Catalyst component 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 donor compound selected from 1,3-diether. The catalyst component is particularly suitable for the production of propylene homopolymers and copolymers.

Background Art

[0002] Catalyst components for the stereospecific polymerization of olefins are disclosed in the art. For the polymerization of propylene, generally, a Ziegler-Natta catalyst is used, which includes a solid catalyst component composed of a magnesium dihalide supported with a titanium compound and an internal electron donor compound, and is used in combination with an aluminum alkyl compound. However, conventionally, when a higher crystallinity of the polymer is desired, an external donor (e.g., alkoxysilane) is also required to obtain higher isotacticity. Phthalic esters, particularly phthalate with diisobutyl groups, are used as internal donors in catalyst preparation. This catalyst system, in which phthalic esters 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 a catalyst system that does not use phthalic esters as electron donors.

[0004] European Patent Application No. 361494 A2, International Patent Application No. 02 / 100904, and International Patent Application No. 2021 / 063930 describe solid catalyst components for the polymerization of olefins containing 1,3 - diethers characterized by a specific structure as internal electron donor compounds. Despite generally good performance, there is still a need for catalyst components without phthalate donors 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 catalyst component even in the absence of an external donor.

Summary of the Invention

[0006] Therefore, one object 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 an electron donor of at least formula (I).

[0007]

Chemical Formula

Modes for Carrying Out the Invention

[0008] Preferably, R 1 and R 2 are the same and are C 1 - C 4It is selected from linear or branched alkyl, 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, the R 4 groups are independently selected from hydrogen, C 1 ~C 10 hydrocarbon groups and halogens. More preferably, they are selected from hydrogen, C 1 ~C 4 linear or branched alkyl groups and halogens. Even more preferably, only one or two of the R 4 groups are C 1 ~C 4 linear or branched alkyl groups or halogens. Preferred alkyl groups are methyl, isopropyl or t-butyl groups, and preferred halogens are Cl and F. Structures in which all R 4 groups are hydrogen are also preferred.

[0011] The R 3 groups are preferably selected from hydrogen, C 1 ~C 10 hydrocarbon groups and halogens. When R 3 is a hydrocarbon group, it is preferably selected from C 1 ~C 4 linear or branched alkyl groups, optionally C 1 ~C 4 linear alkyl groups substituted and linked together to form a C6 saturated ring, and particularly preferred alkyl groups are methyl, ethyl and isobutyl groups.

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

[0013] According to a preferred embodiment, X is carbon and R 3is hydrogen, C 1 ~C 20 a hydrocarbon group or a halogen. Preferably, the hydrocarbon group is C 1 ~C 4 selected from linear or branched alkyl groups, more preferably selected from methyl groups. Most preferably, one R 3 is selected from hydrogen and the remaining two are selected from methyl groups.

[0014] Another group of preferred structures is where X is carbon and R 3 is hydrogen or a halogen group, preferably selected from Cl and F, more preferably selected from F. Most preferably, at least two of the R 3 are selected from F, and more preferably, all R 3 groups are F.

[0015] According to another preferred embodiment, X is Si and R 3 is hydrogen or a hydrocarbon group, preferably selected from C 1 ~C 4 linear or branched alkyl groups, more preferably selected from methyl groups or ethyl groups. Most preferably, all R 3 groups are selected from methyl groups.

[0016] Specific examples of the compounds of formula (I) that can be advantageously used include the following. 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, 2-cyclohexyl-2-(3,3,3-tribromopropyl)-1,3-dimethoxypropane, 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-fluoro-propyl)-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)-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-diphenylethoxypropane, 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-fluoro-propyl)-1,3-diphenylethoxypropane, 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-triphenylpropyl)-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-diphenylethylpentyl)-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-methoxy-propane, 2-cyclohexyl-2-(3,3-difluorobutyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-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-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-fluoro-propyl)-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-methoxy-propane, 2-cyclohexyl-2-(3-chloro-3-isobutyl-5-methylhexyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3-bromo-3-isobutyl-5-methylhexyl)-1-ethoxy-3-propoxy-propane, 2-cyclohexyl-2-(3-fluoro-3-isobutyl-5-methylhexyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3-fluoro-3-isopentyl-6-methylheptyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3-chloro-3-isopentyl-6-methylhept, (Chir)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3-bromo-3-isopentyl-6-methylheptyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-diphenylbutyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-diphenylpropyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3,3-triphenylpropyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3,3-tris(4-chlorophenyl)propyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-diphenylmethylbutyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3-methylpentyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3-ethylpentyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-diphenylethylpentyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3-isopropyl-4-methylpentyl)-1-ethoxy-3-methoxy-propane, 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-methoxy-propane, 2-cyclohexyl-2-(2-triphenylsilylethyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(2-methyldiphenylsilylethyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(2-diphenylmethylphenylsilylethyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(2-(tris(4-chlorophenyl)silyl)ethyl)-1-ethoxy-3-isobutoxy-propane, 2-cyclohexyl-2-(2-(bis(4-chlorophenyl)(methyl)silyl)ethyl)-1-ethoxy-3-methoxy-propane, 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-methylcyclohexyl)-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-methylcyclohexyl)-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-methoxy-propane, 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-dimethoxypropane, 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)cyclohexylethyl)-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-fluorenylethyl)-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-dichloropropyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-dichloro-3-fluoro-propyl)-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-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-methoxy-propane, 2-(4-(tert-Butyl)cyclohexyl)-2-(3,3-dimethylbutyl)-1,3-dimethoxypropane, 2-(2-Isopropyl-5-methylcyclohexyl)-2-(3-methylpentyl)-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-triphenylsilylethyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(2-methyldiphenylsilylethyl)-1-ethoxy-3-methoxy-propane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(2-dimethylphenylsilylethyl)-1-ethoxy-3-methoxy-propane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(2-(tris(4-chlorophenyl)silyl)ethyl)-1-ethoxy-3-isobutoxy-propane, 2-(3,5-dimethylcyclohexyl)-2-(2-(bis(4-chlorophenyl)(methyl)silyl)ethyl)-1-ethoxy-3-methoxy-propane.,

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

[0018] Preferably, the molar ratio of the Mg atom 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, more preferably in the range of 3:1 to 45.0:1, still more preferably in the range of 5.0:1 to 30.0:1, and particularly more preferably in the range of 6.0:1 to 25.0:1.

[0019] Additional electron donors may, in principle, be present in the catalyst component of the present disclosure. Preferably, they are selected from mono-esters or di-esters of aromatic or aliphatic carboxylic acids. More preferably, they are selected from esters of aliphatic dicarboxylic acids such as malonate, succinate, glutarate, etc. described in International Patent No. 99 / 57160. The additional donor may be present in an amount of less than 0.1 to 50.0% mol, preferably 0.5 to 45.0%, based on the total molar amount of the bifunctional electron donor. When the additional donor is different from the ester of the aliphatic dicarboxylic acid, its amount is preferably less than 10% mol, more preferably less than 8% mol, based on the total molar amount of the electron donor.

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

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

[0022] As described above, the catalyst component of the present invention contains, in addition to the above 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 TiCl 4 and TiCl 3 , and further, Ti haloalcoholates of the formula Ti(OR 5 ) n-y X y can also be used, where n is the valence of titanium, y is a number from 1 to n -1 , X is a halogen, and R 5 i is a hydrocarbon group having 1 to 10 carbon atoms.

[0023] The preparation of the solid catalyst component can be carried out according to several methods. According to a preferred method, the solid catalyst component has the formula Ti(OR5 ) m-y X y (where m is the valence of titanium and y is a number from 1 to m.) a titanium compound, preferably TiCl 4 is prepared by reacting with magnesium chloride derived from an adduct of the formula MgCl 2 ·pR 6 OH (where p is a number from 0.1 to 6, preferably from 2 to 3.5, and R 6 is a hydrocarbon group having 1 to 18 carbon atoms.) The adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct and operating with stirring at the melting point of the adduct (100 - 130 °C). Thereafter, the emulsion is rapidly quenched, whereby the adduct solidifies in the form of spherical particles. Examples of spherical adducts produced according to this procedure are described in U.S. Patent No. P4,399,054 and U.S. Patent No. P4,469,648. The adduct thus obtained can be reacted directly with the Ti compound or, alternatively, can be subjected to pre-heat-controlled dealcoholization (80 - 130 °C) to obtain an adduct in which the molar number of alcohol is less than 3, preferably from 0.1 to 2.5, more preferably from 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 highly dealcoholized adducts such that the molar number of alcohol per mole of Mg is less than 2. Using these dealcoholized adducts, the conventional diether donors are fixed to a much lower extent and the performance of the derived catalyst is reduced.

[0025] In a preferred method of manufacturing the catalyst of the present invention, the reaction with the Ti compound is carried out by adding the adduct (dealcoholized or as it is) to cold TiCl 4Among them, it can generally be carried out by suspending at 0 °C. Preferably, the adduct is used in an amount such that the concentration is 20 to 100 g / l, preferably 30 to 90 g / l. According to a preferred embodiment, the electron donor (I) is added to the system at the start of this stage of the reaction, preferably when the temperature of the mixture is in the range of 10 °C to 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 to 25:1, preferably 2:1 to 25:1, more preferably 2:1 to 15:1, particularly 3:1 to 10:1. Then, the temperature is gradually increased to reach a temperature of 90 to 130 °C and held at this temperature for 0.5 to 3 hours. When the reaction time is completed, the stirring is stopped, the slurry is allowed to settle, and the liquid phase is removed. TiCl 4 The second stage of the treatment with is carried out, preferably at a temperature of 70 to 130 °C. When the reaction time is completed, the 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 TiCl 4 can be carried out in the absence of an electron donor under the same conditions as above. The solid thus obtained can then be washed with a liquid hydrocarbon and dried under mild conditions. The catalyst based on the electron donor of formula (I) of the present invention is produced at a relatively high Mg / ID molar ratio (13 to 20), and even when the amount of ID fixed on the catalyst is such that the ID / Ti molar ratio is in the range of 0.3 to 0.6, it can provide very good performance. When used at the same high Mg / ID ratio, the prior art diether donor is fixed to a much lower extent and the performance of the derived catalyst is reduced.

[0026] The solid catalyst component may also contain a small amount of additional metal compound 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 compound containing no metal-carbon bond contains an element selected from Cu, Zn, and Bi. Preferred compounds are oxides, carbonates, alkoxylates, carboxylates, and halides of the aforementioned metals. Among these, ZnO, ZnCl 2 , CuO, CuCl 2 , copper diacetate, BiCl 3、 bismuth carbonate, and bismuth carboxylate are preferred. BiCl 3、 bismuth carbonate, and bismuth carboxylate are particularly preferred.

[0028] The compound can be added during the production of the aforementioned magnesium alcohol adduct, or dispersed in a titanium compound in liquid form and introduced into the catalyst, and then reacted with the adduct. In any case, the final amount of the metal in the final catalyst component ranges from 0.1 to 10% by weight, preferably from 0.3 to 8% by weight, and most preferably from 0.5 to 5% by weight based on 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 with an organoaluminum compound according to a known method.

[0030] In particular, an object of the present invention is a catalyst for the polymerization of an olefin CH 2 =CHR (wherein R is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms), and the catalyst contains a product obtained by bringing the following into contact. (i) The solid catalyst component disclosed above (ii) an alkylaluminum compound and, optionally, (iii) an external electron donor compound.

[0031] The alkyl-Al compound (ii) is preferably selected from trialkylaluminum compounds such as triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, etc. Also, alkylaluminum halides, alkylaluminum hydrides, or alkylaluminum sesquichlorides, such as AlEt 2 Cl and Al 2 Et 3 Cl 3 can also be used by mixing with the above-mentioned trialkylaluminum compounds.

[0032] The catalyst component of the present invention provides highly stereoregular polypropylene even when polymerizing in the absence of an external donor. This is proven by the amount of the xylene-insoluble fraction being 97.5% by weight or more, preferably 98% by weight or more. In addition, the above-mentioned stereoregular polypropylene can be obtained in a very high yield. In particular, when polymerizing in liquid propylene at 70 °C for 2 hours, the polymerization activity is 100 kg pol / g cat or higher, more preferably 115 kg pol / g cat or higher. In some cases, the activity may exceed 130 kg pol / g cat .

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

[0034] Another class of preferred external donor compounds is the silicon compound of the formula (R 7 ) a (R 8 ) b Si(OR 9 ) c , wherein 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. R 7 , R8 and R 9 is an alkyl, cycloalkyl, or aryl radical having from 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 is selected from branched alkyl, cycloalkyl or aryl groups having from 3 to 10 carbon atoms optionally containing a heteroatom, and R 9 is a C 1 -C 10 alkyl group, in particular a methyl group, a silicon compound. 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, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane. Further, when a is 0, c is 3, R 8 is a branched alkyl or cycloalkyl group optionally containing a heteroatom, and R 9 is a methyl group, a silicon compound is also preferred. Examples of such preferred silicon compounds include cyclohexyltrimethoxysilane, t-butyltrimethoxysilane, and texyltrimethoxysilane.

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

[0036] Accordingly, a further object of the present invention is a (co)polymerization method of an olefin CH 2 =CHR (wherein R is hydrogen or a hydrocarbon group having from 1 to 12 carbon atoms) carried out in the presence of a catalyst comprising the following reaction product: (i) The solid catalyst component of the present invention, (ii) an alkylaluminum compound, and (iii) optionally an electron donor compound (external donor).

[0037] The polymerization process 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 a reaction medium. Further, it is also possible to operate in one or more fluidized bed reactors or mechanically stirred bed reactors to carry out the polymerization process in the gas phase.

[0038] The catalyst of the present invention can be directly introduced into the reactor and used as it is in the polymerization process. In a preferred embodiment, the catalyst can be prepolymerized before being introduced into the first polymerization reactor. The term "prepolymerization" used in this technology means a catalyst that has been subjected to a polymerization step at a low conversion degree. According to the present invention, when the amount of the polymer produced is about 0.1 to about 1000 grams per gram of the solid catalyst component, the catalyst is considered to be prepolymerized.

[0039] The prepolymerization can be carried out using an α-olefin selected from the same group of olefins disclosed above. In particular, it is particularly preferred to prepolymerize ethylene or a mixture thereof with one or more α-olefins in an amount up to 20 mol%. Preferably, the conversion rate of the prepolymerized catalyst component is from about 0.2 grams to about 500 grams per gram of the solid catalyst component.

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

[0041] The polymerization is usually carried out at a temperature of 20 to 120 °C, preferably 40 to 80 °C. When the polymerization is carried out in the gas phase, the operating pressure is generally 0.5 to 5 MPa, preferably 1 to 4 MPa. In bulk polymerization, the operating pressure is generally 1 to 8 MPa, preferably 1.5 to 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 above catalyst can be used for the (co)polymerization of propylene and ethylene to produce various types of products of propylene homopolymers and copolymers in particular. Considering the high activity and stereospecificity, the catalyst of the present invention can be advantageously used for the production of a propylene / ethylene copolymer with a low xylene-soluble content and a high-purity polypropylene polymer with a very low content of metals such as halogen (Cl) and Ti, Mg, Al. In particular, when used for the production of a propylene / ethylene copolymer in which the ethylene content ranges from 0.1 to 6% wt based on the total weight of propylene and ethylene, the catalyst of the present disclosure can provide a copolymer with a low amount of xylene-soluble substances.

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

[0044] Such polymer compositions are preferably produced by a multi-step process comprising at least two different polymerization stages carried out in different reactors. Usually, the first step of producing a crystalline propylene homopolymer or copolymer can be carried out either in the gas phase or in the liquid phase. Gas phase polymerization can be carried out in a fluidized bed or stirred bed fixed bed reactor, or in a gas phase reactor comprising two interconnected polymerization zones, one of which operates under high fluidization conditions and the other is a zone where the polymer flows under the action of gravity. The liquid phase process can be carried out either in slurry, solution, or bulk (liquid monomer). The latter technique is most preferred and can be carried out in various types of reactors such as continuous stirred tank reactors, loop reactors, plug flow reactors, etc. Preferably, the first step is carried out in the gas phase. In this step and / or subsequent steps, hydrogen can be used as a molecular weight regulator.

[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, may contain a small amount of diene if necessary, and the solubility in xylene at 25 °C may be at least 60% wt.

[0047] The following examples are presented to illustrate the invention and are not intended to limit the invention itself. Characteristic Evaluation Measurement of Porosity

[0048] Porosity and Surface Area by Mercury: Measurements are carried out using a Pascal 140 - 240 series porosimeter manufactured by Carlo Erba. Porosity is determined by the intrusion of mercury under pressure. For this measurement, a calibrated dilatometer (capillary diameter 3 mm) CD connected to a mercury tank and a high vacuum pump 3P (manufactured by Carlo Erba) was used. The measured sample was placed in a dilatometer. Next, the apparatus was placed under high vacuum and maintained in this state for about 20 minutes. Next, the dilatometer was connected to a mercury reservoir, and the dilatometer was slowly filled with mercury until it reached a height of 10 cm marked on the dilatometer. The valve connecting the dilatometer to the vacuum pump was closed, and the mercury pressure was gradually increased to 100 kPa with nitrogen. Then, the calibrated dilatometer was transferred to an autoclave containing a high-pressure oil substance so that the pressure value reached a maximum of 200 MPa. Due to the influence of pressure, mercury penetrated into the pores of the particles, and accordingly, the mercury level decreased. Porosity (cm 3 / g), pore size distribution curve, and average pore diameter were directly calculated from the integrated pore size distribution curve, which is a function of both the volume reduction of mercury and the applied pressure value. All of these data were provided and processed by a computer related to a porosimeter equipped with dedicated software provided by Carlo Erba. After calculation, the average pore radius is given as the weighted average of the single average pore radius contributions at each porosity interval. Determination of X.I.

[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 about 60 minutes. The final solution was cooled to 25 °C while continuously stirring, and the insoluble polymer was filtered. Next, the filtrate was evaporated at 140 °C in a nitrogen stream to a constant weight. The content of the xylene-soluble fraction is expressed as a percentage relative to the original 2.5 grams and is then expressed as X.I.% by difference. Determination of Donor

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

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

[0052] The content of the comonomer (ethylene) was measured by NMR spectroscopy. Determination of Tm It was measured by differential scanning calorimetry (DSC). 6 (1 mg of the weight was weighed, heated to 220 (1 °C at a rate of 20 °C / min in a nitrogen stream, 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. Then, the sample was remelted to 220 °C (1 at a temperature increase rate of 20 °C / min. The melting scan was recorded, a thermogram was obtained, and the melting temperature and crystallization temperature were read from this. Measurement of Intrinsic Viscosity (I.V.)

[0053] For the xylene-soluble fraction, the intrinsic viscosity was measured. The sample was dissolved in tetralin at 135 °C and poured into a capillary viscometer. The viscometer tube (Ubbelohde type) is surrounded by a cylindrical glass jacket, and this setting enables temperature control by the circulating temperature-controlled liquid. The time for the meniscus to descend was measured by a photoelectric device. The passage of the meniscus in front of the upper lamp activated a counter equipped with a crystal oscillator. When the meniscus passed through the lower lamp, the counter stopped and the efflux time was recorded. This was converted to the value of the intrinsic viscosity by Huggins' equation (Huggins, M.L., J. Am. Chem. Soc., 1942, 64, 2716) on the condition that the efflux time of the pure solvent under the same experimental conditions (the same viscometer and the same temperature) was known. A single polymer solution was used to determine [η]. Measurement of Flexural Modulus

[0054] The flexural modulus was measured in accordance with ISO 178 and ISO 1873-2. Measurement of Tensile Modulus The tensile modulus was measured in accordance with ISO 527 and ISO 1873-2. Measurement of Charpy

[0055] Charpy impact test conforming to ISO 179-1eA and ISO 1873-2 of Propylene / Ethylene Copolymer 13 Determination of 13C NMR Spectrum

[0056] Of the heterophasic copolymer and its XI and XS fractions 13 The 13C NMR spectra were acquired on a Bruker AV-600 spectrometer equipped with a cryoprobe operating at 120 °C, Fourier transform mode, 160.91 MHz. S (( The carbon peak (nomenclature according to "Monomer Sequence Distribution in Ethylene-propylene Rubber Measured by 13 13C NMR. 3. Use of Reaction Probability Mode" C. J. Carman, R. A. Harrington, and C. E. Wilkes, Macromolecules, 1977, 10, 536) was used as the internal standard at 29.9 ppm. The sample was dissolved in 1,1,2,2-tetrachloroethane-d 2 at 120 °C to a concentration of 8% wt / v. Each spectrum was acquired using a 90° pulse, a 15 s delay between pulses, and CPD to remove 1H-13C coupling. A spectral window of 9000 Hz was used and 512 transients were saved to 32K data points.

[0057] Spectral assignment, evaluation of the triad distribution, and composition were carried out according to Kakugo ("Carbon-13 NMR Measurement of Monomer Sequence Distribution of Ethylene-Propylene Copolymers Prepared with δ-Titanium Trichloride-Diethylaluminum Chloride" M. Kakugo, Y. Naito, K. Mizunuma, and T. Miyatake, Macromolecules, 1982, 15, 1150) using the following equations. PPP = 100T ββ / SPPE = 100T βδ / SEPE = 100Tδδ / 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) (where P%mol is the molar percentage of propylene content, MW E and MW P are the molecular weights of ethylene and propylene, respectively.) Examples MgCl 2 General procedure for the production of *pEtOH adduct

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

[0061] To a 1 L round-bottom flask equipped with a mechanical stirrer, a thermometer, and a condenser, ethanol (400 mL) and potassium tert-butoxide (50 g, 0.4 mol) were added. 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 collected with ethyl acetate (200 mL). The organic phase was washed with water (2 × 100 mL) and 10% NaHCO 3 and evaporated to give 26 g of diethyl 2-cyclohexylmalonate as a pale yellow oil (purity 99% (GC), yield 27%). 1 HNMR (δ, 400 MHz, CDCl 3 ): 4.2 (q, 4H, OCH 2 ), 3.2 (d, 1H, CH malonic), 2.1 (m, 1H, CH cyclohexyl), 1.8 - 0.8 (m, 16H, OCH 2 CH 3 + cyclohexyl. Step 2: Synthesis of diethyl 2-cyclohexyl-2-isopentylmalonate

[0062] To a 500 mL round-bottom flask equipped with a mechanical stirrer, a thermometer, and a condenser, tetrahydrofuran (120 mL), diethyl 2-cyclohexylmalonate (26 g, 105 mmol), and sodium hydride (95%, 3 g, 119 mmol) were added. The temperature was raised to 40 °C, and the evolution of gas was observed. After 1 hour, when the evolution of gas ceased, isopentyl bromide (20 g, 130 mmol) was added over 30 minutes. After refluxing the mixture for 25 hours, it was 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 give 23 g of diethyl 2-cyclohexyl-2-isopentylmalonate as a pale yellow oil (purity 95% (GC), yield 67%). 1 HNMR (δ, 400 MHz, CDCl 3): 4.1 (q, 4H, OCH 2 ), 1.7 (m, 3H, CH cyclohexyl + α-CH 2 isopentyl), 1.6 - 1.3 (m, 8H, cyclohexyl), 1.2 (m, 7H, OCH 2 CH 3 + γ-CH isopentyl), 1.0 (m, 4H, cyclohexyl + β-CH 2 isopentyl), 0.8 (d, 6H, (CH 3 ) 2 isopentyl). Step 3: Synthesis of 2-cyclohexyl-2-isopentyl-1,3-propanediol

[0063] To a 500 mL round-bottom flask equipped with a mechanical stirrer, thermometer, and condenser, tetrahydrofuran (100 mL), diethyl 2-cyclohexyl-2-isopentylmalonate (95%, 23 g, 70 mmol), and lithium aluminum hydride (95%, 3 g, 77 mmol) were added. After refluxing the mixture for 16 hours, it was 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 then evaporated to give 15 g of 2-cyclohexyl-2-isopentylmalonate-1,3-propanediol as a colorless viscous oil (purity 98% (GC), yield 92%). 1 HNMR (δ, 400 MHz, CDCl 3 ): 4.9 - 4.6 (dd, 4H, OCH 2 ), 2.2 (s, 2H, OH), 1.9 - 1.1 (m, 16H, cyclohexyl + isopentyl), 0.9 (d, 6H, (CH 3 ) 2 isopentyl). Step 4: Synthesis of 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane

[0064] To 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 evolution), 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), evaporated, and 16 g of 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane (purity 99% (GC), yield 98%) was obtained as a colorless oil. 1 HNMR (δ, 400 MHz, CDCl 3 ): 3.2 (s, 6H, CH 3 O), 3.1 (s, 4H, OCH 2 ), 1.8 - 1.0 (m, 16H, cyclohexyl + isopentyl), 0.8 (d, 6H, (CH 3 ) 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] Using 1-iodo-3,3,3-trifluoro-n-propane as the alkylating agent, this derivative was prepared 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%. 1 HNMR (δ, 400 MHz, CDCl 3 ): 4.2 (q, 4H, OCH 2 ), 2.2 - 1.5 (m, 10H, cyclohexyl + 3,3,3-trifluoro-n-propyl), 1.2 (t, 6H, OCH 2 CH 3), 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 HNMR (δ, 400 MHz, CDCl 3 ): 3.7 - 3.5 (dd, 4H, OCH 2 ), 2.5 (s, 2H, OH), 2.0 (m, 2H, β - CH 2 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 HNMR (δ, 400 MHz, CDCl 3 ): 3.2 (s, 6H, CH 3 O), 3.1 (s, 4H, OCH 2 ), 2.1 (m, 2H, β - CH 2 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] This derivative was produced according to the synthesis described in Example 1 - Step 2 using 1-bromo-3-methylpentane as the alkylating agent. The product is a colorless oil with a purity of 92% and a yield of 82%. 1 HNMR(δ, 400 MHz, CDCl 3 ): 4.2 (q, 4H, OCH 2 ), 2.1 - 1.5 (m, 8H, cyclohexyl + 3-methylpentyl), 1.3 (t, 6H, OCH 2 CH 3 ), 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 produced 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 HNMR (δ, 400 MHz, CDCl 3 ): 3.7 - 3.5 (dd, 4H, OCH 2 ), 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 produced 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 HNMR (δ, 400 MHz, CDCl 3 ): 3.3 (s, 6H, CH 3 O), 3.2 (s, 4H, OCH 2 ), 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] This derivative was prepared according to the synthesis described in Example 1 - Step 2, using 1-bromo-3-ethylpentane as the alkylating agent. The product is a yellow oil with a purity of 87% and a yield of 77%. 1 HNMR (δ, 400 MHz, CDCl 3 ): 4.2 (q, 4H, OCH 2 ), 2.1 - 1.5 (m, 8H, cyclohexyl + 3-ethylpentyl), 1.2 (t, 6H, OCH 2 CH 3 ), 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 prepared according to the synthesis described in Step 3 of Example 1. The product is a colorless viscous oil with a purity of 86% and a yield of 95%. 1 HNMR (δ, 400 MHz, CDCl 3 ): 3.7 - 3.5 (dd, 4H, OCH 2 ), 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 prepared according to the synthesis described in Step 4 of Example 1. The product is a colorless oil with a purity of 95% and a yield of 86%. 1 HNMR (δ, 400 MHz, CDCl 3 ): 3.2 (s, 6H, CH 3 O), 3.1 (s, 4H, OCH 2 ), 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] This derivative was prepared according to the synthesis described in Example 1 - Step 2 using 1-Bromo-3,5-dimethylhexane as the alkylating agent. The product is a brown oily substance with a purity of 92% and a yield of 78%. 1 HNMR (δ, 400 MHz, CDCl 3 ): 4.2 (q, 4H, OCH 2 ), 1.9 - 1.3 (m, 10H, cyclohexyl + 3,5-dimethylhexyl), 1.2 (t, 6H, OCH 2 CH 3 ), 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 oily substance with a purity of 96% and a yield of 96%. 1 HNMR (δ, 400 MHz, CDCl 3 ): 3.7 - 3.5 (dd, 4H, OCH 2 ), 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 oily substance with a purity of 96% and a yield of 94%. 1 HNMR (δ, 400 MHz, CDCl 3): 3.3 (s, 6H, CH 3 O), 3.2 (s, 4H, OCH 2 ), 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] This derivative was prepared according to the synthesis described in Step 2 of Example 1 using n - pentyl bromide as the alkylating agent. The product is a pale yellow oily substance with a purity of 90% and a yield of 80%. 1 HNMR (δ, 400 MHz, CDCl 3 ): 4.1 (q, 4H, OCH 2 ), 1.9 - 1.6 (m, 8H, cyclohexyl + n - pentyl), 1.4 - 0.9 (m, 17H, OCH 2 CH 3 + cyclohexyl + n - pentyl), 0.8 (t, 3H, CH 3 n - 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 oily substance with a purity of 98% and a yield of 75%. 1 HNMR (δ, 400 MHz, CDCl 3 ): 3.9 - 3.7 (dd, 4H, OCH 2 ), 2.2 (s, 2H, OH), 1.8 - 1.0 (m, 19H, cyclohexyl + n - pentyl), 0.9 (t, 3H, CH 3 n - pentyl). Step 3: Synthesis of 2 - cyclohexyl - 2 - n - pentyl - 1,3 - dimethoxypropane

[0079] 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 98% and a yield of 96%. 1 HNMR (δ, 400 MHz, CDCl 3 ): 3.3 (s, 6H, CH 3 O), 3.2 (s, 4H, OCH 2 ), 1.8 - 1.0 (m, 19H, cyclohexyl + n - pentyl), 0.9 (t, 3H, CH 3 n - pentyl). Synthesis of 2 - cyclohexyl - 2 - n - butyl - 1,3 - dimethoxypropane Step 1: Synthesis of diethyl 2 - cyclohexyl - 2 - n - butylmalonate

[0080] Using n - butyl bromide as the alkylating agent, this derivative was produced according to the synthesis described in Step 2 of Example 1. The product is a pale yellow oily substance with a purity of 96% and a yield of 79%. 1 HNMR (δ, 400 MHz, CDCl 3 ): 4.1 (q, 4H, OCH 2 ), 1.9 - 1.6 (m, 8H, cyclohexyl + n - butyl), 1.4 - 0.9 (m, 15H, OCH 2 CH 3 + cyclohexyl + n - butyl), 0.8 (t, 3H, CH 3 n - butyl). Step 2: Synthesis of 2 - cyclohexyl - 2 - n - butyl - 1,3 - propanediol

[0081] 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 99% and a yield of 85%. 1 HNMR (δ, 400 MHz, CDCl 3 ): 3.9 - 3.7 (dd, 4H, OCH 2), 2.2 (s, 2H, OH), 1.8 - 1.0 (m, 17H, cyclohexyl + n - butyl), 0.9 (t, 3H, CH 3 n - butyl). Step 3: Synthesis of 2 - cyclohexyl - 2 - n - butyl - 1,3 - dimethoxypropane

[0082] This derivative was produced 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 HNMR (δ, 400 MHz, CDCl 3 ): 3.3 (s, 6H, CH 3 O), 3.2 (s, 4H, OCH 2 ), 1.8 - 1.1 (m, 17H, cyclohexyl + n - butyl), 0.9 (t, 3H, CH 3 n - butyl). Synthesis of 2 - cyclohexyl - 2 - isobutyl - 1,3 - dimethoxypropane Step 1: Synthesis of diethyl 2 - cyclohexyl - 2 - isobutylmalonate

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

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

[0085] This derivative was produced 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 HNMR (δ, 400 MHz, CDCl 3 ): 3.3 (s, 6H, CH 3 O), 3.3 (s, 4H, OCH 2 ), 1.8-1.1 (m, 14H, cyclohexyl + isobutyl), 0.9 (d, 6H, (CH 3 ) 2 isobutyl). Synthesis of 2-cyclopentyl-2-isopentyl-1,3-dimethoxypropane Step 1: Synthesis of diethyl 2-cyclopentylmalonate

[0086] Using cyclopentyl bromide as the alkylating agent, this derivative was produced 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, CDCl 3 ): 1 HNMR (δ, 400 MHz, CDCl 3 ): 4.2 (q, 4H, OCH 2), 3.2 (d, 1H, CH malonic), 2.2 (m, 1H, CH cyclopentyl), 1.7 - 0.8 (m, 14H, OCH 2 CH 3 + cyclopentyl). Step 2: Synthesis of diethyl 2 - cyclopentyl - 2 - isopentylmalonate

[0087] This derivative was prepared according to the synthesis described in Example 1 - Step 2 using isobutyl bromide as the alkylating agent. The product is a pale yellow oily substance with a purity of 92% and a yield of 80%. 1 HNMR (δ, 400 MHz, CDCl 3 ): 4.1 (q, 4H, OCH 2 ), 2.4 (m, 3H, CH cyclopentyl + α - CH 2 isopentyl), 1.6 - 1.3 (m, 8H, cyclopentyl), 1.2 - 1.0 (m, 9H, OCH 2 CH 3 + isopentyl), 0.8 (d, 6H, (CH 3 ) 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 oily substance with a purity of 97% and a yield of 90%. 1 HNMR (δ, 400 MHz, CDCl 3 ): 3.8 - 3.6 (dd, 4H, OCH 2 ), 2.4 (s, 2H, OH), 1.7 - 1.0 (m, 14H, cyclopentyl + isopentyl), 0.9 (d, 6H, (CH 3 ) 2 isopentyl). Step 4: Synthesis of 2 - cyclopentyl - 2 - isopentyl - 1,3 - dimethoxypropane

[0089] This derivative was produced 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 HNMR (δ, 400 MHz, CDCl 3 ): 3.3 (s, 6H, CH 3 O), 3.3 (s, 4H, OCH 2 ), 1.8 - 1.1 (m, 14H, cyclopentyl + isopentyl), 0.9 (d, 6H, (CH 3 ) 2 isopentyl). Preparation of Solid Catalyst Component - General Procedure

[0090] 500 mL of TiCl 4 was introduced into a 1000 mL four-necked round-bottom flask purged with nitrogen at 0 °C. While stirring, 20 grams of fine spherical MgCl 2 ·2.1EtOH adduct (prepared as above) was added. Next, an electron donor of formula (I) in such an amount that Mg / donor was 6 was introduced at 0 °C. The temperature was raised to 100 °C and maintained at this temperature for 120 minutes. Then, stirring was stopped, the liquid was suctioned out, and treatment with TiCl 4 was repeated at 120 °C for 60 minutes. After precipitation and siphoning, the solid was washed with anhydrous isohexane (6 × 100 ml) and dried to obtain a free-flowing powder. The properties of the solid catalyst component thus obtained are shown in Table 1. General Procedure for Bulk Homopolymerization of Propylene

[0091] A 4-liter steel autoclave equipped with a stirrer, a pressure gauge, a thermometer, a catalyst supply system, a monomer supply line, and a thermostat jacket was purged with a nitrogen stream at 70 °C for 1 hour. Then, under a propylene flow, at 30 °C, AlEt 30.76 g, approximately 6 mg of solid catalyst component, and 75 ml of anhydrous hexane containing an external donor (type and amount are described in the table) were charged in this order. The autoclave was closed, and subsequently 2 NL of hydrogen was added. Next, 1.2 kg of liquid propylene was supplied while 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 the polymerization, unreacted propylene was removed, and the polymer was recovered and dried in an oven at 80 °C.

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

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

[0094] [Table 1] [Table 1-1] Examples 13 - 16 Preparation of catalyst

[0095] 500 mL of TiCl was introduced into a 1000 mL four-necked round-bottom flask purged with nitrogen at -3 °C. 4 While stirring, 20 grams of fine spherical MgCl 2 2.1EtOH adduct (prepared as above) was added. Next, for some of the preparations shown in Table 2, BiCl in an amount such that Mg / BiCl 3 becomes 60 mr was charged at -3 °C. 3

[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 suctioned out, and fresh TiCl 42-cyclohexyl-2-isopentyl-1,3-dimethoxypropane as the internal donor was added to achieve the Mg / ID reported in Table 2, and the temperature was raised to 120 °C over 30 minutes with stirring. After stopping the stirring, the liquid was suctioned out, and the treatment with TiCl 4 was repeated at 120 °C for 15 minutes. After precipitation and siphoning treatment, the solid was washed with anhydrous isohexane (6 × 200 ml) and dried to obtain a free-flowing 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] Catalyst preparation was carried out as described in Example 16, except that 9,9-bis(methoxymethyl)fluorene was used instead of 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane as the internal donor. Details of the catalyst preparation, characterization, and results of bulk polymerization of propylene are shown in Table 2.

[0098]

Table 2

Table 2-1

[0099] Microspherical MgCl 2 ·2.8C 2 H 5The initial amount of OH was prepared according to the method described in Example 2 of U.S. Patent No. P4,399,054, but was operated at 3,000 rpm instead of 10,000 rpm. The adduct having an average particle size of 87 μm thus obtained was thermally dealcoholized while raising the temperature from 30 °C to 130 °C in a nitrogen stream until the molar alcohol content per mole of Mg reached 1.16. Using this carrier, a catalyst was prepared and tested according to the general procedure already described. Details of the catalyst preparation, property evaluation, and results of bulk polymerization of propylene are shown in Table 3. Comparative Example 19

[0100] The catalyst preparation was carried out as described in Example 18, except that 9,9-bis(methoxymethyl)fluorene was used instead of 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane as the internal donor. Details of the catalyst preparation, property evaluation, and results of 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, comprising a magnesium halide, a titanium compound having at least one Ti-halogen bond, and at least one electron donor of formula (I). 【Chemical 1】 (I) (Here, R １ and R ２ are, independently, C １ to C ５ alkyl groups, X is Si or C, and R ３ and R ４ groups are, independently, selected from hydrogen C １ to C ２０ hydrocarbon groups and halogens, provided that at least two of R ３ are not hydrogen.)

2. Said R １ and said R ２ are the same, and C １ to C ４ The solid catalyst component according to claim 1, which is selected from a linear or branched alkyl group, more preferably selected from a methyl group.

3. Said R ４ group is independently selected from hydrogen, C １ -C １０ hydrocarbon group and halogen, the solid catalyst component according to any one of the preceding claims.

4. All of the above R ４ groups are hydrogen, the solid catalyst component according to claim 3.

5. Said R ３ is selected from hydrogen, C １ to C １０ a hydrocarbon group and a halogen, and is the solid catalyst component according to any one of the preceding claims.

6. Said R ３ When being a hydrocarbon group, C １ to C ４ linear or branched alkyl group, and C １ to C ４ The solid catalyst component according to any one of the preceding claims, selected from groups that form a C6 saturated ring linked together, optionally substituted with a linear alkyl group of.

7. Said R ３ When being a halogen, the catalyst component according to any one of the preceding claims, which is selected from Cl and F.

8. The solid catalyst component according to any one of Claims 1 to 7, wherein the X is carbon.

9. The solid catalyst component according to any one of the preceding claims, 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 0.3:1 to 1.5:1, more preferably 0.4:1 to 1.3:

1.

10. The solid catalyst component according to any one of Claims 1 to 4, wherein the molar ratio of the 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, more preferably 3:1 to 45.0:

1.

11. The solid catalyst component according to any one of Claims 1 to 6, in which an additional donor selected from the group consisting of esters of aliphatic dicarboxylic acids is present.

12. The solid catalyst component according to any one of Claims 1 to 4, comprising an additional metal compound that does not contain a metal-carbon bond and contains an element selected from Cu, Zn, and Bi.

13. Catalyst CH for olefin polymerization ２ =CHR (R is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms.), and (i) A solid catalyst component according to any one of Claims 1 to 4, (ii) A catalyst for the polymerization of olefins, comprising a reaction product between an alkylaluminum compound.

14. Formula (R ７ ), ａ (R ８ ), ｂ Si(OR ９ ), ｃ (wherein a and b are integers from 0 to 2, c is an integer from 1 to 4, the sum of (a + b + c) is 4, and R ７ , R ８ , and R ９ are alkyl, cycloalkyl or aryl radicals having 1 to 18 carbon atoms and optionally containing heteroatoms). The catalyst according to claim 13, further comprising an external electron donor compound selected from silicon compounds.

15. The (co)polymerization method of olefin CH ２ =CHR (wherein R is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms) carried out in the presence of the catalyst according to any one of claims 13 to 14.

Images