Catalyst components for polymerization of olefins

Abstract

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

Description

Technical Field

[0001] The present disclosure relates to a Ziegler-Natta heterogeneous catalyst component for the polymerization of olefins, in particular 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-diethers. The catalyst component is particularly suitable for the preparation of propylene homopolymers and propylene copolymers. Background Art

[0002] Catalyst components for stereospecific polymerization of olefins are disclosed in the art. About propylene polymerization, Ziegler-Natta catalyst is used, which generally includes a solid catalyst component, which is composed of a magnesium dihalide loaded with a titanium compound and an internal electron donor compound, and is used in combination with an alkyl aluminum compound. However, usually, when a higher polymer crystallinity is desired, an external donor (such as an alkoxysilane) is also required to obtain a higher isotacticity. The ester of phthalic acid, particularly diisobutyl phthalate, is used as an internal donor in the preparation of the catalyst. Phthalic acid esters are used in combination with an alkyl alkoxysilane as an external donor as an internal donor. The catalyst system has good performance in terms of activity, isotacticity and xylene insolubility.

[0003] In some cases, it is desirable to prepare polymers using catalyst systems that do not utilize phthalates as electron donors.

[0004] Patent applications EP361494A2, WO02 / 100904 and WO2021 / 063930 describe solid catalyst components for olefin polymerization, comprising as internal electron donor compound a 1,3-diether characterized by a specific structure. Despite generally good performances, there is still a perceived need for a catalyst component which is free of phthalate donors and which exhibits at the same time 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 provides the catalyst component with very high activity and very high stereospecificity even in the absence of an external donor. Summary of the invention

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

[0007]

[0008] Where R1 and R 2 are independently C1-C5 alkyl groups, X is Si or C, R 3 and R 4 The groups are independently selected from hydrogen, C1-C 20 A hydrocarbon group and a halogen, provided that at least two R 3 Not hydrogen. DETAILED DESCRIPTION

[0009] Preferably, R 1 and R 2 are the same and are selected from C1-C4 straight or branched chain alkyl groups, and more preferably selected from methyl groups.

[0010] The term hydrocarbyl group includes various groups such as alkyl, cycloalkyl, arylalkyl, alkenyl, aryl, arylalkylaryl and hydrocarbyl groups fused together to form a saturated or unsaturated ring.

[0011] Preferably, R 4 The groups are independently selected from hydrogen, C1-C 10 More preferably, they are selected from hydrogen, C1-C4 straight-chain or branched alkyl groups and halogen. Still more preferably, R 4 Only one or two of the groups are C1-C4 straight or branched alkyl groups or halogen. Preferred alkyl groups are methyl, isopropyl or tert-butyl, and preferred halogens are Cl and F. 4 Structures in which the radical is hydrogen are also preferred.

[0012] R 3 The group is preferably selected from hydrogen and C1-C 10 Hydrocarbyl groups and halogens. When R 3 When it is a hydrocarbyl group, it is preferably selected from C1-C4 straight or branched chain alkyl groups, groups linked together to form a C6 saturated ring optionally substituted by C1-C4 straight chain alkyl groups; particularly preferred alkyl groups are methyl, ethyl and isobutyl.

[0013] When R 3 When halogen, it is preferably selected from Cl and F. More preferably, the halogen is F.

[0014] According to a preferred embodiment, X is carbon and R 3 is hydrogen, C1-C 20 Preferably, the hydrocarbon group is selected from a C1-C4 straight or branched alkyl group, more preferably a methyl group. Most preferably, one of R 3 A structure in which one is selected from hydrogen and the remaining two are selected from methyl groups.

[0015] Another preferred group of structures is where X is carbon and R3 are hydrogen or a 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 The groups are those of F.

[0016] According to another preferred embodiment, X is Si, and R 3 is hydrogen or a hydrocarbon group preferably selected from a C1-C4 straight or branched alkyl group, more preferably selected from a methyl or ethyl group. Most preferably, all R 3 The group is selected from the structure of methyl.

[0017] Specific examples of compounds of formula (I) that can be advantageously used 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, 2-cyclohexyl-2-(3,3,3-tribromopropyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3,3-trichloropropyl)-1,3-dimethoxypropane, )-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-bromopropyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-difluoro-3-bromopropyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-difluoro-3-chloropropyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-difluoro-5-methylhexyl)-1,3-dimethoxypropane, 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-tri(4-chlorophenyl)propyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-dimethylbutyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3-methylpentyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3-ethylpentyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-diethylpentyl)-1,3-Dimethoxypropane, 2-cyclohexyl-2-(3-isopropyl-4-methylpentyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3-diisopropyl-4-methylpentyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(cyclohexylethyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(cyclopentylethyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(phenylethyl)-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-dimethylphenylsilylethyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(2-(tri(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-diallyloxypropane, 2-cyclohexyl-2-(3,3-difluorobutyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3,3-dibromobutyl)-1,3-diallyloxy 2-cyclohexyl-2-(3,3-dichlorobutyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3,3,3-trifluoropropyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3,3,3-tribromopropyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3,3,3-trichloropropyl)-1,3-dipropoxypropane, 2-cyclohexyl-2-(3,3-difluoropropyl)-1,3-diallyloxypropane, 2-cyclohexyl-2-(3,3-dibromopropyl)-1,3-dipropoxypropane, 2-cyclohexyl-2-(3,3-dichloropropyl)-1,3-dipropoxypropane, 2-cyclohexyl-2-(3,3-dichloro-3-fluoropropyl)-1,3 -diethoxypropane, 2-cyclohexyl-2-(3,3-dichloro-3-bromopropyl)-1,3-dipropoxypropane, 2-cyclohexyl-2-(3,3-difluoro-3-bromopropyl)-1,3-dibutoxypropane, 2-cyclohexyl-2-(3,3-difluoro-3-chloropropyl)-1,3-dipropoxypropane, 2-cyclohexyl-2-(3,3-difluoro-5-methylhexyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3,3-dichloro-5-methylhexyl)-1,3-dipropoxypropane, 2-cyclohexyl-2-(3-chloro-3-isobutyl-5-methylhexyl)-1,3-diisopentyloxypropane, 2-cyclohexyl-2-(3-bromo-3-isobutyl-5-methylhexyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3-fluoro-3-isobutyl-5-methylhexyl)-1,3-dipropoxypropane, 2-cyclohexyl-2-(3-fluoro-3-isopentyl-6-methylheptyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3-chloro-3-isopentyl-6-methylheptyl)-1,3-dibutoxypropane, 2-cyclohexyl-2-(3-bromo-3-isopentyl-6-methylheptyl)-1,3-dipropoxypropane, 2-cyclohexyl-2-(3,3-diphenylbutyl)-1,3-diallyloxypropane, 2-cyclohexyl-2-(3,3-diphenylpropyl)-1,3-diallyloxypropane, 2-cyclohexyl-2-(3,3,3-triphenylpropyl)-1,3-diallyloxypropane ,3-diethoxypropane, 2-cyclohexyl-2-(3,3,3-tri(4-chlorophenyl)propyl)-1,3-diallyloxypropane, 2-cyclohexyl-2-(3,3-dimethylbutyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3-methylpentyl)-1,3-diallyloxypropane, 2-cyclohexyl-2-(3-ethylpentyl)-1,3-diisopentyloxypropane, 2-cyclohexyl-2-(3,3-diethylpentyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3-isopropyl-4-methylpentyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3,3-diisopropyl-4-methylpentyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3,3-diisopropyl-4-methylpentyl)-1,3-diethoxypropane, 2-cyclohexyl-2- (Cyclohexylethyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(cyclopentylethyl)-1,3-diallyloxypropane, 2-cyclohexyl-2-(phenylethyl)-1,3-diisopentyloxypropane, 2-cyclohexyl-2-(2-trimethylsilylethyl)-1,3-dibutoxypropane, 2-cyclohexyl-2-(2-trimethylsilylethyl)-1,3-dibutoxypropane, 2-cyclohexyl-2-(2-triisopropylsilylethyl)-1,3-diisopentyloxypropane, 2-cyclohexyl-2-(2-triphenylsilylethyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(2-methyldiphenylsilylethyl)-1,3-diethoxypropane, 2-cyclohexyl-2 -(2-dimethylphenylsilylethyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(2-(tri(4-chlorophenyl)silyl)ethyl)-1,3-dibutoxypropane, 2-cyclohexyl-2-(2-(bis(4-chlorophenyl)(methyl)silyl)ethyl)-1,3-dibutoxypropane, 2-cyclohexyl-2-isopentyl-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-difluorobutyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-dibromobutyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-dichlorobutyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-dimethoxybutyl)-1-ethoxy-3-methoxypropane,3-trifluoropropyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3,3-tribromopropyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3,3-trichloropropyl)-1-methoxy-3-allyloxypropane, 2-cyclohexyl-2-(3,3-difluoropropyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-dibromopropyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-dichloropropyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-dichloro-3-fluoropropyl)-1-isobutoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-dichloro- 3-bromopropyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-difluoro-3-bromopropyl)-1-ethoxy-3-isopentyloxypropane, 2-cyclohexyl-2-(3,3-difluoro-3-chloropropyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-difluoro-5-methylhexyl)-1-ethoxy-3-methoxypropane, 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, -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)-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-diphenylpropyl)-1-ethoxy-3-methoxypropane, (3,3,3-triphenylpropyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3,3-tri(4-chlorophenyl)propyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-dimethylbutyl)-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-diethylpentyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3-isopropyl-4-methylpentyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(3,3-diisopropyl-4-methylpentyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(cyclohexylethyl)-1-ethoxy-3-propoxypropane, 2-cyclohexyl-2-(cyclopentylethyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(phenylethyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(2-trimethylsilylethyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(2-trimethylsilylethyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(2-triisopropylsilylethyl)-1-allyloxy-3-methoxypropane, 2-cyclohexyl-2-(2-triphenylsilylethyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(2-methyldiphenylsilane 2-(2-(tri(4-chlorophenyl)silyl)ethyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(2-(bis(4-chlorophenyl)(methyl)silyl)ethyl)-1-ethoxy-3-methoxypropane, 2-cyclohexyl-2-(2-(tri(4-chlorophenyl)silyl)ethyl)-1-ethoxy-3-isobutoxypropane, 2-cyclohexyl-2-(2-(bis(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-diethoxypropane, 2-(2-methylcyclohexyl)-2-(3,3-dichloro-3-bromopropyl)-1,3-dipropoxypropane, 2-(4-methylcyclohexyl)-2-(3,3-difluoro-3-bromopropyl)-1,3-dibutoxypropane, 2-(4-methylcyclohexyl)-2-(3,3-difluoro-3-chloropropyl)-1,3-dipropoxypropane, 2-(4-methylcyclohexyl)-2-(3,3-difluoro-5-methylhexyl)-1,3-diethoxypropane, 2-(4-methylcyclohexyl)-2-(3,3-dichloro-5-methylhexyl)-1,3-Dipropoxypropane, 2-(4-methylcyclohexyl)-2-(3-chloro-3-isobutyl-5-methylhexyl)-1,3-diisopentyloxypropane, 2-(4-methylcyclohexyl)-2-(3-bromo-3-isobutyl-5-methylhexyl)-1,3-diethoxypropane, 2-(3-methylcyclohexyl)-2-(3-fluoro-3-isobutyl-5-methylhexyl)-1 ,3-dipropoxypropane, 2-(4-methylcyclohexyl)-2-(3-fluoro-3-isopentyl-6-methylheptyl)-1,2-(3-methylcyclohexyl)-2-(3-chloro-3-isopentyl-6-methylheptyl)-1,3-dibutoxypropane, 2-(4-methylcyclohexyl)-2-(3-bromo-3-isopentyl-6-methylheptyl)-1,3-dipropoxypropane, 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-tri(4-chlorophenyl)propyl)-1-ethoxy-3-methoxypropane, 2-(2-methylcyclohexyl)-2-(3,3-dimethylbutyl)-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-(phenylethyl)-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-methoxypropane, 2-(4-methylcyclohexyl)-2-(2-dimethylphenylsilylethyl)-1-ethoxy-3-methoxypropane, 2-(4-methylcyclohexyl)-2-(2-(tris(4-chlorophenyl)silyl)ethyl)-1-ethoxy-3-isobutoxypropane, 2-(3-methylcyclohexyl)-2-(2-(bis(4-chlorophenyl)(methyl)silyl)ethyl)-1-ethoxy-3-methoxypropane, 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]heptane-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-isopropyl-5-methylcyclohexyl)-2-(3,3-dichloro-3-fluoropropyl)-1,3-diethoxypropane, 2-(4-(tert-butyl)cyclohexyl)-2-(3,3-dichloro-3-bromopropyl)-1,3-dipropoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-difluoro-3-bromopropyl)-1,3-dibutoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-difluoro-3-chloropropyl)-1,3-dipropoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-difluoro-3-chloropropyl)-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-difluoro-5-methylhexyl)-1,3-diethoxypropane 2-(2-isopropyl-5-methylcyclohexyl)-2-(3-chloro-3-isobutyl-5-methylhexyl)-1,3-diisopentyloxypropane, 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-fluoro-3-isopentyl-5-methylhexyl)-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-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-triphenylpropyl)-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-triphenylpropyl)-1,3-dimethoxypropane,3-tri(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-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 Methoxypropane, 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- 2-(5-methylcyclohexyl)-2-(phenylethyl)-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-methyldiphenyl 2-(2-isopropyl-5-methylcyclohexyl)-2-(2-dimethylphenylsilylethyl)-1-ethoxy-3-methoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(2-(tri(4-chlorophenyl)silyl)ethyl)-1-ethoxy-3-isobutoxypropane, 2-(3,5-dimethylcyclohexyl)-2-(2-(bis(4-chlorophenyl)(methyl)silyl)ethyl)-1-ethoxy-3-methoxypropane.

[0018] Preferably, the molar ratio between the electron donor of formula (I) and Ti atoms in the final solid catalyst component is in the range from 0.3:1 to 1.5:1, and more preferably from 0.4:1 to 1.3:1.

[0019] Preferably, the molar ratio between Mg atoms and the electron donor of formula (I) in the final solid catalyst component is in the range of from 2.5:1 to 50.0:1, more preferably from 3:1 to 45.0:1, more preferably from 5.0:1 to 30.0:1, and even more preferably from 6.0:1 to 25.0:1.

[0020] Additional electron donors may in principle be present in the catalyst components of the present 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 WO99 / 57160. Based on the total molar amount of the bifunctional electron donor, the additional donor may be present in an amount of from 0.1 to less than 50.0 mol%, preferably from 0.5 to 45.0%. If the additional donor is different from the ester of the aliphatic dicarboxylic acid, its amount is preferably less than 10 mol%, and more preferably less than 8 mol%, based on the total molar amount of the electron donor.

[0021] Preferably, the solid catalyst component has a mercury-determined 3 / g porosity, which is related to pores with a radius equal to or less than 1 μm. More preferably, the porosity is higher than 0.30 cm 3 / g, and especially above 0.40cm 3 / g.

[0022] Preferably, the catalyst component has an average particle size ranging from 20 to 150 μm, and more preferably from 40 to 100 μm.

[0023] As explained above, in addition to the above electron donors, the catalyst component of the present invention also includes a titanium compound having at least one Ti-halogen bond and a magnesium halide. Preferred titanium compounds used in the catalyst component of the present invention are TiCl4 and TiCl3; in addition, a compound of the formula Ti(OR 5 ) n-y X y Ti-haloalcoholates, wherein n is the valence of titanium, y is a number between 1 and n-1, X is a halogen, and R 5 is a hydrocarbyl radical having from 1 to 10 carbon atoms.

[0024] The preparation of the solid catalyst component can be carried out according to several methods. According to a preferred method, the solid catalyst component can be prepared by making a 5 ) m-y X y A titanium compound (wherein m is the valence of titanium and y is a number between 1 and m), preferably TiCl4 and a compound derived from the formula MgCl2·pR 6 OH (wherein p is a number between 0.1 and 6, preferably from 2 to 3.5, and R 6The adduct is prepared by reacting an alcohol with magnesium chloride of an adduct of an alcohol (which is a hydrocarbon radical having 1 to 18 carbon atoms). The adduct in spherical form can be suitably prepared by mixing the alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100 to 130° C.). The emulsion is then rapidly quenched, so that the adduct solidifies in the form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648. The adduct thus obtained can be reacted directly with a Ti compound, or it can be previously subjected to a thermally controlled dealcoholation (80 to 130° C.) to obtain an adduct in which the number of moles of alcohol is lower than 3, preferably between 0.1 and 2.5, and even more preferably between 0.5 and 2.3.

[0025] The catalysts based on electron donors of formula (I) of the present disclosure are able to provide very good performances even when prepared starting from highly dealcoholated adducts (e.g. having a mole number of alcohol per mole of Mg of less than 2). When using these dealcoholated adducts, the diether donors of the prior art are immobilized to a very low extent and the derived catalysts provide degraded performances.

[0026] 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-alcoholated or as is) in cold TiCl4, usually at 0°C. Preferably, the adduct is used in an amount so as to have a concentration ranging from 20 to 100 g / l, and preferably from 30 to 90 g / l. According to a preferred embodiment, the electron donor (I) is added to the system at the beginning of the reaction stage and preferably when the temperature of the mixture is in the range of 10°C to 60°C. The electron donor (I) is fed in an amount such that the desired molar ratio in the final catalyst is met. In an embodiment, the Mg / donor (I) molar ratio can be in the range of from 2:1 to 25:1, preferably from 2:1 to 25:1, more preferably from 2:1 to 15:1, and especially from 3:1 to 10:1. The temperature is then gradually increased until a temperature ranging from 90 to 130°C is reached and maintained at this temperature for 0.5 to 3 hours.

[0027] After the reaction time has expired, stirring is stopped, the slurry is allowed to settle, and the liquid phase is removed. A second stage of treatment with TiCl4 is performed, preferably at a temperature ranging from 70 to 130°C. After the reaction time has expired, stirring is stopped, the slurry is allowed to settle, and the liquid phase is removed. Although not essential, additional reaction stages may be performed with titanium compounds, and preferably with TiCl4, under the same conditions described above and in the absence of an electron donor. The solid thus obtained may then be washed with a liquid hydrocarbon under mild conditions and then dried.

[0028] The catalysts based on the electron donor of formula (I) of the present disclosure are able to provide very good performance even when prepared at relatively high Mg / ID molar ratios (13 to 20) and the amount of ID immobilized on the catalyst is such that the ID / Ti molar ratio is in the range of 0.3 to 0.6. When used at the same high Mg / ID ratios, the diether donors of the prior art are immobilized to a very low degree and the derived catalysts provide degraded performance.

[0029] The solid catalyst component may also contain small amounts of additional metal compounds selected from those containing elements belonging to Groups 1 to 15, preferably Groups 11 to 15, of the Periodic Table of the Elements (Iupac version).

[0030] Most preferably, the compound without a metal-carbon bond comprises an element selected from the group consisting of Cu, Zn and Bi. Preferred compounds are oxides, carbonates, alkoxides, carboxylates and halides of the metals. Among them, ZnO, ZnCl2, CuO, CuCl2 and Cu diacetate, BiCl 3、 Bi carbonate and Bi carboxylate. BiCl is particularly preferred. 3、 Bi carbonates and Bi carboxylates.

[0031] The compounds may be added during the preparation of the aforementioned magnesium-alcohol adduct, or they may be introduced into the catalyst by dispersing them in the titanium compound in liquid form and then reacting with the adduct.

[0032] Whichever method is used, the final amount of said metal into the final catalyst component ranges from 0.1 to 10 wt%, preferably from 0.3 to 8 wt% and most preferably from 0.5 to 5 wt% relative to the total weight of the solid catalyst component.

[0033] The solid catalyst components according to the invention are converted into catalysts for olefin polymerization by reacting them with organoaluminum compounds according to known methods.

[0034] In particular, the present invention is directed to a catalyst for the polymerization of olefins CH2=CHR, wherein R is hydrogen or a hydrocarbon radical having 1 to 12 carbon atoms, comprising the product obtained by contacting:

[0035] (i) a solid catalyst component as disclosed above and

[0036] (ii) an alkylaluminum compound and, optionally,

[0037] (iii) External electron donor compounds.

[0038] The alkyl-Al compound (ii) is preferably selected from trialkylaluminum compounds, such as, for example, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides, such as AlEt2Cl and Al2Et3Cl3, possibly mixed with the above-mentioned trialkylaluminum compounds.

[0039] The catalyst components of the present disclosure provide highly stereoregular polypropylene when polymerized even in the absence of an external donor. This can be demonstrated by the amount of xylene insoluble fraction, which can be higher than 97.5 wt. %, and preferably higher than 98 wt. %. It must be noted that the above stereoregular polypropylene is obtained in very high yields. In particular, the polymerization activity is higher than 100 kg when polymerized in liquid propylene at 70° C. for 2 hours. pol / g cat , more preferably higher than 115kg pol / g cat In some cases, the activity can be even higher than 130 kg pol / g cat .

[0040] If used, suitable external electron donor compounds (iii) include silicon compounds, ethers, esters, amines, heterocyclic compounds, and in particular 2,2,6,6-tetramethylpiperidine and ketones.

[0041] Another preferred class of external donor compounds is that of formula (R 7 ) a (R 8 ) b Si(OR 9 ) c A silicon compound wherein a and b are integers from 0 to 2, c is an integer from 1 to 4, and the sum of (a+b+c) is 4; R 7 , R 8 and R 9 is an alkyl, cycloalkyl or aryl radical having 1 to 18 carbon atoms which may optionally contain heteroatoms. Particularly preferred are silicon compounds wherein a is 1, b is 1, c is 2, R 7 and R 8 At least one of is selected from a branched alkyl, cycloalkyl or aryl group having 3 to 10 carbon atoms which may contain a heteroatom, and R 9 It is C1-C 10Alkyl groups, in particular methyl groups. Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), diisopropyldimethoxysilane, (2-ethylpiperidinyl)tert-butyldimethoxysilane, (2-ethylpiperidinyl)tert-hexyldimethoxysilane, (3,3,3-trifluoro-n-propyl) (2-ethylpiperidinyl) dimethoxysilane, methyl (3,3,3-trifluoro-n-propyl) dimethoxysilane. Furthermore, preferred are compounds wherein a is 0, c is 3, R 8 is a branched alkyl or cycloalkyl group optionally containing heteroatoms and R 9 Examples of preferred silicon compounds of this type are cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane and tert-hexyltrimethoxysilane.

[0042] The external electron donor compound (iii) is used in such an amount that the molar ratio between the organoaluminium compound and said electron donor compound (iii) is from 0.1:1 to 500:1, preferably from 1:1 to 300:1 and more preferably from 3:1 to 100:1.

[0043] Therefore, another object of the present invention is to form a process for the (co)polymerization of olefins CH2=CHR, wherein R is hydrogen or a hydrocarbon radical having 1 to 12 carbon atoms, which process is carried out in the presence of a catalyst comprising the reaction product between:

[0044] (i) a solid catalyst component of the present invention;

[0045] (ii) an alkylaluminum compound, and

[0046] (iii) Optional electron donor compound (external donor).

[0047] 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. In addition, the polymerization process can be carried out in the gas phase operating in one or more fluidized beds or mechanically stirred bed reactors.

[0048] The catalyst of the present invention can be used as is in a polymerization process by introducing it directly into a reactor. In a preferred embodiment, the catalyst can be prepolymerized before being introduced into the first polymerization reactor. The term "prepolymerization" used in the art means that the catalyst has been subjected to a polymerization step at a low degree of conversion. According to the present invention, the catalyst is considered to be prepolymerized when the amount of the polymer produced is from about 0.1 to about 1000 g / gram of solid catalyst component at most.

[0049] Prepolymerization can be carried out with the alpha-olefin selected from the same olefin group disclosed above. Especially, it is especially preferred to prepolymerize ethylene or its mixture with one or more alpha-olefins of the amount of up to 20 mol %. Preferably, the conversion rate of the prepolymerized catalyst component is from about 0.2g to about 500g / gram of solid catalyst component at most.

[0050] The prepolymerization step can be carried out in liquid or gas phase at a temperature of from 0°C to 80°C, preferably from 5°C to 50°C. The prepolymerization step can be carried out in-line as part of a continuous polymerization process, or separately in a batch process. It is particularly preferred that the catalyst of the present invention is prepolymerized batchwise with ethylene to produce an amount of polymer ranging from 0.5 to 20 g / gram of catalyst component.

[0051] The polymerization is generally carried out at a temperature ranging from 20 to 120° C., preferably from 40 to 80° C. When the polymerization is carried out in the gas phase, the operating pressure is generally between 0.5 and 5 MPa, preferably between 1 and 4 MPa. In bulk polymerization, the operating pressure is generally between 1 and 8 MPa, preferably between 1.5 and 5 MPa.

[0052] 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 prepare different types of products, particularly propylene homopolymers and copolymers. Considering high activity and stereospecificity, the catalyst of the present disclosure can be advantageously used to prepare propylene / ethylene copolymers with low xylene solubles content and high purity polypropylene polymers with very low content of halogen (Cl) and metals (such as Ti, Mg and Al). In particular, when used to prepare propylene / ethylene copolymers with an ethylene content ranging from 0.1 to 6 wt % by the total weight of propylene and ethylene, the catalyst of the present disclosure can provide copolymers with a low amount of xylene soluble materials.

[0053] These catalysts are also suitable for producing high impact polymer compositions comprising (A) a crystalline propylene homopolymer or copolymer matrix and a significant amount (greater than 50 wt. % in certain applications) of (B) a low crystallinity, highly xylene soluble propylene-ethylene copolymer.

[0054] Such polymer compositions are preferably prepared with a multi-step process comprising at least two different polymerization stages carried out in different reactors. Typically, the first step in preparing a crystalline propylene homopolymer or copolymer can be carried out in gas phase or liquid phase. Gas phase polymerization can be carried out in a fluidized or stirred fixed bed reactor or in a gas phase reactor comprising two interconnected polymerization zones, wherein one polymerization zone works under fast fluidization conditions, and in another polymerization zone, the polymer flows under gravity. The liquid phase process can be a slurry, a solution or a body (liquid monomer). The latter technology is the most preferred and can be carried out in various types of reactors (such as continuously stirred tank reactors, loop reactors or plug flow reactors). Preferably, the first step is carried out in gas phase. In this stage and / or in the continuous stage, hydrogen can be used as a molecular weight regulator.

[0055] 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 polymerization material from the previous polymerization step and the catalyst system.

[0056] The polymer produced in this stage may contain from 15 to 75% by weight of ethylene, optionally with a smaller proportion of diene, and may have a solubility in xylene at 25° C. of at least 60% by weight.

[0057] The following examples are given to illustrate but not to limit the invention itself.

[0058] Characterization

[0059] Determination of porosity.

[0060] Mercury Porosity and Surface Area: The measurements were performed using a Pascal 140-240 series porosimeter manufactured by Carlo Erba.

[0061] Porosity is measured by the intrusion of mercury under pressure. For this determination, a calibrated dilatometer (capillary diameter 3mm) CD3P (manufactured by Carlo Erba) connected to a mercury reservoir and a high vacuum pump is used. The weighed sample is placed in the dilatometer. The device is then placed under high vacuum, and maintained for about 20 minutes under these conditions. The dilatometer is then connected to the mercury reservoir, and mercury is allowed to slowly fill the dilatometer until it reaches the level marked at a height of 10cm on the dilatometer. The valve connecting the dilatometer to the vacuum pump is closed, and then the mercury pressure is gradually increased to 100kPa with nitrogen. Subsequently, the calibrated dilatometer is transferred to an autoclave with high-pressure oil to reach a pressure value of up to 200MPa. Under the effect of pressure, mercury enters the pores of the particles, and the mercury level is reduced accordingly.

[0062] Porosity (cm3 / g), pore distribution curve and average pore diameter are calculated directly from the integral pore distribution curve, which is a function of both the volume reduction of mercury and the applied pressure value. All these data are provided and elaborated by a computer associated with the porosimeter equipped with a dedicated software supplied by Carlo Erba. After calculation, the average pore radius is given as a weighted average of the individual average pore radius contributions for each porosity interval.

[0063] Determination of XI

[0064] About 2.5 grams of polymer and 250 ml of o-xylene are placed in a round-bottom flask provided with a cooler and a reflux condenser and kept under nitrogen. The obtained mixture is heated to 135 ° C and kept for about 60 minutes under stirring. The final solution is allowed to cool to 25 ° C under continuous stirring, and then the insoluble polymer is filtered. The filtrate is then evaporated at 140 ° C in a nitrogen stream to reach constant weight. The content of the xylene soluble fraction is expressed as a percentage of the original 2.5 grams, and then expressed as XI% by difference.

[0065] Determination of donor.

[0066] The content of electron donor was determined by gas chromatography.

[0067] Determination of Melt Flow Rate (MFR).

[0068] The melt flow rate MIL of the polymer is determined according to ISO 1133 (230° C., 2.16 Kg).

[0069] Determination of comonomers.

[0070] The comonomer (ethylene) content was determined via NMR spectroscopy.

[0071] Determination of Tm

[0072] Determined by differential scanning calorimetry (DSC). Weigh 6±1 mg of sample, heat to 220±1°C at a rate of 20°C / min in a nitrogen stream and hold at 220±1°C for 2 minutes, and then cool to 40±2°C at a rate of 20°C / min, whereby hold at this temperature for 2 minutes to crystallize the sample. Then, heat to 220°C±1 at a rate of 20°C / min to melt the sample again. Record the melting scan, obtain the thermogram, and read the melting temperature and crystallization temperature from this.

[0073] Determination of intrinsic viscosity (IV)

[0074] The intrinsic viscosity is measured based on the xylene soluble fraction. The sample is dissolved in tetralin at 135°C and then poured into a capillary viscometer. The viscometer tube (Ubbelohde type) is surrounded by a cylindrical glass jacket; this setup allows temperature control with a circulating thermostatic liquid. The downward passage of the meniscus is timed by a photoelectric device.

[0075] The passage of the meniscus in front of the upper lamp starts a counter with a quartz crystal oscillator. The counter is stopped when the meniscus passes the lower lamp and the outflow time is noted: this is converted into an intrinsic viscosity value by the Huggins equation (Huggins, ML, J. Am. Chem. Soc., 1942, 64, 2716), provided that the flow time of the pure solvent under the same experimental conditions (same viscometer and same temperature) is known. [η] is determined using a single polymer solution.

[0076] Determination of flexural modulus

[0077] Flexural modulus according to ISO 178 and ISO 1873-2

[0078] Determination of tensile modulus

[0079] Tensile modulus according to ISO 527 and ISO 1873-2

[0080] Charpy determination

[0081] Charpy impact test according to ISO 179-1eA and ISO 1873-2

[0082] Propylene / ethylene copolymer 13 C Determination of NMR spectra

[0083] Heterophasic copolymers and their XI and XS fractions 13 C NMR spectra were acquired on a Bruker AV-600 spectrometer equipped with a cryoprobe, operating at 120 °C in Fourier transform mode at 160.91 MHz.

[0084] S ββ Carbon (according to 13 3. Use of the Reaction Probability Model 13C NMR.3. Use of Reaction Probability Mode)" CJ Carman, RA Harrington and CE Wilkes, "Macromolecules", 1977, 10, 536) peak at 29.9 ppm was used as an internal reference. The sample was dissolved in 1,1,2,2-tetrachloroethane-d2 at a concentration of 8 weight / volume % at 120°C. Each spectrum was acquired with a 90° pulse, with a 15 second delay between pulses, and CPD was used to remove 1H-13C coupling. 512 transient data were stored in 32K data points using a spectral window of 9000 Hz.

[0085] Evaluation of spectral assignments, triplet distribution and composition was performed according to Kakugo ("Carbon-13 NMR determination of monomer sequence distribution in 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:

[0086] PPP=100T ββ / S PPE=100T βδ / S EPE=100T δδ / S

[0087] PEP=100s ββ / S PEE=100S βδ / S EEE=100(0.25S γδ +0.5S δδ ) / S

[0088] S=T ββ +T βδ +T δδ +S ββ +S βδ +0.25S γδ +0.5S δδ

[0089] The mole percentage of ethylene content was estimated using the following equation:

[0090] E mol% = 100 × [PEP + PEE + EEE]

[0091] The weight percent ethylene content was estimated using the following equation:

[0092] E weight% = 100 x MW E ×E mol% / (MW E ×E mol% + MW P × P mol %), where P mol % is the molar percentage of propylene content, and MW E and MW P are the molecular weights of ethylene and propylene respectively.

[0093] Examples

[0094] General procedure for the preparation of MgCl2*pEtOH adducts.

[0095] An initial amount of microspheroidal MgCl2*2.8EtOH was prepared according to the method described in Example 2 of USP 4,399,054, but operating at 3,000 rpm instead of 10,000 rpm. A portion of the adduct thus obtained was then thermally dealcoholated in a nitrogen stream at elevated temperatures from 30 to 130°C until the molar alcohol content per mole of Mg was 2.1.

[0096] Preparation of electron donors

[0097] Synthesis of 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane

[0098] Step 1: Synthesis of diethyl 2-cyclohexylmalonate

[0099] In the 1L round-bottom flask equipped with mechanical stirrer, thermometer and condenser, add ethanol (400mL) and potassium tert-butoxide (50g, 0.4mol).Then, in 10 minutes, dropwise add diethyl malonate (63g, 0.4mol), observe the formation of white suspension.The temperature is raised to 76 ℃ and in 30 minutes, add cyclohexyl bromide.The mixture is placed 40 hours under reflux, then remove solvent under vacuum and reclaim slurry with ethyl acetate (200mL).With organic phase water (2 × 100mL) and 10% NaHCO3 washing, then evaporate, thus obtain 26g of 2-cyclohexyl diethyl malonate, be light yellow oily matter, purity 99% (GC), yield 27%. 1HNMR (δ, 400 MHz, CDCl3): 4.2 (q, 4H, OCH2), 3.2 (d, 1H, CH malonic acid), 2.1 (m, 1H, CH cyclohexyl), 1.8-0.8 (m, 16H, OCH2CH3+cyclohexyl).

[0100] Step 2: Synthesis of diethyl 2-cyclohexyl-2-isopentylmalonate

[0101] Tetrahydrofuran (120 mL), diethyl 2-cyclohexylmalonate (26 g, 105 mmol) and sodium hydride (95%, 3 g, 119 mmol) were added to a 500 mL round bottom flask equipped with a mechanical stirrer, a thermometer and a condenser. The temperature was raised to 40° C. and the formation of gas was observed. After 1 hour, the gas evolution disappeared and then isopentyl bromide (20 g, 130 mmol) was added over a period of 30 minutes. The mixture was placed under reflux for 25 hours and then diluted with 300 mL of HCl 1M. The organic phase was diluted with ether (200 mL), washed with water (2×100 mL) and then evaporated to give 23 g of diethyl 2-cyclohexyl-2-isopentylmalonate as a light yellow oil with a purity of 95% (GC) and a yield of 67%. 1 HNMR (δ, 400 MHz, CDCl3): 4.1 (q, 4H, OCH2), 1.7 (m, 3H, CH cyclohexyl + α-CH2 isopentyl), 1.6-1.3 (m, 8H, cyclohexyl), 1.2 (m, 7H, OCH2CH3 + γ-CH isopentyl), 1.0 (m, 4H, cyclohexyl + β-CH2 isopentyl), 0.8 (d, 6H, (CH3)2 isopentyl).

[0102] Step 3: Synthesis of 2-cyclohexyl-2-isopentyl-1,3-propanediol

[0103] Tetrahydrofuran (100 mL), diethyl 2-cyclohexyl-2-isopentylmalonate (95%, 23 g, 70 mmol) and lithium aluminum hydride (95%, 3 g, 77 mmol) were added to a 500 mL round-bottom flask equipped with a mechanical stirrer, a thermometer and a condenser. The mixture was placed under reflux for 16 hours and then diluted with 200 mL of HCl 1M. The organic phase was extracted with 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 with a purity of 98% (GC) and a yield of 92%. 1HNMR (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)2isopentyl).

[0104] Step 4: Synthesis of 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane

[0105] 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 to a 500 mL round-bottom flask equipped with a mechanical stirrer, a thermometer and a condenser. The temperature was raised to 40 ° C (gas evolution) and methyl iodide (20 g, 141 mmol) was added dropwise over 1 hour. Next, the slurry was placed at 40 ° C for 8 hours and then diluted with 200 mL of HCl 1M. The organic phase was diluted with ether (100 mL), washed with water (2×50 mL), and then evaporated to obtain 16 g of 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane as a colorless oil with a purity of 99% (GC) and a yield of 98%. 1 HNMR (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)2isopentyl).

[0106] Synthesis of 2-cyclohexyl-2-(3,3,3-trifluoro-n-propyl)-1,3-dimethoxypropane

[0107] Step 1: Synthesis of diethyl 2-cyclohexyl-2-(3,3,3-trifluoro-n-propyl)malonate

[0108] This derivative was prepared according to the synthesis described in Example 1 - Step 2, using 1-iodo-3,3,3-trifluoro-n-propane as the alkylating agent. The product was a light yellow oil with a purity of 97% and a yield of 50%. 1 HNMR (δ, 400 MHz, CDCl3): 4.2 (q, 4H, OCH2), 2.2-1.5 (m, 10H, cyclohexyl + 3,3,3-trifluoro-n-propane), 1.2 (t, 6H, OCH2CH3), 1.1-0.9 (m, 5H, cyclohexyl + 3,3,3-trifluoro-n-propane).

[0109] Step 2: Synthesis of 2-cyclohexyl-2-(3,3,3-trifluoro-n-propyl)-1,3-propanediol

[0110] This derivative was prepared according to the synthesis described in Example 1 - Step 3. The product was an orange viscous oil with a purity of 98.5% and a yield of 92%. 1 HNMR (δ, 400 MHz, CDCl3): 3.7-3.5 (dd, 4H, OCH2), 2.5 (s, 2H, OH), 2.0 (m, 2H, β-CH23,3,3-trifluoro-n-propyl), 1.8-0.9 (m, 13H, cyclohexyl + 3,3,3-trifluoro-n-propane).

[0111] Step 3: Synthesis of 2-cyclohexyl-2-(3,3,3-trifluoro-n-propyl)-1,3-dimethoxypropane

[0112] This derivative was prepared according to the synthesis described in Example 1 - Step 4. The product was a yellow oil with a purity of 98% and a yield of 95%. 1 HNMR (δ, 400 MHz, CDCl3): 3.2 (s, 6H, CH3O), 3.1 (s, 4H, OCH2), 2.1 (m, 2H, β-CH23, 3, 3-trifluoro-n-propane), 1.8-0.9 (m, 13H, cyclohexyl + 3, 3, 3-trifluoro-n-propane).

[0113] Synthesis of 2-cyclohexyl-2-(3-methylpentyl)-1,3-dimethoxypropane

[0114] Step 1: Synthesis of diethyl 2-cyclohexyl-2-(3-methylpentyl)malonate

[0115] This derivative was prepared according to the synthesis described in Example 1 - Step 2, using 1-bromo-3-methylpentane as the alkylating agent. The product was a colorless oil with a purity of 92% and a yield of 82%. 1 HNMR (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).

[0116] Step 2: Synthesis of 2-cyclohexyl-2-(3-methylpentyl)-1,3-propanediol

[0117] This derivative was prepared according to the synthesis described in Example 1 - Step 3. The product was a yellow viscous oil with a purity of 92% and a yield of 92%. 1 HNMR (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).

[0118] Step 3: Synthesis of 2-cyclohexyl-2-(3-methylpentyl)-1,3-dimethoxypropane

[0119] This derivative was prepared according to the synthesis described in Example 1 - Step 4. The product was distilled using a Vigreaux apparatus at 145°C / 6 mmHg to obtain a colorless oil with a purity of 96% and a yield of 81%. 1 HNMR (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).

[0120] Synthesis of 2-cyclohexyl-2-(3-ethylpentyl)-1,3-dimethoxypropane

[0121] Step 1: Synthesis of diethyl 2-cyclohexyl-2-(3-ethylpentyl)malonate

[0122] 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 was a yellow oil 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).

[0123] Step 2: Synthesis of 2-cyclohexyl-2-(3-ethylpentyl)-1,3-propanediol

[0124] This derivative was prepared according to the synthesis described in Example 1 - Step 3. The product was a colorless viscous oil 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).

[0125] Step 3: Synthesis of 2-cyclohexyl-2-(3-ethylpentyl)-1,3-dimethoxypropane

[0126] This derivative was prepared according to the synthesis described in Example 1 - Step 4. The product was a colorless oil with a purity of 95% and a yield of 86%. 1HNMR (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).

[0127] Synthesis of 2-cyclohexyl-2-(3,5-dimethylhexyl)-1,3-dimethoxypropane

[0128] Step 1: Synthesis of diethyl 2-cyclohexyl-2-(3,5-dimethylhexyl)malonate

[0129] 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 was a brown oil with a purity of 92% and a yield of 78%. 1 HNMR (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).

[0130] Step 2: Synthesis of 2-cyclohexyl-2-(3,5-dimethylhexyl)-1,3-propanediol

[0131] This derivative was prepared according to the synthesis described in Example 1 - Step 3. The product was a yellow viscous oil with a purity of 96% and a yield of 96%. 1 HNMR (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).

[0132] Step 3: Synthesis of 2-cyclohexyl-2-(3,5-dimethylhexyl)-1,3-dimethoxypropane

[0133] This derivative was prepared according to the synthesis described in Example 1 - Step 4. The product was a colorless oil with a purity of 96% and a yield of 94%. 1 HNMR (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).

[0134] Synthesis of 2-cyclohexyl-2-n-pentyl-1,3-dimethoxypropane

[0135] Step 1: Synthesis of diethyl 2-cyclohexyl-2-n-pentylmalonate

[0136] This derivative was prepared according to the synthesis described in Example 1 - Step 2, using n-pentyl bromide as the alkylating agent. The product was a light yellow oil with a purity of 90% and a yield of 80%. 1 HNMR (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, CH3 n-pentyl).

[0137] Step 2: Synthesis of 2-cyclohexyl-2-n-pentyl-1,3-propanediol

[0138] This derivative was prepared according to the synthesis described in Example 1 - Step 3. The product was a colorless viscous oil with a purity of 98% and a yield of 75%. 1 HNMR (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).

[0139] Step 3: Synthesis of 2-cyclohexyl-2-n-pentyl-1,3-dimethoxypropane

[0140] This derivative was prepared according to the synthesis described in Example 1 - Step 4. The product was a colorless oil with a purity of 98% and a yield of 96%. 1 HNMR (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).

[0141] Synthesis of 2-cyclohexyl-2-n-butyl-1,3-dimethoxypropane

[0142] Step 1: Synthesis of diethyl 2-cyclohexyl-2-n-butylmalonate

[0143] This derivative was prepared according to the synthesis described in Example 1 - Step 2, using n-butyl bromide as the alkylating agent. The product was a light yellow oil with a purity of 96% and a yield of 79%. 1HNMR (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, CH3 n-butyl).

[0144] Step 2: Synthesis of 2-cyclohexyl-2-n-butyl-1,3-propanediol

[0145] This derivative was prepared according to the synthesis described in Example 1 - Step 3. The product was a colorless viscous oil with a purity of 99% and a yield of 85%. 1 HNMR (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, CH3 n-butyl).

[0146] Step 3: Synthesis of 2-cyclohexyl-2-n-butyl-1,3-dimethoxypropane

[0147] This derivative was prepared according to the synthesis described in Example 1 - Step 4. The product was a colorless oil with a purity of 98% and a yield of 99%. 1 HNMR (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, CH3 n-butyl).

[0148] Synthesis of 2-cyclohexyl-2-isobutyl-1,3-dimethoxypropane

[0149] Step 1: Synthesis of diethyl 2-cyclohexyl-2-isobutylmalonate

[0150] This derivative was prepared according to the synthesis described in Example 1 - Step 2, using isobutyl bromide as the alkylating agent. The product was a light yellow oil with a purity of 92% and a yield of 80%. 1 HNMR (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).

[0151] Step 2: Synthesis of 2-cyclohexyl-2-isobutyl-1,3-propanediol

[0152] This derivative was prepared according to the synthesis described in Example 1 - Step 3. The product was a colorless viscous oil with a purity of 88% and a yield of 84%. 1 HNMR (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).

[0153] Step 3: Synthesis of 2-cyclohexyl-2-isobutyl-1,3-dimethoxypropane

[0154] This derivative was prepared according to the synthesis described in Example 1 - Step 4. The final product purified by distillation (115°C / 0.5 mmHg) was a colorless oil with a purity of 98% and a yield of 75%. 1 HNMR (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).

[0155] Synthesis of 2-cyclopentyl-2-isopentyl-1,3-dimethoxypropane

[0156] Step 1: Synthesis of diethyl 2-cyclopentylmalonate

[0157] This derivative was prepared according to the synthesis described in Example 1 - Step 1, using cyclopentyl bromide as the alkylating agent. The product was a colorless oil with a purity of 99% and a yield of 56%. 1 HNMR (δ, 400MHz, CDCl3): 1 HNMR (δ, 400 MHz, CDCl3): 4.2 (q, 4H, OCH2), 3.2 (d, 1H, CH malonic acid), 2.2 (m, 1H, CH cyclopentyl), 1.7-0.8 (m, 14H, OCH2CH3+cyclopentyl).

[0158] Step 2: Synthesis of diethyl 2-cyclopentyl-2-isopentylmalonate

[0159] This derivative was prepared according to the synthesis described in Example 1 - Step 2, using isobutyl bromide as the alkylating agent. The product was a light yellow oil with a purity of 92% and a yield of 80%. 1HNMR (δ, 400MHz, CDCl3): 4.1 (q, 4H, OCH2), 2.4 (m, 3H, CH2 cyclopentyl + α-CH2 isopentyl), 1.6-1.3 (m, 8H, cyclopentyl), 1.2-1.0 (m, 9H, OCH2CH 3+ isopentyl), 0.8 (d, 6H, (CH3)2isopentyl).

[0160] Step 3: Synthesis of 2-cyclopentyl-2-isopentyl-1,3-propanediol

[0161] This derivative was prepared according to the synthesis described in Example 1 - Step 3. The product was a colorless viscous oil with a purity of 97% and a yield of 90%. 1 HNMR (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)2isopentyl).

[0162] Step 4: Synthesis of 2-cyclopentyl-2-isopentyl-1,3-dimethoxypropane

[0163] This derivative was prepared according to the synthesis described in Example 1 - Step 4. The final product was a colorless oil with a purity of 98% and a yield of 92%. 1 HNMR (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)2isopentyl).

[0164] Preparation of Solid Catalyst Components—General Procedure.

[0165] At 0° C., 500 mL of TiCl4 was introduced into a 1000 mL four-necked round-bottom flask purged with nitrogen. While stirring, 20 grams of microspherical MgCl2.2.1 EtOH adduct (prepared as described above) was added. Then, an amount of electron donor of formula (I) was charged at 0° C. so that Mg / donor was 6.

[0166] The temperature was raised to 100° C. and maintained at this value for 120 minutes. Afterwards, stirring was stopped, the liquid was siphoned off and the treatment with TiCl4 was repeated at 120° C. for 60 minutes. After settling and siphoning, the solid was washed with anhydrous isohexane (6×100 ml) and dried to obtain a free-flowing powder. The characterization of the solid catalyst component thus obtained is reported in Table 1.

[0167] General Procedure for Bulk Homopolymerization of Propylene

[0168] A 4-liter steel autoclave equipped with a stirrer, pressure gauge, thermometer, catalyst feed system, monomer feed line and thermostatic jacket was purged with a stream of nitrogen at 70° C. for 1 hour. Then, at 30° C. under a stream of propylene, 75 ml of anhydrous hexane (containing 0.76 g of AlEt3), about 6 mg of a solid catalyst component, and, when used, an external donor (type and amount reported in the table) were loaded in sequence. The autoclave was closed and 2 NL of hydrogen were subsequently added. Then, under stirring, 1.2 kg of liquid propylene was fed. The temperature was raised to 70° C. within 10 minutes and polymerization was carried out at this temperature for 2 hours. At the end of the polymerization, unreacted propylene was removed; the polymer was recovered and dried in an oven at 80° C.

[0169] Examples 1 to 5 and Comparative Examples 6 to 10. Polymerization of propylene.

[0170] The catalysts of Inventive Examples 1 to 5 and Comparative Examples 6 to 9 were prepared according to the general procedure described above using the donors described in Table 1. Catalyst characterization and results for bulk polymerization of propylene are reported in Table 1.

[0171] Table 1.

[0172]

[0173]

[0174] Examples 11 to 16

[0175] Catalyst preparation

[0176] Into a 1000 mL four-necked round-bottom flask purged with nitrogen, 500 mL of TiCl4 were introduced at -3°C. While stirring, 20 grams of microspherical MgCl2.2.1 EtOH adduct (prepared as described above) were added. Then, for some preparations indicated in Table 2, an amount of BiCl3 was charged at -3°C to give a Mg / BiCl3 of 60 mr.

[0177] In all preparations, the temperature was raised to 100°C and maintained at this value for 30 minutes. Afterwards, stirring was stopped and the liquid was siphoned off, fresh TiCl4 and 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane as internal donor were added to have the Mg / ID reported in Table 2, and the temperature was raised to 120°C under stirring for 30 minutes. After stopping stirring, the liquid was siphoned off and the treatment with TiCl4 was repeated at 120°C for 15 minutes. After settling and siphoning, 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 propylene bulk polymerization results are reported in Table 2.

[0178] Comparative Example 17

[0179] Catalyst preparation

[0180] Catalyst preparation was performed 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 catalyst preparation, characterization, and propylene bulk polymerization results are reported in Table 2.

[0181] Table 2

[0182]

[0183] TEAL / C donor molar ratio 20

[0184] Example 18

[0185] An initial amount of microspheroidal MgCl2.2.8C2H5OH was prepared according to the method described in Example 2 of USP 4,399,054, but operating at 3,000 rpm instead of 10,000 rpm. The adduct thus obtained, having an average particle size of 87 μm, was then thermally dealcoholated in a nitrogen stream at elevated temperatures from 30 to 130°C until the molar alcohol content per mole of Mg was 1.16. Using this support, the catalyst was prepared and tested according to the general procedure already described. Details of the catalyst preparation, characterization and bulk polymerization results of propylene are reported in Table 3.

[0186] Comparative Example 19

[0187] Catalyst preparation was performed 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 catalyst preparation, characterization, and propylene bulk polymerization results are reported in Table 3.

[0188] Table 3

[0189]

[0190] TEAL / ED molar ratio=4.

Claims

1. A solid catalyst component for olefin polymerization, comprising a magnesium halide, a titanium compound having at least one Ti-halogen bond and at least one electron donor of formula (I) Where R 1 and R 2 are independently C1-C5 alkyl groups, X is Si or C, R 3 and R 4 The groups are independently selected from hydrogen, C1-C 20 a hydrocarbon group and a halogen, provided that R 3 At least two of them are not hydrogen.

2. The solid catalyst component according to claim 1, wherein R 1 and R 2 are the same and are selected from C1-C4 straight or branched alkyl groups, and more preferably selected from methyl groups.

3. A solid catalyst component according to any one of the preceding claims, wherein R 4 The groups are independently selected from hydrogen, C1-C 10 Hydrocarbyl groups and halogens.

4. The solid catalyst component according to claim 3, wherein all R 4 The radical is hydrogen.

5. A solid catalyst component according to any one of the preceding claims, wherein R 3 Selected from hydrogen, C1-C 10 Hydrocarbyl groups and halogens.

6. A solid catalyst component according to any one of the preceding claims, wherein when R 3 When it is a hydrocarbyl group, it is selected from a C1-C4 straight chain or branched alkyl group and a group linked together to form a C6 saturated ring which is optionally substituted by a C1-C4 straight chain alkyl group.

7. The catalyst component according to any one of the preceding claims, wherein when R 3 When it is halogen, it is selected from Cl and F.

8. A solid catalyst component according to any one of the preceding claims 1 to 7, wherein X is carbon.

9. A solid catalyst component according to any one of the preceding claims, wherein the molar ratio between the electron donor of formula (I) and Ti atoms in the final solid catalyst component is in the range of from 0.3:1 to 1.5:1, and more preferably from 0.4:1 to 1.3:

1.

10. A solid catalyst component according to any one of the preceding claims, wherein the molar ratio between Mg atoms and the electron donor of formula (I) in the final solid catalyst component is in the range of from 2.5:1 to 50.0:1, more preferably 3:1 to 45.0:

1.

11. A solid catalyst component according to any one of the preceding claims, wherein an additional donor selected from the group consisting of esters of aliphatic dicarboxylic acids is present.

12. A solid catalyst component according to any one of the preceding claims, comprising an additional metal compound which is free of metal-carbon bonds and comprises an element selected from the group consisting of Cu, Zn and Bi.

13. A catalyst for the polymerization of olefins CH2=CHR, wherein R is hydrogen or a hydrocarbon radical having 1 to 12 carbon atoms, said catalyst comprising the reaction product between: (i) a solid catalyst component according to any one of the preceding claims, and (ii) Alkyl aluminum compounds.

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

15. A process for the (co)polymerization of olefins CH2=CHR, wherein R is hydrogen or a hydrocarbon radical having 1 to 12 carbon atoms, carried out in the presence of a catalyst as defined in one or more of claims 13 to 14.

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