Catalyst components for olefin polymerization

Abstract

The solid catalyst component for the polymerization of olefins, which contains magnesium halide, a titanium compound having at least one Ti-halogen bond, and at least one 1,3-diether of a specific formula, has high polymerization activity and stereospecificity even in the absence of an external donor.

Description

[Technical Field]

[0001] The present invention relates to a Ziegler-Natta heterogeneous catalyst component for the polymerization of olefins, particularly propylene, comprising a magnesium dihalide, a Ti compound having at least one Ti-halogen bond, and at least one electron-donating compound selected from 1,3-diethers. The catalyst component is particularly suitable for the production of propylene homopolymers and copolymers. [Background technology]

[0002] Catalytic components for the stereospecific polymerization of olefins have been disclosed in the art. For the polymerization of propylene, Ziegler-Natta catalysts are generally used, which include a solid catalyst component comprising a titanium compound used in combination with an aluminum alkyl compound and a magnesium dihalide supported with an internal electron donor compound. However, conventionally, when a higher degree of crystallinity of the polymer is desired, an external donor (e.g., alkoxysilane) is also required to obtain higher isotacticity. Phthalates, particularly diisobutyl phthalates, are used as internal donors in catalyst preparation. This catalytic system, in which phthalates are used as internal donors in combination with alkylalkoxysilanes as external donors, exhibits excellent performance in terms of activity, isotacticity, and xylene insolubility.

[0003] In some cases, it may be desirable to produce polymers using catalytic systems that do not use phthalate esters as electron donors.

[0004] European Patent Application No. 361494A2, International Patent Application No. 02 / 100904, and International Patent Application No. 2021 / 063930 describe solid catalyst components for olefin polymerization containing 1,3-diethers characterized by a specific structure as internal electron donor compounds. Despite generally good performance, there is still a need for phthalate-free catalyst components that simultaneously exhibit very high polymerization activity and very high stereospecificity.

[0005] The applicant has surprisingly found that a specific group of 1,3-diethers used as internal donors impart very high activity and very high stereospecificity to the catalytic component, even in the absence of external donors. [Overview of the project]

[0006] Therefore, one of the objectives of this patent application is a solid catalyst component for the polymerization of olefins comprising a magnesium halide, a titanium compound having at least a Ti-halogen bond, and at least an electron donor of formula (I).

[0007] [ka] (I) (In the formula, R 1 and R 2 R is independently a C1-C5 alkyl group, where X is Si or C, and R is 3 and R 4 The group consists of hydrogen, C1-C, and C1-C13 20 Selected from hydrocarbon groups and halogens, however, R 3 At least two of them are not hydrogen. [Modes for carrying out the invention]

[0008] Preferably, R 1 and R 2 These are identical and are selected from C1-C4 linear or branched alkyl groups, more preferably selected from methyl groups.

[0009] The term "hydrocarbon group" includes individual groups such as alkyl, cycloalkyl, arylalkyl, alkenyl, aryl, alkylaryl, etc., and hydrocarbon groups fused to form saturated or unsaturated rings.

[0010] Preferably, R 4 groups are independently selected from hydrogen, C1-C 10 hydrocarbon groups and halogen. More preferably, they are selected from hydrogen, C1-C4 straight-chain or branched alkyl groups and halogen. Even more preferably, only one or two of the R 4 groups are C1-C4 straight-chain or branched alkyl groups or halogen. Preferred alkyl groups are methyl group, isopropyl group or t-butyl group, and preferred halogens are Cl and F. The structure in which all R 4 groups are hydrogen is also preferred.

[0011] R 3 groups are preferably selected from hydrogen, C1-C 10 hydrocarbon groups and halogen. When R 3 is a hydrocarbon group, it is preferably selected from C1-C4 straight-chain or branched alkyl groups, optionally substituted with C1-C4 straight-chain alkyl groups, groups that are linked together to form a C6 saturated ring, and particularly preferred alkyl groups are methyl group, ethyl group and isobutyl group.

[0012] R 3 When it is halogen, it is preferably selected from Cl and F, and more preferably F.

[0013] According to a preferred embodiment, X is carbon, and R 3 is hydrogen, C1-C 20 hydrocarbon group or halogen. Preferably, the hydrocarbon group is selected from C1-C4 straight-chain or branched alkyl groups, more preferably selected from methyl group. Most preferably, the structure is such that one R 3 is selected from hydrogen and the remaining two are selected from methyl groups.

[0014] Another group of preferred structures is one where X is carbon and R 3 is a hydrogen or halogen group, preferably selected from Cl and F, more preferably selected from F. Most preferably R 3 At least two of the structures are selected from F, and more preferably all R 3 This structure has F as its base.

[0015] According to another preferred embodiment, X is Si, and R 3 R is a hydrogen or hydrocarbon group, preferably selected from C1-C4 linear or branched alkyl groups, more preferably selected from methyl or ethyl groups. Most preferably all R 3 This structure is one in which the group is selected from methyl groups.

[0016] Specific examples of compounds of formula (I) that can be used advantageously include: 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-difluorobutyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-dibromobutyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-dichlorobutyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3,3-trifluoropropyl)-1,3-dimethoxypropane, and 2-cyclohexyl-2-(3,3,3-tribromopropyl)-1,3-dimethoxypropane. Propane, 2-cyclohexyl-2-(3,3,3-trichloropropyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-difluoropropyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-dibromopropyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-dichloropropyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-dichloro-3-fluoropropyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3 -Dichloro-3-bromo-propyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-difluoro-3-bromo-propyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-difluoro-3-chloro-propyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-difluoro-5-methylhexyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-dichloro-5-methylhexyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-( 3-Chloro-3-isobutyl-5-methylhexyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3-bromo-3-isobutyl-5-methylhexyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3-fluoro-3-isobutyl-5-methylhexyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3-fluoro-3-isopentyl-6-methylheptyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3-chloro-3-isopentyl-6-methylheptyl)-1,3-Dimethoxypropane, 2-Cyclohexyl-2-(3-Bromo-3-Isopentyl-6-Methylheptyl)-1,3-Dimethoxypropane, 2-Cyclohexyl-2-(3,3-Diphenylbutyl)-1,3-Dimethoxypropane, 2-Cyclohexyl-2-(3,3-Diphenylpropyl)-1,3-Dimethoxypropane, 2-Cyclohexyl-2-(3,3,3-Triphenylpropyl)-1,3-Dimethoxypropane, 2-Cyclohexyl-2-(3,3,3-Tris(4-Chlorophenyl)propyl)-1,3-Dimethoxypropane 2-Cyclohexyl-2-(3,3-diphenylmethylbutyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3-methylpentyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3-ethylpentyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3,3-diphenylethylpentyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3-isopropyl-4-methylpentyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3,3-diphenylisopropyl-4- Methylpentyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(cyclohexylethyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(chloropentylethyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(phenethyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(2-trimethylsilylethyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(2-triisopropylsilylethyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(2-triphenylsilylethyl) (Ethyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(2-methyldiphenylsilylethyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(2-diphenylmethylphenylsilylethyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(2-(tris(4-chlorophenyl)silyl)ethyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(2-(bis(4-chlorophenyl)(methyl)silyl)ethyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-isopentyl-1,3-Diphenylallyloxypropane, 2-Cyclohexyl-2-(3,3-difluorobutyl)-1,3-diphenylethoxypropane, 2-Cyclohexyl-2-(3,3-dibromobutyl)-1,3-diphenylallyloxypropane, 2-Cyclohexyl-2-(3,3-dichlorobutyl)-1,3-diphenylethoxypropane, 2-Cyclohexyl-2-(3,3,3-trifluoropropyl)-1,3-diphenylethoxypropane, 2-Cyclohexyl-2-(3,3,3-tribromopropyl)-1,3-diphenyl Toxypropane, 2-cyclohexyl-2-(3,3,3-trichloropropyl)-1,3-diphenylpropoxypropane, 2-cyclohexyl-2-(3,3-difluoropropyl)-1,3-diphenylallyloxypropane, 2-cyclohexyl-2-(3,3-dibromopropyl)-1,3-diphenylethoxypropane, 2-cyclohexyl-2-(3,3-dichloropropyl)-1,3-diphenylpropoxypropane, 2-cyclohexyl-2-(3,3-dichloro-3-fluoropropyl)-1,3-diphenylethoxypropane Cypropane, 2-Cyclohexyl-2-(3,3-Dichloro-3-bromo-propyl)-1,3-Diphenylpropoxypropane, 2-Cyclohexyl-2-(3,3-Difluoro-3-bromo-propyl)-1,3-Diphenylbutoxypropane, 2-Cyclohexyl-2-(3,3-Difluoro-3-chloro-propyl)-1,3-Diphenylpropoxypropane, 2-Cyclohexyl-2-(3,3-Difluoro-5-methylhexyl)-1,3-Diphenylethoxypropane, 2-Cyclohexyl-2-(3,3-Dichloro-5- Methylhexyl)-1,3-diphenylpropoxypropane, 2-cyclohexyl-2-(3-chloro-3-isobutyl-5-methylhexyl)-1,3-diphenylisopentoxypropane, 2-cyclohexyl-2-(3-bromo-3-isobutyl-5-methylhexyl)-1,3-diphenylethoxypropane, 2-cyclohexyl-2-(3-fluoro-3-isobutyl-5-methylhexyl)-1,3-diphenylpropoxypropane, 2-cyclohexyl-2-(3-fluoro-3-isopentyl-6-methylheptyl)-1,3-Diphenylethoxypropane, 2-Cyclohexyl-2-(3-chloro-3-isopentyl-6-methylheptyl)-1,3-Diphenylbutoxypropane, 2-Cyclohexyl-2-(3-bromo-3-isopentyl-6-methylheptyl)-1,3-Diphenylpropoxypropane, 2-Cyclohexyl-2-(3,3-Diphenylbutyl)-1,3-Diphenylallyloxypropane, 2-Cyclohexyl-2-(3,3-Diphenylpropyl)-1,3-Diphenylallyloxypropane, 2-Cyclohexyl-2-(3,3,3-Tri Phenylpropyl)-1,3-diphenylethoxypropane, 2-cyclohexyl-2-(3,3,3-tris(4-chlorophenyl)propyl)-1,3-diphenylallyloxypropane, 2-cyclohexyl-2-(3,3-diphenylmethylbutyl)-1,3-diphenylethoxypropane, 2-cyclohexyl-2-(3-methylpentyl)-1,3-diphenylallyloxypropane, 2-cyclohexyl-2-(3-ethylpentyl)-1,3-diphenylisopentoxypropane, 2-cyclohexyl-2-(3,3-diphenyl (Tylpentyl)-1,3-diphenylethoxypropane, 2-cyclohexyl-2-(3-isopropyl-4-methylpentyl)-1,3-diphenylethoxypropane, 2-cyclohexyl-2-(3,3-diphenylisopropyl-4-methylpentyl)-1,3-diphenylethoxypropane, 2-cyclohexyl-2-(cyclohexylethyl)-1,3-diphenylethoxypropane, 2-cyclohexyl-2-(chloropentylethyl)-1,3-diphenylallyloxypropane, 2-cyclohexyl-2-(phenethyl)-1,3- Diphenylisopentoxypropane, 2-cyclohexyl-2-(2-trimethylsilylethyl)-1,3-diphenylbutoxypropane, 2-cyclohexyl-2-(2-triisopropylsilylethyl)-1,3-diphenylisopentoxypropane, 2-cyclohexyl-2-(2-triphenylsilylethyl)-1,3-diphenylethoxypropane, 2-cyclohexyl-2-(2-methyldiphenylsilylethyl)-1,3-diphenylethoxypropane, 2-cyclohexyl-2-(2-diphenylmethylphenylsilylethyl)-1,3-Diphenylethoxypropane, 2-Cyclohexyl-2-(2-(tris(4-chlorophenyl)silyl)ethyl)-1,3-Diphenylbutoxypropane, 2-Cyclohexyl-2-(2-(bis(4-chlorophenyl)(methyl)silyl)ethyl)-1,3-Diphenylbutoxypropane, 2-Cyclohexyl-2-Isopentyl-1-Ethoxy-3-Methoxypropane, 2-Cyclohexyl-2-(3,3-Difluorobutyl)-1-Ethoxy-3-Methoxypropane, 2-Cyclohexyl Chlohexyl-2-(3,3-dibromobutyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-dichlorobutyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3,3-trifluoropropyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3,3-tribromopropyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3,3-trichloropropyl)-1-methoxy C-3-allyloxy-propane, 2-cyclohexyl-2-(3,3-difluoropropyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-dibromopropyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-dichloropropyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-dichloro-3-fluoropropyl)-1-isobutoxy-3-methoxy-propane, 2-cyclohexyl- 2-(3,3-dichloro-3-bromo-propyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-difluoro-3-bromo-propyl)-1-ethoxy-3-isopentoxy-propane, 2-cyclohexyl-2-(3,3-difluoro-3-chloro-propyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-difluoro-5-methylhexyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-Dichloro-5-methylhexyl)-1-ethoxy-3-methoxypropane, 2-Cyclohexyl-2-(3-chloro-3-isobutyl-5-methylhexyl)-1-ethoxy-3-methoxypropane, 2-Cyclohexyl-2-(3-bromo-3-isobutyl-5-methylhexyl)-1-ethoxy-3-propoxypropane, 2-Cyclohexyl-2-(3-fluoro-3-isobutyl-5-methylhexyl)-1-ethoxy-3-methoxypropane, 2-Cyclohexyl-2-(3-fluoro-3-isopentyl-6-methylheptyl)-1-ethoxy-3-methoxypropane, 2-Cyclohexyl-2-(3-chloro-3-isopentyl-6-methylheptyl, (Tyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3-bromo-3-isopentyl-6-methylheptyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-diphenylbutyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-diphenylpropyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3,3-triphenylpropyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3,3-tris(4-chlorophenyl)propyl)-1-ethoxy Xy-3-methoxypropane, 2-cyclohexyl-2-(3,3-diphenylmethylbutyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3-methylpentyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3-ethylpentyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-diphenylethylpentyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3-isopropyl-4-methylpentyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-Diphenylisopropyl-4-methylpentyl)-1-ethoxy-3-methoxy-propane, 2-Cyclohexyl-2-(cyclohexylethyl)-1-methoxy-3-propoxy-propane, 2-Cyclohexyl-2-(chloropentylethyl)-1-ethoxy-3-methoxy-propane, 2-Cyclohexyl-2-(phenethyl)-1-ethoxy-3-methoxy-propane, 2-Cyclohexyl-2-(2-trimethylsilylethyl)-1-ethoxy-3-methoxy-propane, 2-Cyclohexyl-2-(2-triisopropylsilylethyl)- 1-Allyloxy-3-methoxypropane, 2-Cyclohexyl-2-(2-triphenylsilylethyl)-1-ethoxy-3-methoxypropane, 2-Cyclohexyl-2-(2-methyldiphenylsilylethyl)-1-ethoxy-3-methoxypropane, 2-Cyclohexyl-2-(2-diphenylmethylphenylsilylethyl)-1-ethoxy-3-methoxypropane, 2-Cyclohexyl-2-(2-(tris(4-chlorophenyl)silyl)ethyl)-1-ethoxy-3-isobutoxypropane, 2-Cyclohexyl-2-(2-(Bi (4-chlorophenyl)(methyl)silyl)ethyl)-1-ethoxy-3-methoxypropane, 2-(3-methylcyclohexyl)-2-isopentyl-1,3-dimethoxypropane, 2-(2-methylcyclohexyl)-2-(3,3-difluorobutyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(3,3-dibromobutyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(3,3-dichlorobutyl)-1,3-dimethoxypropane, 2-(2-methylcyclohexyl)-2-(3,3 ,3-trifluoropropyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(3,3,3-tribromopropyl)-1,3-dimethoxypropane, 2-(2-methylcyclohexyl)-2-(3,3,3-trichloropropyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(3,3-difluoropropyl)-1,3-dimethoxypropane, 2-(3-methylcyclohexyl)-2-(3,3-dibromopropyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(3,3-Dichloropropyl)-1,3-Dimethoxypropane, 2-(4-Methylcyclohexyl)-2-(3,3-Dichloro-3-Fluoropropyl)-1,3-Diphenylethoxypropane, 2-(2-Methylcyclohexyl)-2-(3,3-Dichloro-3-Bromopropyl)-1,3-Diphenylpropoxypropane, 2-(4-Methylcyclohexyl)-2-(3,3-Difluoro-3-Bromopropyl)-1,3-Diphenylbutoxypropane, 2-(4-Methylcyclohexyl)-2-(3,3-Difluoro- 3-chloropropyl)-1,3-diphenylpropoxypropane, 2-(4-methylcyclohexyl)-2-(3,3-difluoro-5-methylhexyl)-1,3-diphenylethoxypropane, 2-(4-methylcyclohexyl)-2-(3,3-dichloro-5-methylhexyl)-1,3-diphenylpropoxypropane, 2-(4-methylcyclohexyl)-2-(3-chloro-3-isobutyl-5-methylhexyl)-1,3-diphenylisopentoxypropane, 2-(4-methylcyclohexyl)-2-(3- Bromo-3-isobutyl-5-methylhexyl)-1,3-diphenylethoxypropane, 2-(3-methylcyclohexyl)-2-(3-fluoro-3-isobutyl-5-methylhexyl)-1,3-diphenylpropoxypropane, 2-(4-methylcyclohexyl)-2-(3-fluoro-3-isopentyl-6-methylheptyl)-1,3-diphenylethoxypropane, 2-(3-methylcyclohexyl)-2-(3-chloro-3-isopentyl-6-methylheptyl)-1,3-diphenylbutoxypropane, 2 -(4-methylcyclohexyl)-2-(3-bromo-3-isopentyl-6-methylheptyl)-1,3-diphenylpropoxypropane, 2-(4-methylcyclohexyl)-2-(3,3-diphenylbutyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(3,3-diphenylpropyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(3,3,3-triphenylpropyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(3,3,3-Tris(4-chlorophenyl)propyl)-1-ethoxy-3-methoxy-propane, 2-(2-methylcyclohexyl)-2-(3,3-diphenylmethylbutyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(3-methylpentyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(3-ethylpentyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(3,3-diethylpentyl)-1,3-dimethoxypropane, 2-(4-methylcyclo Hexyl)-2-(3-isopropyl-4-methylpentyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(3,3-diisopropyl-4-methylpentyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(cyclohexylethyl)-1,3-dimethoxypropane, 2-(3-methylcyclohexyl)-2-(cyclopentylethyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(phenethyl)-1,3-dimethoxypropane, 2-(3-methyl Lucyclohexyl)-2-(2-trimethylsilylethyl)-1,3-dimethoxypropane, 2-(3-methylcyclohexyl)-2-(2-triisopropylsilylethyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(2-triphenylsilylethyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-(2-methyldiphenylsilylethyl)-1-ethoxy-3-methoxypropane, 2-(4-methylcyclohexyl)-2-(2-dimethylphenylsilylethyl)-1 -Ethoxy-3-methoxy-propane, 2-(4-methylcyclohexyl)-2-(2-(tris(4-chlorophenyl)silyl)ethyl)-1-ethoxy-3-isobutoxy-propane, 2-(3-methylcyclohexyl)-2-(2-(bis(4-chlorophenyl)(methyl)silyl)ethyl)-1-ethoxy-3-methoxy-propane, 2-(3,5-dimethylcyclohexyl)-2-isopentyl-1,3-dimethoxypropane, 2-(4-(tert-butyl)cyclohexyl)-2-(3,3-difluorobutyl)-1,3-Dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-dibromobutyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-dichlorobutyl)-1,3-dimethoxypropane, 2-(4-(tert-butyl)cyclohexyl)-2-(3,3,3-trifluoropropyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3,3-tribromopropyl)-1,3-dimethoxypropane , 2-cyclohexyl-2-(3,4-dimethylpentyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,4,4-trimethylpentyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,5-dimethylhexyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3-cyclopropylbutyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-dicyclohexylpropyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3-phenylbutyl)-1,3-di Methoxypropane, 2-cyclohexyl-2-(3-methyl-4,4,4-trifluorobutyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3-trifluoromethyl-4,4,4-trifluorobutyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3-benzyl-4,4,4-trifluorobutyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-((2,6-dimethyl)cyclohexylethyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-((3,3,5-trimethyl) (Crohexylethyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(2-(1,7,7-trimethylbicyclo[3.1.1]heptan-6-yl)ethyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3,3-dibenzylpropyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(9-fluoroenylethyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-isopentyl-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3-methylhexyl)-1,3-Dimethoxypropane, 2-(4-methylcyclohexyl)-2-(3-methylhexyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3,3-triphenylpropyl)-1,3-dimethoxypropane, 2-(4-(tert-butyl)cyclohexyl)-2-(3,3,3-trichloropropyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-difluoropropyl)-1,3-dimethoxypropane, 2-(3,5-dimethylcyclohexyl)-2-(3,3-dibromopropyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3, 3-Dichloro-3-fluoropropyl)-1,3-diethoxypropane, 2-(4-(tert-butyl)cyclohexyl)-2-(3,3-dichloro-3-bromo-propyl)-1,3-dipropoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-difluoro-3-bromo-propyl)-1,3-dibutoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-difluoro-3-bromo-propyl)-1,3-dibutoxypropane, 2-(2-isopropyl-5-methyl Lucyclohexyl)-2-(3,3-difluoro-3-chloro-propyl)-1,3-dipropoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-difluoro-5-methylhexyl)-1,3-diethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-dichloro-5-methylhexyl)-1,3-dipropoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3-chloro-3-isobutyl-5-methylhexyl)-1,3-diisopentoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3-bromo-3-isobutyl-5-methylhexyl)-1,3-diethoxypropane, 2-(3,5-dimethylcyclohexyl)-2-(3-fluoro-3-isobutyl-5-methylhexyl)-1,3-dipropoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3-fluoro-3-isopentyl- 6-methylheptyl)-1,3-diethoxypropane, 2-(3,5-dimethylcyclohexyl)-2-(3-chloro-3-isopentyl-6-methylheptyl)-1,3-dibutoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3-bromo-3-isopentyl-6-methylheptyl)-1,3-dipropoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-diphenylbutyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3- Diphenylpropyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3,3-triphenylpropyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3,3-tris(4-chlorophenyl)propyl)-1-ethoxy-3-methoxypropane, 2-(4-(tert-butyl)cyclohexyl)-2-(3,3-dimethylbutyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3-methyl Pentyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3-ethylpentyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-diethylpentyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3-isopropyl-4-methylpentyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-diisopropyl-4-methylpentyl)-1,3-Dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(cyclohexylethyl)-1,3-dimethoxypropane, 2-(3,5-dimethylcyclohexyl)-2-(cyclopentylethyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(phenethyl)-1,3-dimethoxypropane, 2-(3,5-dimethylcyclohexyl)-2-(2-trimethylsilylethyl)-1,3-dimethoxypropane, 2-(3,5-dimethylcyclohexyl)-2-(2-triisopropylsilylethyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(2-tri Phenylsilylethyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(2-methyldiphenylsilylethyl)-1-ethoxy-3-methoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(2-dimethylphenylsilylethyl)-1-ethoxy-3-methoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(2-(tris(4-chlorophenyl)silyl)ethyl)-1-ethoxy-3-isobutoxypropane, 2-(3,5-dimethylcyclohexyl)-2-(2-(bis(4-chlorophenyl)(methyl)silyl)ethyl)-1-ethoxy-3-methoxypropane.

[0017] Preferably, the molar ratio of the electron donor of formula (I) to the Ti atoms in the final solid catalyst component is in the range of 0.3:1 to 1.5:1, and more preferably in the range of 0.4:1 to 1.3:1.

[0018] Preferably, the molar ratio of Mg atoms to the electron donor of formula (I) in the final solid catalyst component is in the range of 2.5:1 to 50.0:1, more preferably 3:1 to 45.0:1, even more preferably 5.0:1 to 30.0:1, and particularly more preferably 6.0:1 to 25.0:1.

[0019] Additional electron donors may, in principle, be present in the catalyst components of this disclosure. Preferably, they are selected from monoesters or diesters of aromatic or aliphatic carboxylic acids. More preferably, they are selected from esters of aliphatic dicarboxylic acids, such as malonates, succinates, and glutarates, as described in International Patent No. 99 / 57160. The additional donors may be present in an amount of 0.1 to less than 50.0% molar, preferably 0.5 to 45.0%, based on the total molar amount of the bifunctional electron donors. If the additional donors are different from aliphatic dicarboxylic acid esters, their amount is preferably less than 10% molar, more preferably less than 8% molar, based on the total molar amount of the electron donors.

[0020] Preferably, the solid catalyst component has a porosity of at least 0.20 cm² as measured by the mercury method for pores with a radius of 1 μm or less. 3 The density is / g. More preferably, the porosity is 0.30 cm². 3 Higher than / g, especially 0.40cm 3 Higher than / g

[0021] Preferably, the average particle size of the catalyst component is 20 to 150 μm, and more preferably 40 to 100 μm.

[0022] As described above, the catalyst component of the present invention includes, in addition to the electron donor, a titanium compound having at least a Ti-halogen bond and a Mg halide. Preferred titanium compounds used in the catalyst component of the present invention are TiCl4 and TiCl3, and furthermore, the titanium compound of formula Ti(OR 5 ) n-y X y Ti haloaloolates can also be used, where n is the valence of titanium and y is 1 to n. -1 The number of halogens, X is halogen, R 5 i is a hydrocarbon group having 1 to 10 carbon atoms.

[0023] The solid catalyst component can be prepared according to several methods. According to a preferred method, the solid catalyst component is a compound of the formula Ti(OR 5 ) m-y Xy A titanium compound, preferably TiCl4, (where m is the valence of titanium and y is the number from 1 to m) can be prepared by reacting it with magnesium chloride derived from an adduct of formula MgCl2. ·pR 6 OH(wherein p is a number from 0.1 to 6, preferably from 2 to 3.5, R 6 The adduct is a hydrocarbon group having 1 to 18 carbon atoms. The adduct can be appropriately prepared into a spherical shape by mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon that is immiscible with the adduct and operating with stirring at the melting point of the adduct (100 to 130°C). The emulsion is then rapidly quenched, thereby solidifying the adduct in the form of spherical particles. Examples of spherical adducts produced according to this procedure are described in U.S. Patents P4,399,054 and P4,469,648. The adduct thus obtained can be reacted directly with a Ti compound, or it can be subjected to pre-controlled de-alcoholization (80 to 130°C) to obtain an adduct in which the number of moles of alcohol is less than 3, preferably 0.1 to 2.5, and more preferably 0.5 to 2.3.

[0024] The catalyst based on the electron donor of formula (I) of the present invention can exhibit very good performance even when produced from a highly dealcoholized adduct, for example, one in which the number of moles of alcohol per mole of Mg is less than 2. When these dealcoholized adducts are used, the conventional diether donor is immobilized to a much lower degree, and the performance of the derived catalyst deteriorates.

[0025] In a preferred method for producing the catalyst of the present invention, the reaction with the Ti compound can be carried out by suspending the adduct (de-alcoholized or as is) in cold TiCl4, generally at 0°C. Preferably, the adduct is used in an amount such that its concentration is 20-100 g / l, preferably 30-90 g / l. According to a preferred embodiment, the electron donor (I) is added to the system at the start of this step of the reaction, preferably when the temperature of the mixture is in the range of 10°C-60°C. The electron donor (I) is supplied in an amount such that the desired molar ratio is satisfied in the final catalyst. In one embodiment, the Mg / donor (I) molar ratio may be in the range of 2:1-25:1, preferably 2:1-25:1, more preferably 2:1-15:1, and particularly 3:1-10:1. The temperature is then gradually increased to 90-130°C and held at this temperature for 0.5-3 hours. Once the reaction time is complete, stirring is stopped, the slurry is allowed to settle, and the liquid phase is removed. The second stage of treatment with TiCl4 is carried out, preferably at a temperature of 70-130°C. Once the reaction time is complete, stirring is stopped, the slurry is allowed to settle, and the liquid phase is removed. Although not essential, an additional reaction step with a titanium compound, preferably TiCl4, can be carried out under the same conditions as above, in the absence of an electron donor. The solid thus obtained can then be washed with liquid hydrocarbons under mild conditions and dried. The catalyst based on the electron donor of formula (I) of the present invention can be manufactured with a relatively high Mg / ID molar ratio (13-20) and can provide very good performance even when the amount of ID immobilized on the catalyst is such that the ID / Ti molar ratio is in the range of 0.3-0.6. When used with the same high Mg / ID ratio, conventional diether donors are immobilized to a much lower degree, and the performance of the derived catalyst deteriorates.

[0026] The solid catalyst component may also contain a small amount of additional metal compounds selected from those containing elements belonging to groups 1 to 15, preferably groups 11 to 15, of the periodic table (IUPAC version).

[0027] Most preferably, the metal-carbon bond-free compound contains an element selected from Cu, Zn, and Bi. Preferred compounds are oxides, carbonates, alkoxylates, carboxylates, and halides of the metal. Among these, ZnO, ZnCl2, CuO, CuCl2, Cu diacetate, BiCl 3、 Bi carbonates and Bi carboxylates are preferred. 3、 Bi carbonates and Bi carboxylates are particularly preferred.

[0028] The compound can be added during the production of the aforementioned magnesium alcohol adduct, or it can be dispersed in a titanium compound in liquid form and introduced into a catalyst, which is then reacted with the adduct. In any method used, the final amount of the metal in the final catalyst component is in the range of 0.1 to 10% by weight, preferably 0.3 to 8% by weight, and most preferably 0.5 to 5% by weight, relative to the total weight of the solid catalyst component.

[0029] The solid catalyst component according to the present invention is converted into a catalyst for olefin polymerization by reacting it with an organoaluminum compound according to a known method.

[0030] In particular, the object of the present invention is a catalyst for the polymerization of olefins CH2=CHR (wherein R is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms), which comprises a product obtained by contacting the following: (i) Solid catalyst components disclosed above (ii) Alkylaluminum compounds and, optionally, (iii) External electron donor compounds.

[0031] The alkyl-Al compound (ii) is preferably selected from among trialkylaluminum compounds such as triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum. Alternatively, alkylaluminum halides, alkylaluminum hydrides, or alkylaluminum sesquichlorides, such as AlEt2Cl and Al2Et3Cl3, can be used in combination with the above trialkylaluminum compounds.

[0032] The catalyst component of the present invention provides highly stereoregular polypropylene even when polymerization is carried out in the absence of an external donor. This is demonstrated by the fact that the amount of xylene-insoluble fraction is 97.5% by weight or more, preferably 98% by weight or more. Furthermore, the above stereoregular polypropylene can be obtained in very high yield. In particular, when polymerized in liquid propylene at 70°C for 2 hours, the polymerization activity is 100 kg pol / g cat Higher, more preferably 115kg pol / g cat Higher. In some cases, activity is 130 kg pol / g cat It can sometimes exceed that.

[0033] When used, suitable external electron donor compounds (iii) include silicon compounds, ethers, esters, amines, heterocyclic compounds, particularly 2,2,6,6-tetramethylpiperidine and ketones.

[0034] Another class of preferred external donor compounds is given by formula (R 7 ) a (R 8 ) b Si(OR 9 ) c This is a silicon compound, where a and b are integers from 0 to 2, c is an integer from 1 to 4, and the sum (a+b+c) is 4. 7 , R 8 , and R 9is an alkyl, cycloalkyl, or aryl radical having 1 to 18 carbon atoms and optionally containing a heteroatom. Particularly preferred is when a is 1, b is 1, c is 2, and R 7 and R 8 At least one of them is selected from branched alkyl, cycloalkyl, or aryl groups having 3 to 10 carbon atoms, which optionally contain a heteroatom, and R 9 C1~C 10 The silicon compound is an alkyl group, particularly a methyl group. Examples of such preferred silicon compounds include methylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), diisopropyldimethoxysilane, (2-ethylpiperidinyl)t-butyldimethoxysilane, (2-ethylpiperidinyl)texyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2-ethylpiperidinyl)dimethoxysilane, and methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane. Furthermore, a is 0, c is 3, and R 8 is optionally a branched alkyl or cycloalkyl group containing a heteroatom, and R 9 Silicon compounds in which the group is a methyl group are also preferred. Examples of such preferred silicon compounds include cyclohexyltrimethoxysilane, t-butyltrimethoxysilane, and texyltrimethoxysilane.

[0035] The external electron donor compound (iii) is used in such an amount that the molar ratio of the organoaluminum compound to the electron donor compound (iii) is 0.1:1 to 500:1, preferably 1:1 to 300:1, and more preferably 3:1 to 100:1.

[0036] Therefore, a further object of the present invention is a method for (co)polymerizing olefins CH2=CHR (wherein R is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms) in the presence of a catalyst comprising the following reaction products: (i) Solid catalyst component of the present invention, (ii) alkylaluminum compounds and, (iii) Optional electron-donating compound (external donor).

[0037] Polymerization processes can be carried out according to known techniques, such as slurry polymerization using an inert hydrocarbon solvent as a diluent, or bulk polymerization using a liquid monomer (e.g., propylene) as the reaction medium. Furthermore, it is also possible to carry out the polymerization process in the gas phase by operating in one or more fluidized bed reactors or mechanically agitated bed reactors.

[0038] The catalyst of the present invention can be used directly in the polymerization process by introducing it directly into the reactor. In a preferred embodiment, the catalyst may be prepolymerized before being introduced into the first polymerization reactor. As used in this art, the term “prepolymerization” refers to a catalyst that has been subjected to the polymerization process to a low degree of conversion. According to the present invention, the catalyst is considered to have been prepolymerized when the amount of polymer produced is about 0.1 to about 1000 grams per gram of solid catalyst component.

[0039] Prepolymerization can be carried out using (-olefins) selected from the same group of olefins disclosed earlier. In particular, it is especially preferable to prepolymerize ethylene or a mixture thereof with one or more (-olefins) in amounts up to 20 mol%. Preferably, the conversion rate of the prepolymerization catalyst component is from about 0.2 grams to about 500 grams per gram of solid catalyst component.

[0040] The prepolymerization step can be carried out in the liquid or gas phase at a temperature of 0° to 80°C, preferably 5° to 50°C. The prepolymerization step can be performed inline as part of a continuous polymerization process or separately in a batch process. It is particularly preferable to batch prepolymerize the catalyst of the present invention with ethylene to produce an amount of polymer ranging from 0.5 to 20 grams per gram of catalyst component.

[0041] Polymerization is typically carried out at a temperature of 20–120°C, preferably 40–80°C. When polymerization is carried out in the gas phase, the operating pressure is generally 0.5–5 MPa, preferably 1–4 MPa. In bulk polymerization, the operating pressure is generally 1–8 MPa, preferably 1.5–5 MPa.

[0042] Preferred alpha-olefins to be (co)polymerized are ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene. In particular, the catalysts described above can be used in the (co)polymerization of propylene and ethylene to produce a variety of products, especially homopolymers and copolymers of propylene. Given their high activity and stereospecificity, the catalysts of the present invention can be advantageously used in the production of propylene / ethylene copolymers with low xylene soluble content, as well as high-purity polypropylene polymers with very low content of halogens (Cl) and metals such as Ti, Mg, and Al. In particular, when used in the production of propylene / ethylene copolymers in which the ethylene content is in the range of 0.1 to 6% wt based on the total weight of propylene and ethylene, the catalysts of the present disclosure can provide copolymers with a low amount of xylene soluble substances.

[0043] These catalysts are also suitable for producing high-impact polymer compositions comprising (A) a crystalline propylene homopolymer or copolymer matrix and, in certain applications, a substantial amount of (B) a low-crystalline, xylene-soluble propylene-ethylene-based copolymer exceeding 50%.

[0044] Such polymer compositions are preferably produced in a multi-stage process involving at least two different polymerization stages carried out in different reactors. Typically, the first step in producing a crystalline propylene homopolymer or copolymer can be carried out in either the gas phase or the liquid phase. Gas-phase polymerization can be carried out in a fixed-bed reactor with a fluidized bed or agitated bed, or in a gas-phase reactor containing two interconnected polymerization zones (one of which operates under fast fluidization conditions and the other in which the polymer flows under the action of gravity). The liquid-phase process can be carried out with a slurry, solution, or bulk (liquid monomer). This latter technique is most preferred and can be carried out in various types of reactors such as continuous agitated tank reactors, loop reactors, and plug-flow reactors. Preferably, the first step is carried out in the gas phase. Hydrogen can be used as a molecular weight modifier in this stage and / or subsequent stages.

[0045] In the second stage of the polymerization process, the propylene-ethylene copolymer (B) is preferably produced in a conventional fluidized bed gas-phase reactor in the presence of the polymer material and catalyst system obtained from the preceding polymerization step.

[0046] The polymer produced at this stage may contain 15–75% wt of ethylene, and optionally a small amount of diene, and its solubility in xylene at 25°C may be at least 60% wt.

[0047] The following examples are provided to illustrate the present invention and are not intended to limit the invention itself. Characteristic evaluation Measurement of porosity

[0048] Porosity and surface area due to mercury: The measurements are performed using a Carlo Erba Pascal 140-240 series porosity meter. Porosity is determined by the intrusion of pressurized mercury. A calibrated dilatometer (capillary diameter 3 mm) CD3P (Carlo Erba) connected to a mercury tank and a high-vacuum pump is used for this measurement. A weighed sample was placed in the dilatometer. The apparatus was then placed under high vacuum and maintained for approximately 20 minutes. Next, the dilatometer was connected to a mercury reservoir, and mercury was slowly filled into the dilatometer until it reached a marked height of 10 cm. The valve connecting the dilatometer to the vacuum pump was closed, and the mercury pressure was gradually increased to 100 kPa using nitrogen. The calibrated dilatometer was then transferred to an autoclave containing a high-pressure oil to reach a maximum pressure of 200 MPa. Due to the pressure, the mercury enters the pores of the particles, and the mercury level decreases accordingly. Porosity (cm 3 The pore size distribution curve and average pore diameter (per g) were calculated directly from the integral pore size distribution curve, which is a function of both the volume reduction of mercury and the applied pressure. All of this data was provided and processed by a porosimeter-related computer equipped with specialized software provided by Carlo Erba. After calculation, the average pore radius is given as a weighted average of the single average pore radius contributions at each porosity interval. Decision XI

[0049] Approximately 2.5 grams of polymer and 250 ml of o-xylene were placed in a round-bottom flask equipped with a condenser and a reflux condenser and stored under nitrogen. The resulting mixture was heated to 135°C and stirred for approximately 60 minutes. The final solution was cooled to 25°C with continuous stirring, and the insoluble polymer was filtered out. The filtrate was then evaporated under a nitrogen stream at 140°C to a constant weight. The content of the xylene-soluble fraction was expressed as a percentage of the original 2.5 grams, and then expressed as 10% by the difference. Decision on the donor

[0050] The electron donor content was measured by gas chromatography. Measurement of Melt Flow Rate (MFR)

[0051] The polymer melt flow rate (MIL) was measured according to ISO 1133 (230°C, 2.16 kg). Comonomer determination

[0052] The comonomer (ethylene) content was measured by NMR spectroscopy. Tm's decision The sample was measured using differential scanning calorimetry (DSC). A sample weighing 6 mg was weighed and heated to 220 (1°C) in a nitrogen stream at a rate of 20°C / min. It was maintained at 220 (1°C) for 2 minutes, then cooled to 40 (>2°C) at a rate of 20°C / min and maintained at this temperature for 2 minutes to crystallize the sample. The sample was then remelted to 220 (1°C) at a temperature increase rate of 20°C / min. A melting scan was recorded, a thermogram was obtained, and the melting and crystallization temperatures were read from it. Measurement of intrinsic viscosity (IV)

[0053] The intrinsic viscosity of the xylene-soluble fraction was measured. The sample was dissolved in tetrahydronaphthalene at 135°C and poured into a capillary viscometer. The viscometer tube (Ubbelohde type) was surrounded by a cylindrical glass jacket, allowing for temperature control using a circulating temperature-controlled liquid. The time it took for the meniscus to descend was measured using a photoelectric device. The passage of the meniscus in front of the upper lamp activated a counter equipped with a quartz oscillator. The counter stopped when the meniscus passed the lower lamp, and the efflux time was recorded. This was converted to an intrinsic viscosity value using Huggins' formula (Huggins, ML, J. Am. Chem. Soc., 1942, 64, 2716), provided that the efflux time of the pure solvent under the same experimental conditions (same viscometer and same temperature) was known. A single polymer solution was used to determine [η]. Measurement of flexural modulus

[0054] The flexural modulus was measured according to ISO 178 and ISO 1873-2. Measurement of Tensile Modulus The tensile modulus was measured according to ISO 527 and ISO 1873-2. Charpy measurement

[0055] Charpy impact test in accordance with ISO 179-1eA and ISO 1873-2 Propylene / ethylene copolymer 13 Determination of CNMR spectrum

[0056] Heterophase copolymer and its XI and XS fractions 13 The ¹ S (( Carbon peak (Nomenclature is "Monomer Sequence Distribution in Ethylene-propylene Rubber Measured by 13 ¹³C NMR. 3. Use of Reaction Probability Mode (following CJ Carman, RA Harrington, and CE Wilkes, Macromolecules, 1977, 10, 536) was used as an internal reference at 29.9 ppm. Samples were dissolved in 1,1,2,2-tetrachloroethane-d2 at 120°C to a concentration of 8% wt / v. Each spectrum was acquired using a 90° pulse, a 15-second delay between pulses, and CPD to remove 1H-13C coupling. Using a 9000 Hz spectral window, 512 transients were stored in 32K data points.

[0057] Spectral assignment, evaluation of triad distribution, and composition were performed according to Kakugo ("Carbon-13 NMR Measurement of Monomer Sequence Distribution of Ethylene-Propylene Copolymer Prepared with δ-Titanium Trichloride-Diethylaluminum Chloride," M. Kakugo, Y. Naito, K. Mizunuma, and T. Miyatake, Macromolecules, 1982, 15, 1150) using the following formula. PPP=100T ββ / SPPE=100T βδ / SEPE=100T δδ / S PEP=100S ββ / SPEE=100S βδ / SEEE=100(0.25Sγ δ +0.5S δδ ) / S S=T ββ +T βδ +T δδ +S ββ +S βδ +0.25Sγ δ +0.5S δδ

[0058] The molar percentage of ethylene content was evaluated using the following formula. E%mol=100([PEP+PEE+EEE]

[0059] The weight percentage of ethylene content was evaluated using the following formula. E%wt=100(MW E (E%mol / (MW E (E%mol+MW P (P%mol) (wherein P%mol is the molar percentage of propylene content, MW) E and MW P (These are the molecular weights of ethylene and propylene, respectively.) Examples General procedure for the preparation of MgCl2*pEtOH adducts

[0060] The initial amount of microspherical MgCl2*2.8EtOH was prepared according to the method described in Example 2 of U.S. Patent No. P4,399,054, but operated at 3,000 rpm instead of 10,000 rpm. Next, a portion of the adduct thus obtained was subjected to thermal dealcoholization in a nitrogen stream, with the temperature increasing from 30°C to 130°C, until the molar alcohol content per mole of Mg reached 2.1. Preparation of an electron donor Synthesis of 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane Step 1: Synthesis of diethyl 2-cyclohexylmalonate

[0061] Ethanol (400 mL) and potassium tert-butoxide (50 g, 0.4 mol) were added to a 1 L round-bottom flask equipped with a mechanical stirrer, thermometer, and condenser. Subsequently, diethyl malonate (63 g, 0.4 mol) was added dropwise over 10 minutes, and the formation of a white suspension was observed. The temperature was raised to 76°C, and cyclohexyl bromide was added over 30 minutes. After refluxing the mixture for 40 hours, the solvent was removed under vacuum, and the slurry was recovered with ethyl acetate (200 mL). The organic phase was washed with water (2 × 100 mL) and 10% NaHCO3, and evaporated to obtain 26 g of diethyl 2-cyclohexylmalonate (purity 99% (GC), yield 27%) as a pale yellow oily substance. 1 1H NMR (δ, 400 MHz, CDCl3): 4.2 (q, 4H, OCH2), 3.2 (d, 1H, CH Malonic), 2.1 (m, 1H, CH Cyclohexyl), 1.8-0.8 (m, 16H, OCH2CH3+ Cyclohexyl). Step 2: Synthesis of diethyl 2-cyclohexyl-2-isopentylmalonate

[0062] In a 500 mL round-bottom flask equipped with a mechanical stirrer, thermometer, and condenser, tetrahydrofuran (120 mL), diethyl 2-cyclohexylmalonic acid (26 g, 105 mmol), and sodium hydride (95%, 3 g, 119 mmol) were added. The temperature was raised to 40°C, and gas generation was observed. After 1 hour, when gas generation ceased, isopentyl bromide (20 g, 130 mmol) was added over 30 minutes. The mixture was refluxed for 25 hours, then diluted with 300 mL of 1 M HCl, the organic phase was diluted with diethyl ether (200 mL), washed with water (2 × 100 mL), and evaporated to obtain 23 g of diethyl 2-cyclohexyl-2-isopentylmalonate (purity 95% (GC), yield 67%) as a pale yellow oily substance. 1 1H NMR (δ, 400 MHz, CDCl3): 4.1 (q, 4H, OCH2), 1.7 (m, 3H, CH2-cyclohexyl + α-CH2-isopentyl), 1.6-1.3 (m, 8H, cyclohexyl), 1.2 (m, 7H, OCH2CH3 + γ-CH2-isopentyl), 1.0 (m, 4H, cyclohexyl + β-CH2-isopentyl), 0.8 (d, 6H, (CH3)2-isopentyl). Step 3: Synthesis of 2-cyclohexyl-2-isopentyl-1,3-propanediol

[0063] In a 500 mL round-bottom flask equipped with a mechanical stirrer, thermometer, and condenser, tetrahydrofuran (100 mL), diethyl 2-cyclohexyl-2-isopentyl malonate (95%, 23 g, 70 mmol), and lithium aluminum hydride (95%, 3 g, 77 mmol) were added. The mixture was refluxed for 16 hours and then diluted with 200 mL of 1 M HCl. The organic phase was extracted with diethyl ether (200 mL), washed with water (2 × 100 mL), and evaporated to obtain 15 g of 2-cyclohexyl-2-isopentyl malonate-1,3-propanediol (purity 98% (GC), yield 92%) as a colorless viscous oil. 11H NMR (δ, 400 MHz, CDCl3): 4.9–4.6 (dd, 4H, OCH2), 2.2 (s, 2H, OH), 1.9–1.1 (m, 16H, cyclohexyl + isopentyl), 0.9 (d, 6H, (CH3)2 isopentyl). Step 4: Synthesis of 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane

[0064] In a 500 mL round-bottom flask equipped with a mechanical stirrer, thermometer, and condenser, tetrahydrofuran (70 mL), 2-cyclohexyl-2-isopentyl-1,3-propanediol (98%, 15 g, 64 mmol), and sodium hydride (95%, 3 g, 128 mmol) were added. The temperature was raised to 40 °C (gas generation), and methyl iodide (20 g, 141 mmol) was added dropwise over 1 hour. Subsequently, the slurry was left at 40 °C for 8 hours, and then diluted with 200 mL of 1 M HCl. The organic phase was diluted with diethyl ether (100 mL), washed with water (2 × 50 mL), and evaporated to obtain 16 g of 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane (purity 99% (GC), yield 98%) as a colorless oil. 1 1H NMR (δ, 400 MHz, CDCl3): 3.2 (s, 6H, CH3O), 3.1 (s, 4H, OCH2), 1.8-1.0 (m, 16H, cyclohexyl + isopentyl), 0.8 (d, 6H, (CH3)2 isopentyl). Synthesis of 2-cyclohexyl-2-(3,3,3-trifluoro-n-propyl)-1,3-dimethoxypropane Step 1: Synthesis of diethyl 2-cyclohexyl-2-(3,3,3-trifluoro-n-propyl)malonate

[0065] The derivative was prepared using 1-iodo-3,3,3-trifluoro-n-propane as the alkylating agent, according to the synthesis described in Example 1-Step 2. The product was a pale yellow oil with a purity of 97% and a yield of 50%. 11H NMR (δ, 400 MHz, CDCl3): 4.2 (q, 4H, OCH2), 2.2 - 1.5 (m, 10H, cyclohexyl + 3,3,3 - trifluoro - n - propyl), 1.2 (t, 6H, OCH2CH3), 1.1 - 0.9 (m, 5H, cyclohexyl + 3,3,3 - trifluoro - n - propyl). Step 2: Synthesis of 2 - cyclohexyl - 2 - (3,3,3 - trifluoro - n - propyl) - 1,3 - propanediol

[0066] This derivative was prepared according to the synthesis described in Step 3 of Example 1. The product is an orange viscous oil with a purity of 98.5% and a yield of 92%. 1 1H NMR (δ, 400 MHz, CDCl3): 3.7 - 3.5 (dd, 4H, OCH2), 2.5 (s, 2H, OH), 2.0 (m, 2H, β - CH2 3,3,3 - trifluoro - n - propyl), 1.8 - 0.9 (m, 13H, cyclohexyl + 3,3,3 - trifluoro - n - propyl). Step 3: Synthesis of 2 - cyclohexyl - 2 - (3,3,3 - trifluoro - n - propyl) - 1,3 - dimethoxypropane

[0067] This derivative was prepared according to the synthesis described in Step 4 of Example 1. The product is a yellow oil with a purity of 98% and a yield of 95%. 1 1H NMR (δ, 400 MHz, CDCl3): 3.2 (s, 6H, CH3O), 3. (s, 4H, OCH2), 2.1 (m, 2H, β - CH2 3,3,3 - trifluoro - n - propyl), 1.8 - 0.9 (m, 13H, cyclohexyl + 3,3,3 - trifluoro - n - propyl). Synthesis of 2 - cyclohexyl - 2 - (3 - methylpentyl) - 1,3 - dimethoxypropane Step 1: Synthesis of diethyl 2 - cyclohexyl - 2 - (3 - methylpentyl)malonate

[0068] The derivative was prepared using 1-bromo-3-methylpentane as the alkylating agent, according to the synthesis described in Example 1-Step 2. The product is a colorless oil with a purity of 92% and a yield of 82%. 1 1H NMR (δ, 400 MHz, CDCl3): 4.2 (q, 4H, OCH2), 2.1-1.5 (m, 8H, cyclohexyl + 3-methylpentyl), 1.3 (t, 6H, OCH2CH3), 1.2-0.8 (m, 16H, cyclohexyl + 3-methylpentyl). Step 2: Synthesis of 2-cyclohexyl-2-(3-methylpentyl)-1,3-propanediol

[0069] This derivative was prepared according to the synthesis described in Step 3 of Example 1. The product is a yellow, viscous oil with a purity of 92% and a yield of 92%. 1 1H NMR (δ, 400 MHz, CDCl3): 3.7-3.5 (dd, 4H, OCH2), 2.7 (s, 2H, OH), 1.6-0.8 (m, 24H, cyclohexyl + 3-methylpentyl). Step 3: Synthesis of 2-cyclohexyl-2-(3-methylpentyl)-1,3-dimethoxypropane

[0070] This derivative was prepared according to the synthesis described in Step 4 of Example 1. The product was distilled at 145°C / 6 mmHg using a Vigreaux apparatus to obtain a colorless oil with a purity of 96% and a yield of 81%. 1 1H NMR (δ, 400 MHz, CDCl3): 3.3 (s, 6H, CH3O), 3.2 (s, 4H, OCH2), 1.8-1.0 (m, 18H, cyclohexyl + 3-methylpentyl), 0.8 (m, 6H, 3-methylpentyl). Synthesis of 2-cyclohexyl-2-(3-ethylpentyl)-1,3-dimethoxypropane Step 1: Synthesis of diethyl 2-cyclohexyl-2-(3-ethylpentyl)malonate

[0071] Using 1-bromo-3-ethylpentane as the alkylating agent, this derivative was produced according to the synthesis described in Example 1 - Step 2. The product is a yellow oily substance with a purity of 87% and a yield of 77%. 1 HNMR (δ, 400 MHz, CDCl3): 4.2 (q, 4H, OCH2), 2.1 - 1.5 (m, 8H, cyclohexyl + 3-ethylpentyl), 1.2 (t, 6H, OCH2CH3), 1.1 - 0.8 (m, 18H, cyclohexyl + 3-ethylpentyl). Step 2: Synthesis of 2-cyclohexyl-2-(3-ethylpentyl)-1,3-propanediol

[0072] This derivative was produced according to the synthesis described in Step 3 of Example 1. The product is a colorless viscous oily substance with a purity of 86% and a yield of 95%. 1 HNMR (δ, 400 MHz, CDCl3): 3.7 - 3.5 (dd, 4H, OCH2), 2.2 (s, 2H, OH), 1.6 - 0.8 (m, 26H, cyclohexyl + 3-ethylpentyl). Step 3: Synthesis of 2-cyclohexyl-2-(3-ethylpentyl)-1,3-dimethoxypropane This derivative was produced according to the synthesis described in Step 4 of Example 1. The product is a colorless oily substance with a purity of 95% and a yield of 86%. 1 HNMR (δ, 400 MHz, CDCl3): 3.2 (s, 6H, CH3O), 3.1 (s, 4H, OCH2), 1.8 - 1.0 (m, 20H, cyclohexyl + 3-ethylpentyl), 0.8 (m, 6H, 3-ethylpentyl). Synthesis of 2-cyclohexyl-2-(3,5-dimethylhexyl)-1,3-dimethoxypropane Step 1: Synthesis of diethyl 2-cyclohexyl-2-(3,5-dimethylhexyl)malonate

[0073] The derivative was prepared using 1-bromo-3,5-dimethylhexane as the alkylating agent, according to the synthesis described in Example 1-Step 2. The product is a brown oily substance with a purity of 92% and a yield of 78%. 1 1H NMR (δ, 400 MHz, CDCl3): 4.2 (q, 4H, OCH2), 1.9-1.3 (m, 10H, cyclohexyl + 3,5-dimethylhexyl), 1.2 (t, 6H, OCH2CH3), 1.1-0.8 (m, 8H, cyclohexyl + 3,5-dimethylhexyl), 0.7 (m, 10H, 3,5-dimethylhexyl). Step 2: Synthesis of 2-cyclohexyl-2-(3,5-dimethylhexyl)-1,3-propanediol

[0074] This derivative was prepared according to the synthesis described in Step 3 of Example 1. The product is a yellow, viscous oil with a purity of 96% and a yield of 96%. 1 1H NMR (δ, 400 MHz, CDCl3): 3.7-3.5 (dd, 4H, OCH2), 2.3 (s, 2H, OH), 1.7-0.8 (m, 18H, cyclohexyl + 3,5-dimethylhexyl), 0.7 (m, 10H, 3,5-dimethylhexyl). Step 3: Synthesis of 2-cyclohexyl-2-(3,5-dimethylhexyl)-1,3-dimethoxypropane

[0075] This derivative was prepared according to the synthesis described in Step 4 of Example 1. The product is a colorless oil with a purity of 96% and a yield of 94%. 1 1H NMR (δ, 400 MHz, CDCl3): 3.3 (s, 6H, CH3O), 3.2 (s, 4H, OCH2), 1.8-0.9 (m, 18H, cyclohexyl + 3,5-dimethylhexyl), 0.7 (m, 10H, 3,5-dimethylhexyl).

[0076] Synthesis of 2-cyclohexyl-2-n-pentyl-1,3-dimethoxypropane Step 1: Synthesis of diethyl 2-cyclohexyl-2-n-pentylmalonate

[0077] The derivative was prepared using n-pentyl bromide as the alkylating agent, according to the synthesis described in step 2 of Example 1. The product was a pale yellow oil with a purity of 90% and a yield of 80%. 1 1H NMR (δ, 400 MHz, CDCl3): 4.1 (q, 4H, OCH2), 1.9-1.6 (m, 8H, cyclohexyl + n-pentyl), 1.4-0.9 (m, 17H, OCH2CH3 + cyclohexyl + n-pentyl), 0.8 (t, 3H, CH3n-pentyl). Step 2: Synthesis of 2-cyclohexyl-2-n-pentyl-1,3-propanediol

[0078] This derivative was prepared according to the synthesis described in Step 3 of Example 1. The product is a colorless, viscous oil with a purity of 98% and a yield of 75%. 1 1H NMR (δ, 400 MHz, CDCl3): 3.9-3.7 (dd, 4H, OCH2), 2.2 (s, 2H, OH), 1.8-1.0 (m, 19H, cyclohexyl + n-pentyl), 0.9 (t, 3H, CH3n-pentyl). Step 3: Synthesis of 2-cyclohexyl-2-n-pentyl-1,3-dimethoxypropane

[0079] This derivative was prepared according to the synthesis described in step 4 of Example 1. The product is a colorless oil with a purity of 98% and a yield of 96%. 1 1H NMR (δ, 400 MHz, CDCl3): 3.3 (s, 6H, CH3O), 3.2 (s, 4H, OCH2), 1.8-1.0 (m, 19H, cyclohexyl + n-pentyl), 0.9 (t, 3H, CH3n-pentyl). Synthesis of 2-cyclohexyl-2-n-butyl-1,3-dimethoxypropane Step 1: Synthesis of diethyl 2-cyclohexyl-2-n-butylmalonate

[0080] The derivative was prepared using an n-butyl bromide as the alkylating agent, according to the synthesis described in step 2 of Example 1. The product was a pale yellow oil with a purity of 96% and a yield of 79%. 1 1H NMR (δ, 400 MHz, CDCl3): 4.1 (q, 4H, OCH2), 1.9-1.6 (m, 8H, cyclohexyl + n-butyl), 1.4-0.9 (m, 15H, OCH2CH3 + cyclohexyl + n-butyl), 0.8 (t, 3H, CH3n-butyl). Step 2: Synthesis of 2-cyclohexyl-2-n-butyl-1,3-propanediol

[0081] This derivative was prepared according to the synthesis described in Step 3 of Example 1. The product is a colorless, viscous oil with a purity of 99% and a yield of 85%. 1 1H NMR (δ, 400 MHz, CDCl3): 3.9-3.7 (dd, 4H, OCH2), 2.2 (s, 2H, OH), 1.8-1.0 (m, 17H, cyclohexyl + n-butyl), 0.9 (t, 3H, CH3n-butyl). Step 3: Synthesis of 2-cyclohexyl-2-n-butyl-1,3-dimethoxypropane

[0082] This derivative was prepared according to the synthesis described in step 4 of Example 1. The product is a colorless oil with a purity of 98% and a yield of 99%. 1 1H NMR (δ, 400 MHz, CDCl3): 3.3 (s, 6H, CH3O), 3.2 (s, 4H, OCH2), 1.8-1.1 (m, 17H, cyclohexyl + n-butyl), 0.9 (t, 3H, CH3n-butyl). Synthesis of 2-cyclohexyl-2-isobutyl-1,3-dimethoxypropane Step 1: Synthesis of diethyl 2-cyclohexyl-2-isobutylmalonate

[0083] Using isobutyl bromide as the alkylating agent, the derivative was prepared according to the synthesis described in Example 1-Step 2. The product was a pale yellow oil with a purity of 92% and a yield of 80%. 1 1H NMR (δ, 400 MHz, CDCl3): 4.1 (q, 4H, OCH2), 1.9-1.6 (m, 8H, cyclohexyl + n-butyl), 1.4-0.9 (m, 12H, OCH2CH3 + cyclohexyl + n-butyl), 0.8 (d, 6H, (CH3)2-isobutyl). Step 2: Synthesis of 2-cyclohexyl-2-isobutyl-1,3-propanediol

[0084] This derivative was prepared according to the synthesis described in Step 3 of Example 1. The product was a colorless, viscous oil with a purity of 88% and a yield of 84%. 1 1H NMR (δ, 400 MHz, CDCl3): 3.9–3.7 (dd, 4H, OCH2), 2.3 (s, 2H, OH), 1.8–1.0 (m, 14H, cyclohexyl + isobutyl), 0.9 (d, 6H, (CH3)2-isobutyl). Step 3: Synthesis of 2-cyclohexyl-2-isobutyl-1,3-dimethoxypropane

[0085] This derivative was prepared according to the synthesis described in Step 4 of Example 1. The final product was purified by distillation (115°C / 0.5 mmHg) to obtain a colorless oil with a purity of 98% and a yield of 75%. 1 1H NMR (δ, 400 MHz, CDCl3): 3.3 (s, 6H, CH3O), 3.3 (s, 4H, OCH2), 1.8-1.1 (m, 14H, cyclohexyl + isobutyl), 0.9 (d, 6H, (CH3)2-isobutyl). Synthesis of 2-cyclopentyl-2-isopentyl-1,3-dimethoxypropane Step 1: Synthesis of diethyl 2-cyclopentyl malonate

[0086] The derivative was prepared using cyclopentyl bromide as the alkylating agent, according to the synthesis described in Step 1 of Example 1. The product is a colorless oil with a purity of 99% and a yield of 56%. 1 HNMR (δ, 400 MHz, CDCl3): 1 1H NMR (δ, 400 MHz, CDCl3): 4.2 (q, 4H, OCH2), 3.2 (d, 1H, CH3 Malonic), 2.2 (m, 1H, CH3 Cyclopentyl), 1.7-0.8 (m, 14H, OCH2CH3+ Cyclopentyl). Step 2: Synthesis of diethyl 2-cyclopentyl-2-isopentylmalonate

[0087] Using isobutyl bromide as the alkylating agent, the derivative was prepared according to the synthesis described in Example 1-Step 2. The product was a pale yellow oil with a purity of 92% and a yield of 80%. 1 1H NMR (δ, 400 MHz, CDCl3): 4.1 (q, 4H, OCH2), 2.4 (m, 3H, CH3 cyclopentyl + α-CH2 isopentyl), 1.6-1.3 (m, 8H, cyclopentyl), 1.2-1.0 (m, 9H, OCH2CH3 3 + Isopentyl), 0.8 (d, 6H, (CH3)2 isopentyl). Step 3: Synthesis of 2-cyclopentyl-2-isopentyl-1,3-propanediol

[0088] This derivative was prepared according to the synthesis described in Step 3 of Example 1. The product is a colorless, viscous oil with a purity of 97% and a yield of 90%. 1 1H NMR (δ, 400 MHz, CDCl3): 3.8-3.6 (dd, 4H, OCH2), 2.4 (s, 2H, OH), 1.7-1.0 (m, 14H, cyclopentyl + isopentyl), 0.9 (d, 6H, (CH3)2 isopentyl). Step 4: Synthesis of 2-cyclopentyl-2-isopentyl-1,3-dimethoxypropane

[0089] This derivative was prepared according to the synthesis described in step 4 of Example 1. The final product is a colorless oil with a purity of 98% and a yield of 92%. 1 1H NMR (δ, 400 MHz, CDCl3): 3.3 (s, 6H, CH3O), 3.3 (s, 4H, OCH2), 1.8-1.1 (m, 14H, cyclopentyl + isopentyl), 0.9 (d, 6H, (CH3)2 isopentyl). Preparation of Solid Catalyst Components - General Procedure

[0090] 500 mL of TiCl4 was introduced into a 1000 mL four-necked round-bottom flask purged with nitrogen at 0°C. While stirring, 20 grams of microspherical MgCl2·2,1EtOH adduct (prepared as described above) was added. Next, an amount of electron donor of formula (I) such that the Mg / donor ratio was 6 was added at 0°C. The temperature was raised to 100°C and maintained for 120 minutes. Afterward, stirring was stopped, the liquid was aspirated, and the treatment with TiCl4 was repeated at 120°C for 60 minutes. Following precipitation and siphon treatment, the solid was washed with anhydrous isohexane (6 × 100 ml) and dried to obtain a fluid powder. The properties of the solid catalyst components obtained in this way are shown in Table 1. General procedure for bulk homopolymerization of propylene

[0091] A 4-liter steel autoclave equipped with a stirrer, pressure gauge, thermometer, catalyst supply system, monomer supply line, and thermostat jacket was purged with a nitrogen stream at 70°C for 1 hour. Then, under a propylene stream at 30°C, 75 ml of anhydrous hexane containing 30.76 g of AlEt, approximately 6 mg of solid catalyst component, and, if used, an external donor (type and amount listed in the table) was added in that order. The autoclave was closed, followed by the addition of 2 NL of hydrogen. Next, 1.2 kg of liquid propylene was supplied with stirring. The temperature was raised to 70°C in 10 minutes, and polymerization was carried out at this temperature for 2 hours. At the end of polymerization, unreacted propylene was removed, the polymer was recovered, and dried in an oven at 80°C.

[0092] Examples 1-5 and Comparative Examples 6-10: Polymerization of Propylene

[0093] The catalysts of Examples 1-5 and Comparative Examples 6-9 of the present invention were prepared using the donors listed in Table 1 and following the general procedure described above. The catalyst properties and the results of bulk polymerization of propylene are shown in Table 1.

[0094] [Table 1] [Table 1-1] Examples 13-16 Catalyst preparation

[0095] 500 mL of TiCl4 was introduced into a 1000 mL four-necked round-bottom flask purged with nitrogen at -3°C. While stirring, 20 grams of microspherical MgCl2 2.1EtOH adduct (prepared as described above) was added. Next, for some of the preparations shown in Table 2, BiCl3 was added at -3°C in an amount that resulted in a Mg / BiCl3 ratio of 60 mr.

[0096] In all preparations, the temperature was raised to 100°C and maintained at this value for 30 minutes. Then, stirring was stopped, the liquid was aspirated, and fresh TiCl4 and 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane as an internal donor were added to the Mg / ID ratio reported in Table 2. The temperature was then raised to 120°C for 30 minutes with stirring. After stopping stirring, the liquid was aspirated, and the treatment with TiCl4 was repeated at 120°C for 15 minutes. After precipitation and siphon treatment, the solid was washed with anhydrous isohexane (6 × 200 ml) and dried to obtain a fluid powder. Details of the catalyst preparation, characterization, and results of bulk polymerization of propylene are shown in Table 2. Comparative Example 17 Catalyst preparation

[0097] The catalyst was prepared as described in Example 16, except that 9,9-bis(methoxymethyl)fluorene was used as the internal donor instead of 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane. Details of the catalyst preparation, characterization, and results of the bulk polymerization of propylene are shown in Table 2.

[0098] [Table 2] [Table 2-1] TEAL / C donor molar ratio 20 Example 18

[0099] The initial amount of microspherical MgCl2·2.8C2H5OH was prepared according to the method described in Example 2 of U.S. Patent No. P4,399,054, but operated at 3,000 rpm instead of 10,000 rpm. The adduct thus obtained, with an average particle size of 87 μm, was subjected to thermal dealcoholization in a nitrogen stream, increasing the temperature from 30°C to 130°C until the molar alcohol content per mole of Mg reached 1.16. Using this support, catalysts were prepared and tested according to the general procedure already described. Details of catalyst preparation, characterization, and the results of bulk polymerization of propylene are shown in Table 3. Comparative Example 19

[0100] The catalyst was prepared as described in Example 18, except that 9,9-bis(methoxymethyl)fluorene was used as the internal donor instead of 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane. Details of the catalyst preparation, characterization, and results of the bulk polymerization of propylene are shown in Table 3.

[0101] [Table 3] TEAL / ED molar ratio = 4

Claims

1. A solid catalyst component for the polymerization of olefins, Magnesium halide, titanium compound having at least one Ti-halogen bond, and at least one compound of formula (I) (I) (wherein, R １ and R ２ are independently C １ - C ５ alkyl groups, X is Si or C, and R ３ and R ４ groups are independently selected from hydrogen, C １ - C ２０ hydrocarbon groups and halogen, provided that at least two of R ３ are not hydrogen) It includes an electron donor, and The molar ratio of the electron donor in formula (I) to the Ti atoms in the final solid catalyst component is in the range of 0.3:1 to 1.5:

1. A solid catalyst component for olefin polymerization, wherein the molar ratio of Mg atoms in the final solid catalyst component to the electron donor of formula (I) is in the range of 2.5:1 to 50.0:

1.

2. The aforementioned R １ and R ２ They are identical, C １ -C ４ A solid catalyst component according to claim 1, selected from a linear or branched alkyl group.

3. All of the aforementioned R ４ The solid catalyst component according to claim 2, wherein the base is hydrogen.

4. The aforementioned R ３ If it is a hydrocarbon group, C １ ~C ４ Linear or branched alkyl groups, and C １ ~C ４ The solid catalyst component according to claim 2, which is optionally substituted with a linear alkyl group and selected from groups that are linked together to form a C6 saturated ring.

5. The solid catalyst component according to claim 1, wherein the molar ratio of the electron donor of formula (I) to the Ti atoms in the final solid catalyst component is in the range of 0.4:1 to 1.3:

1.

6. The solid catalyst component according to claim 1, wherein the molar ratio of Mg atoms in the final solid catalyst component to the electron donor of formula (I) is in the range of 3:1 to 45.0:

1.

7. The solid catalyst component according to claim 1, wherein there is an additional donor selected from the group consisting of esters of aliphatic dicarboxylic acids.

8. The solid catalyst component according to claim 1, comprising an additional metal compound that does not contain metal-carbon bonds and contains an element selected from Cu, Zn, and Bi.

9. A catalyst for polymerization of olefin CH2=CHR (where R is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms), (i) A solid catalyst component according to any one of claims 1 to 8, (ii) A catalyst for the polymerization of olefins, comprising a reaction product with an alkylaluminum compound.

10. The process is carried out in the presence of the catalyst described in claim 9, olefin CH ２ A method for (co)polymerization of CHR (wherein R is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms).

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