n-heptyl terephthalate, di-n-octyl terephthalate, diison-octyl terephthalate, di-2, 2-dimethylhexyl terephthalate, di-2-ethylhexyl terephthalate, di-n-nonyl terephthalate, diisononyl terephthalate, diisodecyl terephthalate, di-n-butyl terephthalate, di-isobutyl terephthalate, di-n-butyl terephthalate, di-hexyl terephthalate, di, Di (2, 2-dimethylethylheptyl) terephthalate, n-butyl isohexyl terephthalate, n-butyl (2-ethylhexyl) terephthalate, n-hexyl n-pentyl terephthalate, n-pentyl isohexyl terephthalate, isopentyl (heptyl) terephthalate, terephthalic acid, n-pentyl (2-ethylhexyl) terephthalate, n-pentyl (isononyl) terephthalate, isopentyl (n-decyl) terephthalate, n-pentyl (undecyl) terephthalate, isopentyl (isohexyl) terephthalate, n-hexyl (2-ethylhexyl) terephthalate, n-hexyl (isononyl) terephthalate, n-hexyl (n-decyl) terephthalate, n-heptyl (2-ethylhexyl) terephthalate, n-heptyl (isononyl) terephthalate, n-heptyl (neodecyl) terephthalate, n-hexyl (iso-hexyl) terephthalate, n-hexyl (iso-nonyl) terephthalate, n-hexyl (n-decyl) terephthalate, n-hexyl (iso-decyl) terephthalate, n-hexyl (neo, And 2-ethylhexyl (isononyl) terephthalate. These esters may be used alone or in combination of two or more.

Among these diesters, it is recommended to use one or a mixture of two or more of diethyl phthalate, dipropyl butyl phthalate, diisopropyl terephthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, di-n-butyl terephthalate, diisobutyl terephthalate, di-n-octyl terephthalate, diisooctyl terephthalate, di-2-ethylhexyl terephthalate, and diisodecyl phthalate.

Particularly preferably, among the polycarboxylic acid ester compounds, a succinic acid ester compound selected from the group consisting of those of the general formula (VI):

wherein the radical R¹And R²Equal to or different from each other, is a C1-C20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group, optionally comprising heteroatoms; r³-R⁶Wherein at least two radicals are different from hydrogen and are selected from C¹-C²⁰Linear or branched alkyl, alkenyl, cycloalkyl, arylAn aralkyl or alkaryl radical, optionally containing hetero atoms, and, in addition, a radical R³-R⁶May be joined together to form a ring. R¹And R²Preferred are C1-C8 alkyl, cycloalkyl, aryl, aralkyl and alkaryl groups. Particularly preferred are compounds wherein R is¹And R²Selected from primary alkyl groups, in particular branched primary alkyl groups. Suitable R¹And R²Examples of (B) are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Particularly preferred are ethyl, isobutyl and neopentyl.

One of the preferred classes of compounds described by the general formula (VI) is that wherein R is³-R⁵Is hydrogen and R⁶Are branched alkyl, cycloalkyl, aryl, aralkyl and alkaryl groups having from 3 to 10 carbon atoms. Particularly preferred are compounds wherein R is⁶Is a branched primary alkyl group or cycloalkyl group having 3 to 10 carbon atoms. Specific examples of suitable mono-substituted succinate compounds are diethyl sec-butylsuccinate, diethyl hexylsuccinate, diethyl cyclopropylsuccinate, diethyl norbornylsuccinate, diethyl perhydrosuccinate, diethyl trimethylsuccinate, diethyl methoxysuccinate, diethyl p-methoxyphenylsuccinate, diethyl p-chlorophenylsuccinate, diethyl phenylsuccinate, diethyl cyclohexylsuccinate, diethyl benzylsuccinate, diethyl cyclohexylmethylsuccinate, diethyl tert-butylsuccinate, diethyl isobutylsuccinate, diethyl isopropylsuccinate, diethyl neopentylsuccinate, diethyl isopentylsuccinate, diethyl (1-trifluoromethylethyl) succinate, diethyl fluorenylsuccinate, phenyl succinic acid (1-ethoxycarbonyldiisobutyl ester) (1- (ethoxycarbonyldiisobutylphenyl succinate), Diisobutyl sec-butylsuccinate, diisobutyl hexylsuccinate, diisobutyl cyclopropylsuccinate, diisobutyl norbornyl succinate, diisobutyl perhydrosuccinate, diisobutyl trimethylsilylsuccinate, diisobutyl methoxysuccinate, diisobutyl p-methoxyphenylsuccinate, diisobutyl p-chlorophenoxysuccinate, diisobutyl cyclohexylsuccinate, diisobutyl perfluoropropylsuccinate,Diisobutyl benzylsuccinate, diisobutyl cyclohexylmethylsuccinate, diisobutyl tert-butylsuccinate, diisobutyl isobutylsuccinate, diisobutyl isopropylsuccinate, diisobutyl neopentylsuccinate, diisobutyl isopentylsuccinate, diisobutyl (1-trifluoromethylethyl) succinate, diisobutyl fluorenylsuccinate, dipentyl sec-butylsuccinate, dipentyl hexylsuccinate, dipentyl cyclopropylsuccinate, dineopentyl norbornyl succinate, dineopentyl perhydrosuccinate, dineopentyl trimethylsilylsuccinate, dineopentyl methoxysuccinate, dineopentyl p-methoxyphenylsuccinate, dineopentyl p-chlorophenylsuccinate, dineopentyl phenylsuccinate, dineopentyl cyclohexylsuccinate, dineopentyl benzylsuccinate, dineopentyl cyclohexylmethylsuccinate, Di-neopentyl tert-butylsuccinate, di-neopentyl isobutylsuccinate, di-neopentyl isopropylsuccinate, di-neopentyl neopentylsuccinate, di-neopentyl isopentylsuccinate, (di-neopentyl 1-trifluoromethylethyl) succinate, di-neopentyl fluorenylsuccinate.

Another class of preferred compounds among those within formula (VI) is that wherein R is³-R⁶At least two of which are different from hydrogen and are selected from C1-C20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl groups, optionally containing heteroatoms. Particularly preferred are compounds in which two groups other than hydrogen are attached to the same carbon atom. Specific examples of suitable di-substituted succinates are: diethyl 2, 2-dimethylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl 2-benzyl-2-isopropylsuccinate, diethyl 2-cyclohexylmethyl-2-isobutylsuccinate diethyl __, diethyl 2-cyclopentyl-2-n-butylsuccinate, diethyl 2, 2-diisobutylsuccinate, diethyl 2-cyclohexyl-2-ethylsuccinate, diethyl 2-isopropyl-2-methylsuccinate, diethyl 2-tetradecyl-2-ethylsuccinate, diethyl 2-isobutyl-2-ethylsuccinate, diethyl 2- (1-trifluoromethylethyl) -2-methylsuccinate, diethyl 2-isopentyl-2-isobutylsuccinate, diethyl 2-isopropylsuccinate, diethyl 2-ethylsuccinate, diethyl 2-ethyl-2-isobutylsuccinate, diethyl 2-benzyl-2-isopropylsuccinate, diethyl 2-cyclohexylsuccinate, diethyl 2-isobutylsuccinate, diethyl 2-isopropylsuccinate, Diethyl 2-phenyl-2-n-butylsuccinate and diiso-2, 2-dimethylsuccinateButyl ester, diisobutyl 2-ethyl-2-methylsuccinate, diisobutyl 2-benzyl-2-isopropylsuccinate, diisobutyl 2-cyclohexylmethyl-2-isobutylsuccinate, diisobutyl 2-cyclopentyl-2-n-butylsuccinate, diisobutyl 2, 2-diisobutylsuccinate, diisobutyl 2-cyclohexyl-2-ethylsuccinate, diisobutyl 2-isopropyl-2-methylsuccinate, diisobutyl 2-tetradecyl-2-ethylsuccinate, diisobutyl 2-isobutyl-2-ethylsuccinate, diisobutyl 2- (1-trifluoromethylethyl) -2-methylsuccinate, diisobutyl 2-isopentyl-2-isobutylsuccinate, diisobutyl 2-isopropylsuccinate, Diisobutyl 2-phenyl-2-n-butylsuccinate, dipentyl 2, 2-dimethylsuccinate, dipentyl 2-ethyl-2-methylsuccinate, dipentyl 2-benzyl-2-isopropylsuccinate, dipentyl 2-cyclohexylmethyl-2-isobutylsuccinate, dipentyl 2-cyclopentyl-2-n-butylsuccinate, dipentyl 2, 2-diisobutylsuccinate, dipentyl 2-cyclohexyl-2-ethylsuccinate, dipentyl 2-isopropyl-2-methylsuccinate, dipentyl 2-tetradecyl-2-ethylsuccinate, dipentyl 2-isobutyl-2-ethylsuccinate, dipentyl 2- (1-trifluoromethylethyl) -2-methylsuccinate, dipentyl 2-ethylsuccinate, 2-isopentyl-2-isobutylsuccinic acid dipentyl ester, 2-phenyl-2-n-butylsuccinic acid dipentyl ester.

In addition, particular preference is given to compounds in which at least two radicals other than hydrogen are bonded to different carbon atoms, i.e. R³And R⁵Or R⁴And R⁶. Specific examples of suitable compounds are diethyl 2, 3-bis (trimethylsilyl) succinate, diethyl 2-sec-butyl-3-methylsuccinate, diethyl 2- (3,3, 3-trifluoropropyl) -3-methylsuccinate, diethyl 2, 3-bis (2-ethylbutyl) succinate, diethyl 2, 3-diethyl-2-isopropylsuccinate, diethyl 2, 3-diisopropyl-2-methylsuccinate, diethyl 2, 3-dicyclohexyl-2-methylsuccinate, diethyl 2, 3-dibenzylsuccinate, diethyl 2, 3-diisopropylsuccinate, diethyl 2, 3-bis (cyclohexylmethyl) succinate, diethyl 2, 3-di-tert-butylsuccinate, Diethyl 2, 3-diisobutylsuccinate, diethyl 2, 3-dineopentylsuccinate, diethyl 2, 3-diisopentylsuccinate, 2, 3-bis (1-trifluoromethylethyl) succinateAlkyl) diethyl succinate, diethyl 2, 3-ditetradecylsuccinate, diethyl 2, 3-difluorenylsuccinate, diethyl 2-isopropyl-3-isobutylsuccinate, diethyl 2-tert-butyl-3-isopropylsuccinate, diethyl 2-isopropyl-3-cyclohexylsuccinate, diethyl 2-isopentyl-3-cyclohexylsuccinate, diethyl 2-tetradecyl-3-cyclohexylsuccinate, diethyl 2-cyclohexyl-3-cyclopentylsuccinate, diethyl 2,2, 3, 3-tetramethylsuccinate, diethyl 2,2, 3, 3-tetraethylsuccinate, diethyl 2,2, 3, 3-tetrapropylsuccinate, diethyl 2, 3-diethyl-2, diethyl 3-diisopropylsuccinate, diethyl 2,2, 3, 3-tetrafluorosuccinate, diisobutyl 2, 3-bis (trimethylsilyl) succinate, diisobutyl 2-sec-butyl-3-methylsuccinate, diisobutyl 2- (3,3, 3-trifluoropropyl) -3-methylsuccinate, diisobutyl 2, 3-bis (2-ethylbutyl) succinate, diisobutyl 2, 3-diethyl-2-isopropylsuccinate, diisobutyl 2, 3-diisopropyl-2-methylsuccinate, diisobutyl 2, 3-dicyclohexyl-2-methylsuccinate, diisobutyl 2, 3-dibenzylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-tetrafluorosuccinate, Diisobutyl 2, 3-bis (cyclohexylmethyl) succinate, diisobutyl 2, 3-di-tert-butylsuccinate, diisobutyl 2, 3-diisobutylsuccinate, diisobutyl 2, 3-dineopentylsuccinate, diisobutyl 2, 3-diisopentylsuccinate, diisobutyl 2, 3-bis (1-trifluoromethylethyl) succinate, diisobutyl 2, 3-ditetradecylsuccinate, diisobutyl 2, 3-difluorenylsuccinate, diisobutyl 2-isopropyl-3-isobutylsuccinate, diisobutyl 2-tert-butyl-3-isopropylsuccinate, diisobutyl 2-isopropyl-3-cyclohexylsuccinate, diisobutyl 2-isopentyl-3-cyclohexylsuccinate, diisobutyl 2-cyclohexylsuccinate, Diisobutyl 2-tetradecyl-3-cyclohexylmethylsuccinate, diisobutyl 2-cyclohexyl-3-cyclopentylsuccinate, diisobutyl 2,2, 3, 3-tetramethylsuccinate, diisobutyl 2,2, 3, 3-tetraethylsuccinate, diisobutyl 2,2, 3, 3-tetrapropylsuccinate, diisobutyl 2, 3-diethyl-2, 3-dipropylsuccinate, diisobutyl 2,2, 3, 3-tetrafluorosuccinate, dipentyl 2, 3-bis (trimethylsilyl) succinate, dipentyl 2-sec-butyl-3-methylsuccinate, dipentyl 2- (3,3, 3-tristrimethylsilyl) succinate, and the likeFluoropropyl) -3-methylpenccinate dipentyl 2, 3-bis (2-ethylbutyl) succinate, 2, 3-diethyl-2-isopropylsuccinate dipentyl 2, 3-diisopropyl-2-methylsuccinate, 2, 3-dicyclohexyl-2-methylsuccinate, 2, 3-dibenzylsuccinate dipentyl 2, 3-diisopropylsuccinate, 2, 3-bis (cyclohexylmethyl) succinate, 2, 3-di-tert-butylsuccinate, 2, 3-diisobutylsuccinate dipentyl, 2, 3-dineopentylsuccinate, 2, 3-diisopentylsuccinate, 2, dipentyl 3- (1-trifluoromethylethyl) succinate, dipentyl 2, 3-ditetradecylsuccinate, dipentyl 2, 3-difluorenylsuccinate, dipentyl 2-isopropyl-3-isobutylsuccinate, dipentyl 2-tert-butyl-3-isopropylsuccinate, dipentyl 2-isopropyl-3-cyclohexylsuccinate, dipentyl 2-isopentyl-3-cyclohexylsuccinate, dipentyl 2-tetradecyl-3-cyclohexylmethylsuccinate, dipentyl 2-cyclohexyl-3-cyclopentylsuccinate, dipentyl 2,2, 3, 3-tetramethylsuccinate, dipentyl 2,2, 3, 3-tetraethylsuccinate 2, dipentyl 2,3, 3-tetrapropylsuccinate, dipentyl 2, 3-diethyl-2, 3-diisopropylsuccinate, dipentyl 2,2, 3, 3-tetrafluorosuccinate.

As mentioned above, the radicals R being attached to the same carbon atom³-R⁶Also preferred are compounds of formula (VI) in which two or four are linked together to form a ring. Specific examples of suitable compounds are 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2, 6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2, 5-dimethylcyclopentane, 1- (ethoxycarbonyl) -1- (ethoxyacetylmethyl) -2-methylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxyacetylcyclohexyl) cyclohexane.

The above-mentioned compounds can be used in the form of pure isomers or in the form of mixtures of enantiomers, or in the form of mixtures of positional isomers and enantiomers. When a pure isomer is to be used, it is generally isolated by conventional techniques well known in the art. In particular, some of the succinates of the invention may be used as pure racemic or meso forms, or alternatively as mixtures of the two forms.

Still another preferred Lewis-base-electron-compound B is a diol ester compound selected from the group consisting of the diol esters of the general formula (VII):

in the formula R¹-R⁶、R^1’-R^2’Is the same or different hydrogen, halogen or substituted or unsubstituted straight chain or branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 arylalkyl, C2-C10 alkenyl or C10-C20 condensed ring aryl; but R is^1’And R^2’Not being hydrogen, R¹-R⁶Optionally looped or not looped.

The diol ester compounds may be, for example: 1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol dibenzoate, 2-ethyl-1, 3-propanediol dibenzoate, 2-propyl-1, 3-propanediol dibenzoate, 2-butyl-1, 3-propanediol dibenzoate, 2-dimethyl-1, 3-propanediol dibenzoate, 2-ethyl-2-butyl-1, 3-propanediol dibenzoate, 2-diethyl-1, 3-propanediol dibenzoate, 2-methyl-2-propyl-1, 3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol, 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol dibenzoate, 3-propyl-2, 4-pentanediol dibenzoate, 3-butyl-2, 4-pentanediol dibenzoate, 3-dimethyl-2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 3-propanediol dibenzoate, 3-, 2-Ethyl-1, 3-pentanediol dibenzoate, 2-propyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2, 4-trimethyl-1, 3-pentanediol dibenzoate, 3-methyl-3-butyl-2, 4-pentanediol dibenzoate, 2-propyl-1, 3-pentanediol dibenzoate, 2-methyl-3-butyl-2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-methyl-2, 3-, 2, 2-dimethyl-1, 5-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, and the like. Pentanediol esters and heptanediol esters are preferred.

The solid catalyst component for olefin polymerization comprises a titanium compound, a magnesium compound, at least one 2-substituted amino-phenyl ester compound A selected from the above compounds, and at least one monofunctional or polyfunctional Lewis alkali electron donor compound B of ether, ester, ketone or amine, wherein the precursor of the magnesium compound is selected from at least one of: x_nMg(OR)_2-n，MgCl₂·mROH，R_2- _nMgX_n，MgCl₂/SiO₂，MgCl₂/Al₂O₃Or a mixture of a magnesium halide and a titanium alkoxide, where m is a number from 0.1 to 6, 0 < n > 2, X is halogen, R is C₁-C₂₀A hydrocarbon group of (a); the general formula of the titanium compound is TiX_N(OR)_4-NWherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and N is 1 to 4.

The magnesium compound of the present invention is preferably a magnesium hydrocarbyloxy compound.

The magnesium compound of the present invention is further preferably an alcoholate of a magnesium dihalide.

The titanium compound of the present invention includes titanium tetrachloride, titanium tetrabromide, titanium tetraiodide or an alkyltitanium halide such as methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride or tri-n-butoxytitanium chloride. One or more of these titanium halides may be used in combination. Among them, titanium tetrachloride is preferably used.

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

According to one of the processes, with TiCl₄Or an aromatic hydrocarbon (e.g., toluene, xylene, etc.) solution of titanium alkoxide may be reacted with a magnesium dihydrocarbyloxide compound such as magnesium dialkoxide or magnesium diaryloxide at-25 to 0 deg.C and halogenated at 80 to 130 deg.C. With TiCl₄The treatment with the aromatic hydrocarbon solution of (a) may be repeated one or more times, and the above-mentioned 2-substituted amino-phenyl ester compound a and the second Lewis base electron donor compound B are added in one or more portions in such treatments. The preparation can be carried out, for example, with reference to the preparation of the titanium-containing solid catalyst component disclosed in US 5077357: adding magnesium ethoxide, tetraethoxy titanium, o-cresol, ethanol and chlorobenzene in sequence, and stirring; mixing TiCl₄Adding chlorobenzene solution into the liquid quickly, heating until the chlorobenzene solution is dissolved completely, and continuing heating to a specific temperature; by using N₂Continuously stirring for a certain time after the ethanol reactant is taken away by bubbling, washing once by adopting hot chlorobenzene and twice by adopting isooctane, and then washing by adopting N₂Drying to obtain the carrier. Or according to another example: sequentially mixing TiCl₄Adding tetraethoxy titanium, ethoxy magnesium and o-cresol into chlorobenzene, and stirring; adding ethanol, and continuously stirring for 3h at high temperature after the magnesium ethoxide is dissolved; filtering while hot, washing with warm chlorobenzene once, washing with isooctane once, and finally N₂And (5) drying.

According to another method, an alcoholate or chlorohydrate of magnesium and an excess of TiCl containing in solution the above-mentioned 2-substituted amino-phenyl ester compound A and a second Lewis-base electron-donor compound B₄Reacting at 80-135 deg.C. According to a preferred method, the general formula TiX_n(OR)_4-nWherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is 1 to 4; preference is given to TiCl₄And is represented by the formula MgCl₂The adduct of mROH, where m is a number from 0.1 to 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having from 1 to 20 carbon atoms, to prepare the solid catalyst component. The adduct can be suitably made spherical by the following method: the alcohol and magnesium chloride are mixed in the presence of an inert hydrocarbon immiscible with the adduct, and the emulsion is rapidly quenched, thereby solidifying the adduct in the form of spherical particles. According toMgCl in spherical form prepared by this process₂Examples of mROH adducts are described in US4399054 and US 4469648. The adduct thus obtained can be directly reacted with the titanium compound or it can be previously subjected to a thermal controlled dealcoholation (80-130 ℃) to obtain an adduct in which the number of moles of alcohol is generally lower than 3, preferably between 0.1 and 2.5. Can be prepared by suspending the adduct (dealcoholated or as such) in cold TiCl₄(generally-25-0 ℃) with a titanium compound; the mixture is heated to 80-130 ℃ and held at this temperature for 0.5-2 hours. With TiCl₄The treatment may be performed one or more times. In the presence of TiCl₄The above-mentioned 2-substituted amino-phenyl ester compound A and the second Lewis base electron donor compound B may be added during the treatment, and the treatment may be repeated one or more times.

Another method for preparing the solid catalyst component of the present invention comprises grinding together anhydrous magnesium chloride with the above-described 2-substituted amino-phenyl ester compound A and a second Lewis base electron donor compound B under conditions in which magnesium dichloride is activated. The product thus obtained can be used with an excess of TiCl at a temperature of between 80 and 130 DEG C₄One or more treatments. After the treatment, the mixture is washed with a hydrocarbon solvent until free of chloride ions. According to a further method, the product obtained by co-grinding the magnesium dichloride in the anhydrous state, the titanium compound and the above-mentioned 2-substituted amino-phenyl ester compound A and the second Lewis base electron donor compound B is treated with a halogenated hydrocarbon such as 1, 2-dichloroethane, chlorobenzene, dichloromethane. The treatment is carried out at a temperature between 40 ℃ and the boiling point of the halogenated hydrocarbon for 1 to 4 hours. The product is then typically washed with an inert hydrocarbon solvent such as hexane.

According to another method, the magnesium dichloride is preactivated according to well known methods and then used with an excess of TiCl at a temperature of about 80-135 ℃₄Treatment, wherein the solution contains the 2-substituted amino-phenyl ester compound A and a second Lewis base electron donor compound B. With TiCl₄Treated multiple times and the solid washed with hexane to remove any reacted TiCl₄。

Further processes include, also, the preparation with reference to the titanium-containing solid catalyst component preparation process disclosed in CN 1208045: first, a liquid magnesium compound and a liquid titanium compound are contacted at a low temperature in the presence of a compound selected from the group consisting of alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters, and a solid is precipitated, the temperature at the time of the contact is generally-70 to 200 ℃, preferably-30 to 130 ℃, and the above-mentioned 2-substituted amino-phenyl ester compound A and a second Lewis base electron donor compound are treated during the contact.

Another process for the preparation of the solid catalyst component of the present invention comprises: dissolving a magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphine compound and an inert diluent (the inert diluent is pentane, hexane, heptane, octane, decane, benzene, toluene, xylene and derivatives thereof or a mixture of any of the compounds in any proportion, preferably toluene, heptane or hexane), forming a uniform solution, mixing the uniform solution with a titanium compound, and precipitating a solid in the presence of a precipitation aid; the solid is treated by the 2-substituted amino-phenyl ester compound A and a second Lewis base electron donor compound B, and is loaded on the solid, and if necessary, the solid is treated by titanium tetrahalide and inert diluent, wherein the precipitation assistant is one of organic acid anhydride, organic acid, ether and ketone. The components are calculated by each mole of magnesium halide, the organic epoxy compound is 0.2-10 moles, the organic phosphine compound is 0.1-3 moles, the precipitation aid is 0-1.0 mole, and the Ti compound is 0.5-150 moles.

The solid catalyst component of the present invention can also be used in SiO₂An inorganic oxide such as alumina or a porous resin, activated by a well-known method, and then used with an excess of TiCl at a temperature of about 80 to 135 deg.C₄And (3) treating, namely adding the 2-substituted amino-phenyl ester compound A and a second Lewis alkali electron donor compound B in the treatment process.

The above reaction results in the formation of magnesium halide in active form (generally, crystalline magnesium halide is structured and has little Ti to be supported, thus having low catalytic activity, and to prepare a supported catalyst having high activity, magnesium halide must be subjected to an activation treatment which comprises physically and/or chemically making it into crystallites so that active centers are supported on the surface, edges and defects of magnesium halide, and the treated crystallites of magnesium halide suitable for supporting Ti are referred to as "active magnesium halide"). In addition to these reactions, other methods are known in the literature for forming magnesium halide in active form starting from compounds other than magnesium halide.

In any of the preparation methods, the above electron donor compounds can be added as such or can be prepared in situ by, for example, employing suitable precursors which can be converted in the desired electron donor compound, for example, by means of known chemical reactions such as esterification, transesterification, and the like. Generally, relative to MgCl₂The electron donor compound is used in a molar ratio of 0.01 to 5, preferably 0.05 to 2.0.

In any of the preparation methods, the 2-substituted amino-phenyl ester compound a and the second Lewis base electron donor compound B may be added simultaneously or separately in any combination in any order, in batch or at the time of preparation.

The solid catalyst component of the present invention is converted into a catalyst for olefin polymerization by reaction with an organoaluminum compound according to a known method. In particular, it is an object of the present invention to provide a process for the preparation of the olefin CH₂A catalyst for the polymerization of ═ CHR, where R is hydrogen or a hydrocarbyl group containing 1 to 12 carbon atoms, comprising the product of the reaction of:

(a) the solid catalyst component of the invention contains Mg, Ti and halogen, at least one 2-substituted amino-phenyl ester compound A selected from the above compounds, and a monofunctional or polyfunctional electron donor compound B of ether, ester, ketone or amine,

(b) at least one compound of the general formula AlR_nX_(3-n)Wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; x is halogen, n is an integer of more than or equal to 0 and less than or equal to 3; and, optionally,

(c) at least one external electron donor compound.

Preferably, the alkylaluminum compound (b) is selected from trialkyl compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, trioctylaluminum. It is also possible to use trialkylaluminums with alkylaluminum halides, alkylaluminum hydrides or compounds such as AlEt₂Cl and Al₂Et₃Cl₃Such as alkylaluminum sesquichlorides, alkylaluminoxanes may also be used.

For applications requiring good isotacticity, an external electron donor compound may be used. The external electron donor compound is selected from the compounds with the general formula R_nSi(OR₁)_4-nSiloxane compound of the formula (I), wherein R and R₁Is C₁-C₁₈Optionally a heteroatom; n is an integer of 0-3.

The siloxane compound may specifically be: trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethylsilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-t-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldiethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, di (2-ethylhexyl) dimethoxysilane, di (n-butyldimethoxysilane), di (n, Bis (2-ethylhexyl) diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexyl-n-propyldimethoxysilane, cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, pentylmethyldimethoxysilane, pentylmethyldiethoxysilane, pentylethyldimethoxysilane, pentylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, vinyltrimethoxysilane, 2-ethylhexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3, 5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, 3, 5-dimethylcyclohexylcyclohexyldimethoxysilane, bis (3, 5-dimethylcyclohexyl) dimethoxysilane, pentakis (, Tetrapropoxysilane and tetrabutoxysilane. Among these organosilicon compounds, the following are preferred: di-n-propyldimethoxysilane, di-isopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyl-dimethoxysilane, cyclopentylmethyl-diethoxysilane, cyclopentylethyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane and 3, 5-dimethylcyclopentyldimethoxysilane, and the like. These compounds C may be used alone or in admixture thereof.

Examples of preferred silicon compounds are cyclohexylmethyldimethoxysilane; diisopropyl dimethoxysilane; di-n-butyldimethoxysilane; diisobutyldimethoxysilane; diphenyldimethoxysilane; phenyltriethoxysilane; methyl tert-butyl dimethoxysilane; dicyclopentyldimethoxysilane; 2-ethylpiperidinyl-2-tert-butyldimethoxysilane and (1, 1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1, 1, 1-trifluoro-2-propyl) -methylsulfanyltrimethoxysilane, cyclohexyltrimethoxysilane; t-butyltrimethoxysilane and thexyltrimethoxysilane.

The catalyst of the invention can be used for olefin CH₂In the (co) polymerization of ═ CHR, the olefins mentioned are ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.

For the polymerization of olefins using the catalysts of the present invention, both homopolymerization and copolymerization can be carried out using the catalysts prepared by components a, b or c as described above. The molar ratio of Al in component b to Ti in component a is generally from 1 to 1000, preferably from 50 to 800; when component c is contained, the molar ratio of component c to component b is 0.002 to 10, preferably 0.01 to 2, and most preferably 0.01 to 0.5.

The olefin polymerization catalyst of the present invention preferably comprises the following components or the reaction product of the following components, i.e., does not require the use of an external electron donor:

a) the above solid catalyst component;

b) at least one compound of the formula AlR_nX_(3-n)Wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; x is halogen, n is an integer of 0-3.

The olefin polymerization, homopolymerization and copolymerization preferably employ only the catalysts prepared by components a and b described above, the molar ratio of Al in component b to Ti in component a being from 1 to 1000mol, preferably from 50 to 800.

The feeding sequence of the components is arbitrary, and the component b is preferably added into the polymerization system first and then the component a is added; when component c is used, it is preferred to add component c after component b and finally component a.

The polymerization process in the present invention may be carried out with or without a solvent. The olefin monomer may be in the gas phase or the liquid phase. Further addition of hydrogen can serve as a molecular weight regulator. The polymerization can of course also be carried out without molecular weight regulators. The polymerization temperature is not higher than 200 ℃, preferably 20 to 100 ℃, more preferably 40 to 80 ℃. The polymerization pressure is not more than 10MPa, preferably 1 to 5 MPa. Either continuous polymerization or batch polymerization processes may be used. And the polymerization reaction may be carried out in one, two or more steps.

The olefins to be homopolymerized or copolymerized using the catalyst of the present invention include linear olefins: ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-nonene, 1-decene; branched olefins such as: 3-methyl-1-butene and 4-methyl-1-pentene; dienes such as: butadiene, vinylcyclopentene, and vinylcyclohexene. The catalyst of the present invention is preferably used in polyethylene and polypropylene. These olefins may be used alone or in combination of two or more.

The polymerization of olefins (referred to herein as bulk polymerization) using the catalyst components a, b, c of the present invention is preferably carried out by prepolymerization to increase the isotacticity, particle properties, etc. of the active polymer of the catalyst. The prepolymerization process can also be used for styrene homopolymerization.

The order of addition of the components and monomers in the prepolymerization process is arbitrary. It is preferred to add component b to the olefin gas which contains the inert or to be polymerized and then to add the olefin or olefins to be polymerized after addition of component a. In the course of the olefin prepolymerization using an organosilane, it is advisable to add component b to the prepolymerization system of an inert gas or an olefin gas to be polymerized, then to add component c, then to add component a, and finally to add the olefin.

According to the invention, the 2-substituted amino-phenyl ester compound and another Lewis base compound are used as internal electron donors, especially when the compound is compounded with a diether compound, the activity of the obtained catalyst is obviously higher than that of the 2-substituted amino-phenyl ester compound and the diether compound which are respectively and independently used, the molecular weight distribution of the obtained polyolefin is moderate, and the defect that the diether catalyst is high in activity but narrow in polymer molecular weight distribution can be overcome. The polymer obtained by the catalyst component without the external electron donor still has high isotacticity and ultrahigh activity, and still maintains high-level activity along with the prolonging of polymerization time, and the obtained polyolefin has low ash content. When the 2-substituted amino-phenyl ester compound and the succinate compound are compounded to be used as an internal electron donor, the molecular weight distribution of the obtained polyolefin can be further widened, and the catalyst is suitable for preparing a polymer product with wide molecular weight distribution. In addition, when the 2-substituted amino-phenyl ester compound is compounded with other common electron donor compounds, the performance is improved to different degrees, and the isotacticity of the polymer can be improved by compounding the 2-substituted amino-phenyl ester compound with a phthalic ester compound or a diol ester compound.

Detailed Description

The present invention will be further described with reference to the following examples, which are provided for the purpose of illustration and are not intended to limit the scope of the present invention.

The compounds listed in the examples are given by way of illustration only and are not intended to limit the invention, other compounds falling within the scope of the invention but not mentioned in the examples.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined generally in dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

Determination of the isotacticity of the Polymer

Measured by heptane extraction (6 hours boiling extraction with heptane). Two grams of dried polymer samples were extracted in an extractor with boiling heptane for 6 hours, and the ratio of the weight of the polymer (g) to 2, which was obtained by drying the residue to constant weight, was the isotacticity.

Determination of the molecular weight distribution of the Polymer

The measurement was carried out by PL-220 type gel permeation chromatography using trichlorobenzene as a solvent at 150 ℃ as a standard (polystyrene, flow rate 1.0mL/min, column: 3xPlgel 10um M1 Xed-B300 X7.5nm).

Determination of the Ash content of the Polymer

Determined according to GB/T9345.1-2008.

TABLE 1

TABLE 2

TABLE 3

Polymerization 1

Polymerization evaluation was carried out with a solid catalyst as a component of an olefin polymerization catalyst:

after a 5L stainless steel reactor was sufficiently purged with nitrogen, 5mL of a triethylaluminum hexane solution having a concentration of 0.5mol/L and 1mL of a methylcyclohexyldimethoxysilane (CMMS) hexane solution having a concentration of 0.1mol/L and 10mg of the prepared catalyst were added, 10mL of hexane was then added to flush the feed line, 2L (in a standard state) of hydrogen and 2.5L of purified propylene were further added, the reaction was prepolymerized at 20 ℃ for 5 minutes, and the temperature was raised to 70 ℃ to conduct polymerization at this temperature for 1 hour. After the reaction is finished, cooling the reaction kettle, stopping stirring, discharging a reaction product, and drying to obtain the polymer.

Example 1

In 500mL through nitrogen fully replaced with stirring 5-neck flask, adding 10g diethoxy magnesium and 80mL toluene to prepare suspension, then maintain at-10 ℃ to drop titanium tetrachloride 20mL, after the dropping is finished, slowly heating the system to 10 ℃ and then dropping titanium tetrachloride 60mL, then slowly heating to 90 ℃, adding 3g 2-benzamide-benzoic acid phenyl ester and 1g 9, 9-double methoxy methyl fluorine, then continuing to heat to 120 ℃ and keeping the temperature for 2 hours, then the liquid is filtered by pressure and clean, filtering the liquid, the solid obtained is washed 3 times at 125 ℃ by 120mL titanium tetrachloride. The obtained solid was washed with 150mL of hexane at 60 ℃ for 2 times, washed at room temperature for 2 times, filtered to remove the liquid and dried to obtain solid powder, i.e., a solid catalyst component. The titanium content, internal electron donor content and polymerization data of the solid catalyst component are shown in Table 4.

Examples 2 to 8

The solid catalyst component was prepared as in example 1, except that 2-benzamide-phenyl benzoate was sequentially replaced with the compounds in tables 1 to 3, respectively.

Example 9

The solid catalyst component was prepared as in example 7, except that 9, 9-bismethoxymethylfluorene was replaced with di-n-butyl phthalate.

Example 10

The solid catalyst component was prepared as in example 7, except that 9, 9-bismethoxymethylfluorene was replaced with 2-isopropyl-2-isopentyl-malonic acid ethyl ester.

Example 11

The solid catalyst component was prepared as in example 7, except that 9, 9-bismethoxymethylfluorene was replaced with diethyl 2, 3-diisopropylsuccinate.

Example 12

The solid catalyst component was prepared as in example 7, except that 9, 9-bismethoxymethylfluorene was replaced with 2, 4-pentanediol dibenzoate.

Example 13

Solid catalyst component A solid catalyst component was prepared as in example 7, except that 3g of 2- [ N-benzoyl-N-benzyl ] -4-tert-butyl-benzoic acid phenyl ester and 1g of 9, 9-bismethoxymethylfluorene were changed to 3g of 2- [ N-benzoyl-N-benzyl ] -4-tert-butyl-benzoic acid phenyl ester and 1.5g of 9, 9-bismethoxymethylfluorene.

Example 14

Solid catalyst component A solid catalyst component was prepared as in example 7, except that 3g of 2- [ N-benzoyl-N-benzyl ] -4-tert-butyl-benzoic acid phenyl ester and 1g of 9, 9-bismethoxymethylfluorene were changed to 1.5g of 2- [ N-benzoyl-N-benzyl ] -4-tert-butyl-benzoic acid phenyl ester and 1.5g of 9, 9-bismethoxymethylfluorene.

Example 15

Solid catalyst component A solid catalyst component was prepared as in example 7, except that 3g of 2- [ N-benzoyl-N-benzyl ] -4-tert-butyl-benzoic acid phenyl ester and 1g of 9, 9-bismethoxymethylfluorene were changed to 2g of 2- [ N-benzoyl-N-benzyl ] -4-tert-butyl-benzoic acid phenyl ester and 1.5g of 9, 9-bismethoxymethylfluorene.

Example 16

Solid catalyst component A solid catalyst component was prepared as in example 7, except that 3g of 2- [ N-benzoyl-N-benzyl ] -4-tert-butyl-benzoic acid phenyl ester and 1g of 9, 9-bismethoxymethylfluorene were changed to 3g of 2- [ N-benzoyl-N-benzyl ] -4-tert-butyl-benzoic acid phenyl ester and 0.5g of 9, 9-bismethoxymethylfluorene.

Example 17

A solid catalyst component was prepared as in example 7, except that 3g of 2- [ N-benzoyl-N-benzyl ] -4-tert-butyl-benzoic acid phenyl ester and 1g of 9, 9-bismethoxymethylfluorene were changed to 2g of 2- [ N-benzoyl-N-benzyl ] -4-tert-butyl-benzoic acid phenyl ester and 2g of 9, 9-bismethoxymethylfluorene.

Example 18

The solid catalyst component was prepared as in example 1, except that 2-benzamide-phenyl benzoate was changed to 2- [ N-benzoyl-N-tert-butyl ] -phenyl benzoate.

Example 19

The solid catalyst component was prepared as in example 1, except that 2-benzamide-phenyl benzoate was changed to 2- [ N-benzoyl-N-phenyl ] -4-tert-butyl-phenyl benzoate.

Example 20

In a 500ml 5-neck flask with stirring which was sufficiently purged with nitrogen, 10g of MgCl was charged at-15 ℃₂·3C₂H₅Suspension of OH microspheres and 150mL titanium tetrachloride was prepared, then maintained at-15 ℃ for 1 hour, slowly warmed to 80 ℃ and 3g of 2- [ N-benzoyl-N-benzhydryl ] was added]-4-tert-butyl-phenyl benzoate and 1g of 9, 9-bismethoxymethylfluorene, then the temperature is raised to 110 ℃ and the temperature is kept constant for 1 hour, then the liquid is filtered by pressure and cleaned, the liquid is filtered off, and the obtained solid is washed 3 times at 125 ℃ by 120mL of titanium tetrachloride. The obtained solid was washed with 150mL of hexane at 60 ℃ for 4 times, and the liquid was filtered off and dried to obtain a solid catalyst component.

Example 21

8g of anhydrous magnesium chloride, 38mL of decane and 35mL of 2-ethylhexanol were reacted at 130 ℃ for 2 hours to form a homogeneous solution. 1.7g phthalic anhydride was added to the solution and the mixture was stirred at 130 ℃ for 1 hour to dissolve the phthalic anhydride completely in the homogeneous solution. The resulting homogeneous solution was cooled to room temperature and added dropwise to 200mL of titanium tetrachloride maintained at-20 ℃ over 1 hour; after the addition was complete, the mixture was heated to 110 ℃ over 4 hours, 3g of phenyl 2- [ N-benzoyl-N-benzhydryl ] -4-tert-butyl-benzoate and 1g of 9, 9-bismethoxymethylfluorene were added when the temperature reached 110 ℃ and the mixture was stirred at the above temperature for 2 hours. After 2 hours of reaction, the solid portion was collected by hot filtration. The solid portion was suspended in 275mL of titanium tetrachloride and reacted at 110 ℃ for 2 hours. After the reaction, the solid portion was collected by hot filtration, sufficiently washed with decane and hexane at 110 ℃ and then dried by suction to obtain a solid catalyst component.

Example 22

In a 500mL 5-neck flask with stirring which was sufficiently replaced with nitrogen, 10g of anhydrous magnesium chloride, 150mL of toluene, 17mL of epichlorohydrin and 16mL of tributyl phosphate were added at room temperature, and the temperature was raised to 50 ℃ with stirring and maintained for 2 hours, and the solid was completely dissolved, and then 2.40g of phthalic anhydride was added and maintained for another 1 hour. The solution was cooled to-25 deg.C, 110mL of titanium tetrachloride was added dropwise over 1 hour, the temperature was slowly raised to 80 deg.C, and the solids were gradually washed out during the temperature rise. 3g of 2- [ N-benzoyl-N-benzhydryl ] -4-tert-butyl-benzoic acid phenyl ester and 1g of 9, 9-bismethoxymethylfluorene are added and maintained at 80 ℃ for 1 hour. After filtration, 200mL of toluene is washed twice, then 120mL of toluene and 80mL of titanium tetrachloride are added, the temperature is continuously increased to 110 ℃, the temperature is kept constant for 2 hours, then the liquid is subjected to pressure filtration and filtration, and the treatment is repeated once again. The liquid was filtered off, and the obtained solid was washed with 100mL of dichloroethane 1 time, hexane 4 times, and dried to obtain a solid catalyst component.

Example 23

The solid catalyst component was prepared as in example 20, except that 9, 9-bismethoxymethylfluorene was changed to 2, 4-pentanediol dibenzoate.

Example 24

The solid catalyst component was prepared as in example 21, except that 9, 9-bismethoxymethylfluorene was changed to 2, 4-pentanediol dibenzoate.

Example 25

The solid catalyst component was prepared as in example 22, except that 9, 9-bismethoxymethylfluorene was changed to 2, 4-pentanediol dibenzoate.

Example 26

A solid catalyst component was prepared as in example 20, except that 9, 9-bismethoxymethylfluorene was changed to diethyl 2, 3-diisopropylsuccinate.

Example 27

A solid catalyst component was prepared as in example 21, except that 9, 9-bismethoxymethylfluorene was changed to diethyl 2, 3-diisopropylsuccinate.

Example 28

A solid catalyst component was prepared as in example 22, except that 9, 9-bismethoxymethylfluorene was changed to diethyl 2, 3-diisopropylsuccinate.

Comparative example 1

The solid catalyst component was prepared as in example 1, except that 3g of 2-benzamide-phenyl benzoate and 1g of 9, 9-bismethoxymethylfluorene were changed to 4g of 2-benzamide-phenyl benzoate.

Comparative example 2

The solid catalyst component was prepared as in example 1, except that 3g of 2-benzamide-benzoate and 1g of 9, 9-bismethoxymethylfluorene were changed to 4g of 2-benzamide-4-tert-butyl-benzoate.

Comparative example 3

The solid catalyst component was prepared as in example 1, except that 3g of 2-benzamide-phenyl benzoate and 1g of 9, 9-bismethoxymethylfluorene were changed to 4g of 2-benzimide-phenyl benzoate.

Comparative example 4

The solid catalyst component was prepared as in example 1, except that 3g of 2-benzamide-phenyl benzoate and 1g of 9, 9-bismethoxymethylfluorene were changed to 4g of 2-benzimide-4-methyl-phenyl benzoate.

Comparative example 5

A solid catalyst component was prepared as in example 1, except that 3g of 2-benzamide-phenyl benzoate and 1g of 9, 9-bismethoxymethylfluorene were changed to 4g of 2- (1-naphthamide-N-benzyl) -4-methyl- (1-naphthoic acid) phenyl ester.

Comparative example 6

The solid catalyst component was prepared as in example 1, except that 3g of 2-benzamide-phenyl benzoate and 1g of 9, 9-bismethoxymethylfluorene were changed to 4g of 2- (octylamide-N-hexyl) -4-methyl-phenyloctanoate.

Comparative example 7

Solid catalyst component A solid catalyst component was prepared as in example 1, except that 3g of 2-benzamide-benzoic acid phenyl ester and 1g of 9, 9-bismethoxymethylfluorene were changed to 4g of 2- [ N-benzoyl-N-benzyl ] -4-tert-butyl-benzoic acid phenyl ester.

Comparative example 8

Solid catalyst component A solid catalyst component was prepared as in example 1, except that 3g of 2-benzamide-benzoic acid phenyl ester and 1g of 9, 9-bismethoxymethylfluorene were changed to 4g of 2- [ N-benzoyl-N-benzyl ] -4-methyl-6-methyl-benzoic acid phenyl ester.

Comparative example 9

The solid catalyst component was prepared as in example 1, except that 3g of 2-benzamide-benzoic acid phenyl ester and 1g of 9, 9-bismethoxymethylfluorene were changed to 4g of di-n-butyl phthalate.

Comparative example 10

The solid catalyst component was prepared as in example 1, except that 3g of 2-benzamide-benzoic acid phenyl ester and 1g of 9, 9-bismethoxymethylfluorene were changed to 4g of 9, 9-methoxymethylfluorene.

Comparative example 11

The solid catalyst component was prepared as in example 1, except that 3g of 2-benzamide-phenyl benzoate and 1g of 9, 9-bismethoxymethylfluorene were changed to 4g of 2-isopropyl-2-isopentyl-malonic acid ethyl ester.

Comparative example 12

A solid catalyst component was prepared as in example 1, except that 3g of 2-benzamide-phenyl benzoate and 1g of 9, 9-bismethoxymethylfluorene were changed to 4g of diethyl 2, 3-diisopropylsuccinate.

Comparative example 13

The solid catalyst component was prepared as in example 1, except that 3g of 2-benzamide-benzoic acid phenyl ester and 1g of 9, 9-bismethoxymethylfluorene were changed to 4g of 2, 4-pentanediol dibenzoate.

TABLE 4

DNBP: di-n-butyl phthalate, FLU: 9, 9-methoxymethylfluorene

DIE: 2-isopropyl-2-isoamyl-malonic acid ethyl ester, SUC: 2, 3-Diisopropylsuccinic acid diethyl ester

BRD: 2, 4-pentanediol dibenzoate, "-" indicates that the item is absent

As can be seen from the data in Table 4, when 8 2-substituted amino-phenyl ester compounds and 9, 9-bismethoxymethylfluorene are respectively adopted to compound an internal electron donor as a catalyst component (examples 1-8 and 13-19), the activity of the catalyst is significantly higher than that of a catalyst using the 2-substituted amino-phenyl ester compound alone (comparative examples 1-8) and the 9, 9-bismethoxymethylfluorene alone (comparative example 10) as the internal electron donor, and the molecular weight distribution of the obtained polymer is between the 2-substituted amino-phenyl ester compound and the 9, 9-bismethoxymethylfluorene. When the compounding ratio of only the 2-substituted amino-phenyl ester compound and the 9, 9-bismethoxymethylfluorene is different under other conditions (examples 7, 13-17), the activity of the catalyst and the molecular weight distribution of the obtained polymer are remarkably different, and can be improved to 93.2KgPP/gCat at most, and the molecular weight distribution of the polymer is moderate.

When the 2-substituted amino-phenyl ester compound and the succinate compound were used for the complex (example 11), the obtained polymer had a broader molecular weight distribution than when the 2-substituted amino-phenyl ester compound (comparative example 7) and the succinate compound (comparative example 12) were used alone, respectively.

When the 2-substituted amino-phenyl ester compound and di-n-butyl phthalate are compounded (example 9), the isotacticity of the resulting polymer can be further improved as compared with when the 2-substituted amino-phenyl ester compound (comparative example 7) and di-n-butyl phthalate (comparative example 9) are used alone, respectively. When the 2-substituted amino-phenyl ester compound and the glycol ester compound are compounded (example 12), the polymer isotacticity can be improved (compared with comparative examples 7 and 13).

Polymerization conditions 2

Polymerization evaluation was carried out under the following conditions using a solid catalyst as a component of an olefin polymerization catalyst:

after a 5L stainless steel reaction vessel was sufficiently purged with nitrogen, a triethylaluminum hexane solution having a concentration of 0.5mol/L (the amount of triethylaluminum is shown in Al/Ti in Table 4) and 3 to 5mg of the prepared catalyst were added, 10mL of hexane was added to flush the feed line, 2L (in a standard state) of hydrogen and 2.5L of purified propylene were added, and the reaction was controlled to prepolymerize at 20 ℃ for 5 minutes, warmed to 70 ℃ and polymerized at that temperature for a corresponding time (shown in Table 5). After the reaction is finished, cooling the reaction kettle, stopping stirring, discharging a reaction product, and drying to obtain the polymer. The results are shown in Table 5.

Example 29 example 34

Polymerization was carried out under the polymerization conditions 2 and those shown in Table 5 using CAT-13 as a catalyst, and the polymerization results are shown in Table 5.

Example 35 example 40

Polymerization was carried out under the polymerization conditions 2 and those shown in Table 5 using CAT-17 as a catalyst, and the polymerization results are shown in Table 5.

Comparative example 14

Polymerization was carried out using the catalyst REF-7 under the conditions described in polymerization conditions 2 and Table 5, and the polymerization results are shown in Table 5.

Comparative example 15 to comparative example 19

The polymerization was carried out under the conditions described in polymerization conditions 2 and Table 5 using catalysts REF-9 to REF-13, respectively, and the polymerization results are shown in Table 5.

TABLE 5

As can be seen from the data in Table 5, when CAT-13 and CAT-17 are polymerized by using an ethoxymagnesium carrier and adopting a 2-substituted amino-phenyl ester compound and 9, 9-bis (methoxymethylfluorene) to compound catalysts, an external electron donor compound is not used, the ultrahigh activity can be obtained, which is much higher than that of a non-compound catalyst (comparative examples 14-19) under the same polymerization conditions, and the high isotacticity of more than 98.0% is still maintained. When the polymerization time is extended from 60 minutes to 90 minutes and 120 minutes, the catalyst can maintain the ultra-high activity without deterioration. The ash content of the obtained polypropylene is lower when low Al/Ti is adopted, and can be reduced to 25ppm at least.

Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims

1. A solid catalyst component for the polymerization of olefins comprising Mg, Ti, halogen and at least two electron donors, one electron donor a being a 2-substituted amino-phenyl ester compound selected from the group of compounds of general formula (IV):

wherein the radical R¹、R²、R³And R⁴Identical or different, is H; halogen; c₁-C₂₀A hydrocarbon group of (a); r⁵Is C₁-C₂₀A hydrocarbon group of (a); r⁶And R^6’Identical or different, selected from H; c₁-C₂₀Linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, C₇-C₂₀Alkyl phenyl of (C)₇-C₂₀Phenylalkyl, indenyl;

the other electron donor B is selected from the electron donor compounds of diethers, esters, diketones and diamines;

the molar ratio of the electron donors A and B is 0.02-50.

2. The solid catalyst component according to claim 1 wherein the 2-substituted amino-phenyl ester compound is 2-benzimide-benzoate or 2-benzimide-4-methyl-6-methyl-benzoate.

3. The solid catalyst component according to claim 1 or 2, characterized in that the diether compound is selected from 1, 3-diethers of general formula (V):

wherein: r, R¹、R²、R³、R⁴And R⁵Identical or different, represents H or a linear or branched alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl radical having from 1 to 18 carbon atoms; r⁶And R⁷Identical or different, represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms and an arylalkyl group; optionally, R to R⁷Are linked to form a cyclic structure, optionally comprising one or more heteroatoms selected from halogen, N, O, S, P and Si.

4. The solid catalyst component according to claim 1 or 2, characterized in that the ester compound is selected from succinates of general formula (VI):

wherein the radical R¹And R²Identical or different from each other, is C₁-C₂₀A linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group, optionally comprising heteroatoms; r³-R⁶Wherein at least two radicals are different from hydrogen and are selected from C₁-C₂₀A linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl radical, optionally containing hetero atoms, optionally the radical R³-R⁶Joined together to form a ring.

5. The solid catalyst component according to claim 1 or 2, characterized in that the ester compound is selected from glycol ester compounds of general formula (VII):

in the formula, R¹-R⁶、R^1’-R^2’The same or different, hydrogen, halogen or substituted or unsubstituted straight chain or branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 arylalkyl, C2-C10 alkenyl or C10-C20 condensed ring aryl.

6. The solid catalyst component according to claim 1 or 2, characterized in that the molar ratio of the 2-substituted amino-phenyl ester compound a of general formula (IV) and the electron donor B is between 0.05 and 20.

7. The solid catalyst component according to claim 1 or 2 comprising a titanium compound, a magnesium compound and a reaction product selected from the group consisting of the 2-substituted amino-phenyl ester compound a and an electron donor B, the precursor of the magnesium compound being selected from at least one of: x_nMg(OR)_2-n，MgCl₂·mROH，R_2-nMgX_n，MgCl₂/SiO₂，MgCl₂/Al₂O₃Or a mixture of a magnesium halide and a titanium alkoxide, where m is a number from 0.1 to 6, 0 < n > 2, X is halogen, R is hydrogen or C₁-C₂₀A hydrocarbon group of (a); the general formula of the titanium compound is TiX_N(OR)_4-NWherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and N is 1 to 4.

8. A process for preparing the solid catalyst component for olefin polymerization according to claim 7, comprising: contacting a magnesium compound and a titanium compound with the 2-substituted amino-phenyl ester internal electron donor compound A and the electron donor B to obtain the solid catalyst component.

9. For olefin CH₂A catalyst for the polymerization of ═ CHR, where R is hydrogen or a hydrocarbyl group containing 1 to 12 carbon atoms, characterized in that it comprises the product of the reaction:

(a) the solid catalyst component of any one of claims 1 to 7;

(c) at least one selected from the group consisting of R_nSi(OR₁)_4-nAs an external electron donor compound, wherein R and R₁Is C₁-C₁₈Optionally a heteroatom; n is an integer of 0-3.

10. For olefin CH₂A catalyst for the polymerization of ═ CHR, where R is hydrogen or a hydrocarbyl group containing 1 to 12 carbon atoms, characterized in that it comprises the product of the reaction:

(a) the solid catalyst component of any one of claims 1 to 7;

(b) at least one compound of the general formula AlR_nX_(3-n)Wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; x is halogen, n is an integer of 0-3.

11. For olefins CH₂Process for the polymerization of ═ CHR, comprising homopolymerization, prepolymerization and copolymerization, in which R is hydrogen or a hydrocarbyl group containing from 1 to 12 carbon atoms, carried out in the presence of a catalyst as claimed in claim 9 or 10.