Catalyst components for the polymerization of olefins

Abstract

A solid catalyst component for the polymerization of olefins, which comprises a magnesium halide, a titanium compound having at least Ti-halogen bonds and at least two electron donor compounds, one electron donor compound being selected from a specific class of 1,3-diethers and the other electron donor compound being selected from diether organic compounds, the solid catalyst component having high polymerization activity and stereospecificity even in the absence of an external donor.

Description

Technical Field

[0001] This disclosure relates to a Ziegler-Natta heterogeneous catalyst component for the polymerization of olefins, particularly propylene, comprising a Mg dihalide, a Ti compound having at least one Ti-halogen bond, and at least two electron donor compounds selected from a particular class. Background Technology

[0002] Catalyst components for the stereospecific polymerization of olefins have been disclosed in the art. In propylene polymerization, Ziegler-Natta catalysts are used, which typically comprise a solid catalyst component consisting of magnesium dihalide supported on a titanium compound and an internal electron donor compound, used in combination with an alkyl Al compound. However, external donors (e.g., alkoxysilanes) are often required to achieve higher isotactic regularity when higher polymer crystallinity is desired. Phthalic acid esters, particularly diisobutyl phthalate, are used as internal donors in catalyst preparation. Phthalic acid esters are used as internal donors in combination with alkylalkoxysilanes as external donors. This catalyst system exhibits good performance in terms of activity, isotactic regularity, and xylene insolubility.

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

[0004] Patent applications EP361494A2, WO02 / 100904, and WO2021 / 063930 describe solid catalyst components for olefin polymerization, which include 1,3-diethers characterized by a specific structure as internal electron donor compounds. While generally exhibiting good performance, there is still a perceived need for a catalyst component that is free of phthalate donors and, in the absence of external donors, displays high polymerization activity and high stereospecificity. Furthermore, it is desirable for the catalyst to exhibit good performance even when the most critical component (i.e., the 1,3-diether internal donor) is at low levels.

[0005] The applicant unexpectedly discovered that the above requirements could be met by appropriately combining a specific group of 1,3-diethers with another type of internal donor. Summary of the Invention

[0006] Therefore, one objective of this disclosure relates to a solid catalyst composition comprising magnesium halide, a titanium compound having at least a Ti-halogen bond, and at least two electron donor compounds, one of which (ID1) is selected from 1,3-diethers of formula (I):

[0007] (I)

[0008] Where R 1 and R 2 Independently, it is a C1-C5 alkyl group, where X is Si or C, and R is... 3 and R 4 The groups are independently selected from hydrogen, C1-C. 20 Hydrocarbon groups and halogens, provided there are at least two R groups. 3 It is not hydrogen, and the other electron donor compound (ID2) is selected from organic compounds with two ester groups. The solid catalyst component is further characterized by the fact that the molar ratio between ID2 and ID1 (ID2 / ID1) is in the range of 0.5:1 to less than 1.0:1, and the molar ratio between the sum of ID1 and ID2 (ID1+ID2) and Ti atoms in the final solid catalyst component ((ID1+ID2) / Ti) is in the range of 0.45:1 to 1.70:1, provided that:

[0009] i) When ((ID1+ID2) / Ti) is in the range of 0.45 to 0.70, the molar ratio ID2 / ID1 is in the range of 0.70:1 to 1.0:1; and

[0010] ii) When ((ID1+ID2) / Ti) is in the range of 0.80 to 1.70, the molar ratio ID2 / Ti is in the range of 0.30:1 and 0.70:1. Detailed Implementation

[0011] Preferably, in ID1 of formula (I), R 1 and R 2 The same and selected from C1-C4 straight-chain or branched alkyl groups, and more preferably selected from methyl groups.

[0012] The term hydrocarbon group includes different groups such as alkyl, cycloalkyl, arylalkyl, alkenyl, aryl, alkylaryl, and hydrocarbon groups fused together to form saturated or unsaturated rings.

[0013] Preferably, R 4 The groups are independently selected from hydrogen, C1-C. 10 Hydrocarbon groups and halogens. More preferably, they are selected from hydrogen, C1-C4 straight-chain or branched alkyl groups, and halogens. Even more preferably, R 4 Only one or two of the groups are C1-C4 straight-chain or branched alkyl groups or halogens. Preferred alkyl groups are methyl, isopropyl, or tert-butyl, while preferred halogens are Cl and F. All R... 4 A structure with hydrogen as a radical is also preferred.

[0014] R 3The radical is preferably selected from hydrogen and C1-C. 10 Hydrocarbon groups and halogens. When R 3 When the alkyl group is a hydrocarbon group, it is preferably selected from C1-C4 straight-chain or branched alkyl groups linked together to form a C6 saturated ring that may be substituted by a C1-C4 straight-chain alkyl group; particularly preferred alkyl groups are methyl, ethyl and isobutyl.

[0015] When R 3 When the halogen is halogen, it is preferably selected from Cl and F. More preferably, the halogen is F.

[0016] According to the preferred embodiment, X is carbon and R 3 It is hydrogen, C1-C 20 A hydrocarbon group or a halogen. Preferably, the hydrocarbon group is selected from C1-C4 straight-chain or branched alkyl groups, more preferably from methyl groups. Most preferably, one of the R groups is... 3 The structure is selected from hydrogen and the other two are selected from methyl groups.

[0017] Another preferred structure is one in which X is carbon, and R 3 It is hydrogen or preferably those structures selected from Cl and F, more preferably those selected from halogen groups of F. Most preferably, it is those in which R... 3 At least two of the structures are selected from F, and more preferably all of the R are selected from F. 3 Structures whose radical is F.

[0018] According to another preferred embodiment, X is Si, and R 3 It is hydrogen or preferably a C1-C4 straight-chain or branched alkyl group, more preferably a hydrocarbon group selected from methyl or ethyl. Most preferably, all R... 3 The group is selected from the structure of methyl.

[0019] Specific examples of compounds of formula (I) that may 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-dichloropropyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3,3-difluorobutyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-( ... 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-bromopropyl)-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-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 Alkane, 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 ... 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-(3,3,3-dimethylbutyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3,3,3-diphenylpropyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3,3,3-tris(4-chlorophenyl)propyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3,3-dimethylbutyl)-1,3-dimethoxypropane, 2-Cyclohexyl-2-(3,3-diphenyl)propyl ...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-(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-diallyloxypropane, 2-cyclohexyl-2-(3,3-difluorobutyl)-1,3-diethoxypropane, 2-cyclohexyl -2-(3,3-dibromobutyl)-1,3-diallyloxypropane, 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-(3,3,3-difluoropropyl)-1,3-diallyloxypropane, 2-cyclohexyl-2-(3,3-dibromopropyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3,3-dichloropropyl)-1,3-dipropoxypropane, 2-cyclohexyl-2-(3,3-dichloropropyl)-1,3-dipropoxypropane Propane, 2-cyclohexyl-2-(3,3-dichloro-3-fluoro-propyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3,3-dichloro-3-bromo-propyl)-1,3-dipropoxypropane, 2-cyclohexyl-2-(3,3-difluoro-3-bromo-propyl)-1,3-dibutoxypropane, 2-cyclohexyl-2-(3,3-difluoro-3-chloro-propyl)-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-Diisopentoxypropane, 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 2-Cyclohexyl-2-(3,3,3-triphenylpropyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3,3,3-tris(4-chlorophenyl)propyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3,3,3-dimethylbutyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(3-methylpentyl)-1,3-diethoxypropane, 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-(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-triisopropylsilylethyl)-1,3-diisopentyloxypropane, 2-cyclohexyl-2-(2-triphenylsilylethyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(2-triphenylsilylethyl)-1,3-diethoxypropane, 2-cyclohexyl-2-(2-methyldiphenyl) 2-Cyclohexyl-2-(2-dimethylphenylsilylethyl)-1,3-diethoxypropane, 2-Cyclohexyl-2-(2-(tris(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-methoxy-propane, 2-Cyclohexyl-2-(3,3-difluorobutyl)-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-dibromobutyl)-1-ethoxy-3-methoxy-propane, 2-Cyclohexyl-2-(3,3-dibromobutyl)-1-ethoxy-3-methoxy-propane, 2-Cyclohexyl-2-(3,3-dichlorophenyl)silylethyl)-1,3-dieth ...-ethoxy-3-methoxy-propane, 2-Cyclohexyl-2-(3,3-dichlorophenyl)silylethyl)-1,3-diethoxy-propane, 2-3-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-difluoropropyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-dichloro ... 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-(3,3-dichloro-5-methylhexyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3-chloro-3-isobutyl-5-ethyl ... 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-fluoro-3-isopentyl-6-methylheptyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3-chloro-3-isopentyl-6-methylheptyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-methylhex ... 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-(3,3,3-dimethylbutyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3-methylpentyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-ethylpentyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-ethylpentyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-diphenylpropyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-diphenylpropyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-diphenylpropyl)-1-ethoxy-3-methoxy-propane,3-Diethylpentyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3-isopropyl-4-methylpentyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(3,3-diisopropyl-4-methylpentyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(cyclohexylethyl)-1-ethoxy-3-propoxy-propane, 2-cyclohexyl-2-(cyclopentylethyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(phenylethyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(2-trimethylsilylethyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(2-trimethylsilylethyl)-1-ethoxy-3-methoxy-propane, 2-cyclohexyl-2-(2-triisopropylsilylethyl)-1-ethoxy-3-methoxy-propane Alkylethyl)-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-dimethylphenylsilylethyl)-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-(3,3,3-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-(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-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-diisopentoxypropane, 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)-1,3-diethoxypropane, 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-) 2-(2-methylcyclohexyl)-2-(3,3,3-tris(4-chlorophenyl)propyl)-1-ethoxy-3-methoxy-propane, 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-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-(3,3-dichlorobutyl)-1,3-dimethoxypropane 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-fluorenethyl)-1,3-dimethoxypropane, 2-(4-methylcyclohexyl)-2-isopentyl-1,3-dimethoxypropane, 2-cyclohexyl-2-(3-methylhexyl)-1,3-Dimethoxypropane, 2-(4-methylcyclohexyl)-2-(3-methylhexyl)-1,3-dimethoxypropane, 2-cyclohexyl-2-(3,3,3-triphenylpropyl)-1,3-dimethoxypropane, 2-(4-(tert-butyl)cyclohexyl)-2-(3,3,3-trichloropropyl)-1,3-dimethoxypropane, 2-(2-isopropyl-5-methylcyclohexyl)-2-(3,3-difluoropropyl)-1,3-dimethoxypropane, 2-(3,5-dimethylcyclohexyl)-2-(3,3-dibromopropyl)-1,3-dimethoxypropane, 2- (2-Isopropyl-5-methylcyclohexyl)-2-(3,3-dichloro-3-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-difluoro-5-methylhexyl)-1,3-diethoxypropane, 2-(2-isopropyl-5-methyl) Cyclohexyl)-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-di ...chloro-3-isopentyl-6-methylheptyl)-1,3-diethoxypropane, 2-(3,5-dimethylcyclohexyl)-2-(3-chloro-3-isopentyl-6-methylheptyl)-1,3-diethoxypropane, Cyclohexyl)-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-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 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-5- ... 2-(3,5-dimethylcyclohexyl)-2-(2-trimethylsilylethyl)-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-methyldiphenylmethyl) Silylethyl)-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,

[0020] ID2 is preferably selected from diesters of dicarboxylic acids, or from aromatic or aliphatic diols esterified with monocarboxylic acids.

[0021] Preferred dicarboxylic acids are aliphatic dicarboxylic acids selected from the group consisting of: malonic acid ester, maleic acid ester, citrate ester, succinate ester, glutarate ester, and adipate ester.

[0022] Preferred esterified diols are those disclosed in WO2010 / 078494 and US7,388,061, specific portions of which are hereby incorporated by reference.

[0023] The preferred carboxylic acid esters are selected from malonic acid esters, succinic acid esters and glutaric acid esters.

[0024] Preferred glutarates are those of formula (II):

[0025]

[0026] (II)

[0027] Free radicals that are the same or different from each other R1 to R8 It is H or optionally contains a heteroatom in C1-C 20 Straight-chain or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups, and two or more of the free radicals may also combine to form a ring, provided that... R7 and R8 Both are different from hydrogen.

[0028] One class of interesting substituted glutarates is that where R1 is H and R2 is selected from straight-chain or branched C1-C. 10 Alkyl, cycloalkyl, aryl, arylalkyl, and alkylaryl groups. Preferably, R2 is selected from straight-chain or branched C1-C2 groups. 10 Alkyl, cycloalkyl and arylalkyl groups.

[0029] In a preferred embodiment, in the compound of formula (I), R1 and R2 Both are different from hydrogen and are selected from straight-chain or branched C1-C atoms. 10 Alkyl, cycloalkyl, aryl, arylalkyl, and alkylaryl groups. More preferably, R1 and R2 Both are selected from C2-C5 straight-chain alkyl groups.

[0030] R7 and R8 are preferably primary alkyl, arylalkyl, or alkylaryl groups having 1 to 10 carbon atoms. More preferably, they are primary branched alkyl groups having 1 to 8 carbon atoms. Examples of suitable R7 and R8 groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, and 2-ethylhexyl.

[0031] Specific examples of β-monosubstituted glutarate esters are: 3-methylglutarate diisobutyl ester, 3-phenylglutarate diisobutyl ester, 3-ethylglutarate diethyl ester, 3-n-propylglutarate diethyl ester, 3-isopropylglutarate diethyl ester, 3-isobutylglutarate diethyl ester, 3-phenylglutarate diethyl ester, 3-ethylglutarate diisobutyl ester, 3-isopropylglutarate diisobutyl ester, 3-isobutylglutarate diisobutyl ester, 3-(3,3,3-trifluoropropyl)glutarate diethyl ester, 3-cyclohexylmethylglutarate diethyl ester, 3-tert-butylglutarate diethyl ester, and 2,2'-(3-methylcyclohexane-1,1-diyl)diacetic acid diisobutyl ester.

[0032] Specific examples of disubstituted or trisubstituted glutarates are: diethyl 3,3-dimethylglutarate, diisobutyl 3,3-dimethylglutarate, diethyl 3-methyl-3-isobutylglutarate, diethyl 3-methyl-3-tert-butylglutarate, diisobutyl 3-methyl-3-isobutylglutarate, diethyl 3-methyl-3-phenylglutarate, diethyl 3,3-di-n-propylglutarate, diisobutyl 3,3-di-n-propylglutarate, diethyl 3,3-diisobutylglutarate, diethyl 3-methyl-3-butylglutarate, and diethyl 3,3-diphenylglutarate. Diethyl 3-methyl-3-ethylglutarate, diethyl 3,3-diethylglutarate, diethyl 3-methyl-3-isopropylglutarate, diethyl 3-phenyl-3-n-butylglutarate, diethyl 3-methyl-3-tert-butylglutarate, diethyl 3,3-diisopropylglutarate, diisobutyl 3-methyl-3-phenylglutarate, diisobutyl 3,3-diisobutylglutarate, diisobutyl 3-methyl-3-butylglutarate, diisobutyl 3,3-diphenylglutarate, diisobutyl 3-methyl-3-ethylglutarate, diisobutyl 3,3-diethylglutarate Diisobutyl glutarate, 3-methyl-3-isopropylglutarate diisobutyl ester, 3-phenyl-3-n-butylglutarate diisobutyl ester, 3-methyl-3-tert-butylglutarate diisobutyl ester, 3,3-diisopropylglutarate diisobutyl ester, 3-ethyl-3-n-butylglutarate diethyl ester, 3-ethyl-3-n-butylglutarate diisobutyl ester, 3-isopropyl-3-n-butylglutarate diisobutyl ester, 3-(2-methyl-butyl)-3-ethylglutarate diethyl ester, 3-(2-methyl-butyl)-3-ethylglutarate diethyl ester, 3-(2-methyl-butyl)-3-ethylglutarate diethyl ester Diisobutyl diacid, diethyl 3-n-propyl-3-phenylpentanoate, diisobutyl 3-n-propyl-3-phenylpentanoate, diethyl 2-methyl-3-phenylpentanoate, diethyl 2,2-dimethyl-3-phenylpentanoate, diethyl 2-methyl-3,3-diisobutylpentanoate, diethyl 2-ethyl-3-isopropylpentanoate, diethyl 2-methyl-3-phenylpentanoate, diisobutyl 2,4-dimethyl-3-phenylpentanoate, diisobutyl 2-methyl-3,3-diisobutylpentanoate, and diisobutyl 2-ethyl-3-isopropylpentanoate. Among these, diethyl 3,3-di-n-propylpentanoate and diisobutyl 3,3-di-n-propylpentanoate are the most preferred.

[0033] Preferred succinates are those of formula (III):

[0034]

[0035] (III)

[0036] The free radicals R1 and R2, which may be identical or different from each other, are C1-C radicals that optionally contain heteroatoms. 20Straight-chain or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups; free radicals R3 to R6 that are the same as or different from each other, and are hydrogen or optionally contain heteroatoms in a C1-C group. 20 Straight-chain or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl groups, and radicals R3 to R6 that are attached to the same carbon atom of the succinate chain can be linked together to form a ring.

[0037] R1 and R2 are preferably C1-C8 alkyl, cycloalkyl, aryl, arylalkyl, and alkylaryl groups. Particularly preferred are compounds in which R1 and R2 are selected from primary alkyl groups, especially branched primary alkyl groups. Examples of suitable R1 and R2 groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, and 2-ethylhexyl. Particularly preferred are ethyl, isobutyl, and neopentyl.

[0038] One of the preferred groups of compounds described by formula (III) is one in which R3 to R5 are hydrogen atoms and R6 is a branched alkyl, cycloalkyl, aryl, arylalkyl, and alkylaryl radical having 3 to 10 carbon atoms. Specific examples of suitable monosubstituted succinate compounds are: diethyl sec-butylsuccinate, diethyl tert-hexylsuccinate, diethyl cyclopropylsuccinate, diethyl norbornylsuccinate, diethyl trimethylsilylsuccinate, diethyl methoxysuccinate, diethyl p-methoxyphenylsuccinate, diethyl p-chlorophenylsuccinate, diethyl phenylsuccinate, diethyl cyclohexylsuccinate, diethyl benzylsuccinate, diethyl cyclohexylmethylsuccinate, diethyl tert-butylsuccinate, diethyl isobutylsuccinate, and diethyl cyclohexylsuccinate. Diethyl isopropyl succinate, diethyl neopentyl succinate, diethyl isopentyl succinate, diethyl (1-trifluoromethylethyl) succinate, diethyl fluorenyl succinate, diisobutyl sec-butyl succinate, diisobutyl tert-hexyl succinate, diisobutyl cyclopropyl succinate, diisobutyl norbornyl succinate, diisobutyl chlorophenyl succinate, diisobutyl trimethylsilyl succinate, diisobutyl methoxysuccinate, diisobutyl p-methoxyphenyl succinate, diisobutyl p-chlorophenyl succinate, diisobutyl cyclohexyl succinate Butyl ester, benzyl diisobutyl succinate, cyclohexylmethyl diisobutyl succinate, tert-butyl diisobutyl succinate, isobutyl diisobutyl succinate, isopropyl diisobutyl succinate, neopentyl diisobutyl succinate, isopentyl diisobutyl succinate, (1-trifluoromethylethyl) diisobutyl succinate, phenyl diisobutyl succinate, fluorenyl diisobutyl succinate, sec-butyl dineopentyl succinate, tert-hexyl dineopentyl succinate, cyclopropyl dineopentyl succinate, norbornyl dineopentyl succinate, trimethylsilyl Dipentyl succinate, dipentyl methoxysuccinate, dipentyl p-methoxyphenylsuccinate, dipentyl p-chlorophenylsuccinate, dipentyl phenylsuccinate, dipentyl cyclohexylsuccinate, dipentyl benzylsuccinate, dipentyl cyclohexylmethylsuccinate, dipentyl tert-butylsuccinate, dipentyl isobutylsuccinate, dipentyl isopropylsuccinate, dipentyl neopentylsuccinate, dipentyl isopentylsuccinate, dipentyl (1-trifluoromethylethyl)succinate, dipentyl fluorenylsuccinate.

[0039] Another preferred group of compounds in formula (III) is one in which at least two radicals from R3 to R6 are different from hydrogen and are selected from C1-C radicals that optionally contain heteroatoms. 20Straight-chain or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups. Particularly preferred are compounds in which two radicals different from hydrogen are attached to the same carbon atom. Furthermore, compounds in which at least two radicals different from hydrogen are attached to different carbon atoms of the succinate chain (i.e., R3 and R5 or R4 and R6) are also particularly preferred. Suitable examples of disubstituted succinates are: diethyl 2,2-dimethylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl 2-benzyl-2-isopropylsuccinate, diethyl 2-cyclohexylmethyl-2-isobutylsuccinate, diethyl 2-cyclopentyl-2-n-butylsuccinate, diethyl 2,2-diisobutylsuccinate, diethyl 2-cyclohexyl-2-ethylsuccinate, diethyl 2-isopropyl-2-methylsuccinate, diethyl 2-tetradecyl-2-ethylsuccinate, and diethyl 2-isobutyl-2-ethylsuccinate. Diethyl succinate, 2-(1-trifluoromethyl-ethyl)-2-methylsuccinate, 2-isopentyl-2-isobutylsuccinate, 2-phenyl-2-n-butylsuccinate, 2,2-dimethylsuccinate, 2-ethyl-2-methylsuccinate, 2-benzyl-2-isopropylsuccinate, 2-cyclohexylmethyl-2-isobutylsuccinate, 2-cyclopentyl-2-n-butylsuccinate, 2,2-diisobutylsuccinate, 2-cyclohexyl-2-ethylsuccinate Diisobutyl succinate, 2-isopropyl-2-methylsuccinate, 2-tetradecyl-2-ethylsuccinate, 2-isobutyl-2-ethylsuccinate, 2-(1-trifluoromethyl-ethyl)-2-methylsuccinate, 2-isopentyl-2-isobutylsuccinate, 2-phenyl-2-n-butylsuccinate, dinepentyl 2,2-dimethylsuccinate, dinepentyl 2-ethyl-2-methylsuccinate, dinepentyl 2-benzyl-2-isopropylsuccinate, 2-cyclohexylmethyl-2-ethylsuccinate - Dinepentyl isobutylsuccinate, 2-cyclopentyl-2-n-butylsuccinate, 2,2-diisobutylsuccinate, 2-cyclohexyl-2-ethylsuccinate, 2-isopropyl-2-methylsuccinate, 2-tetradecyl-2-ethylsuccinate, 2-isobutyl-2-ethylsuccinate, 2-(1-trifluoromethyl-ethyl)-2-methylsuccinate, 2-isopentyl-2-isobutylsuccinate, 2-phenyl-2-n-butylsuccinate.

[0040] Furthermore, compounds in which at least two radicals other than hydrogen are attached to different carbon atoms (i.e., R3 and R5 or R4 and R6) are also particularly preferred. Specific examples of suitable compounds are: diethyl 2,3-bis(trimethylsilyl)succinate, diethyl 2,2-sec-butyl-3-methylsuccinate, diethyl 2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diethyl 2,3-bis(2-ethyl-butyl)succinate, diethyl 2,3-diethyl-2-isopropylsuccinate, diethyl 2,3-diisopropyl-2-methylsuccinate, diethyl 2,3-dicyclohexyl-2-methyldiethyl-2,3-dibenzylsuccinate, diethyl 2,3-diisopropylsuccinate, diethyl 2,3-bis(cyclohexylmethyl)succinate, diethyl 2,3-di-tert-butylsuccinate, diethyl 2,3-diisobutylsuccinate, and so on. Diethyl 2,3-dineopentyl succinate, diethyl 2,3-diisopentyl succinate, diethyl 2,3-(1-trifluoromethyl-ethyl) succinate, diethyl 2,3-tetradecyl succinate, diethyl 2,3-fluorenyl succinate, diethyl 2-isopropyl-3-isobutyl succinate, diethyl 2-tert-butyl-3-isopropyl succinate, diethyl 2-isopropyl-3-cyclohexyl succinate, diethyl 2-isopentyl-3-cyclohexyl succinate, diethyl 2-tetradecyl-3-cyclohexylmethyl succinate, diethyl 2-cyclohexyl-3-cyclopentyl succinate, diethyl 2,3-diethyl-2-isopropyl succinate, diisobutyl 2,3-diisopropyl-2-methyl succinate, diethyl 2,3- Dicyclohexyl-2-methylsuccinate diisobutyl ester, 2,3-dibenzylsuccinate diisobutyl ester, 2,3-diisopropylsuccinate diisobutyl ester, 2,3-bis(cyclohexylmethyl)succinate diisobutyl ester, 2,3-di-tert-butylsuccinate diisobutyl ester, 2,3-diisobutylsuccinate diisobutyl ester, 2,3-dineopentylsuccinate diisobutyl ester, 2,3-diisopentylsuccinate diisobutyl ester, 2,3-(1-trifluoromethyl-ethyl)succinate diisobutyl ester, 2,3-tetradecylsuccinate diisobutyl ester, 2,3-fluorenylsuccinate diisobutyl ester, 2-isopropyl-3-isobutylsuccinate diisobutyl ester, 2-tert-butyl-3-isopropylsuccinate diisobutyl ester, 2-isopropyl-3-cyclohexylsuccinate diisobutyl ester Diisobutyl succinate, 2-isopentyl-3-cyclohexylsuccinate, 2-tetradecyl-3-cyclohexylmethylsuccinate, 2-cyclohexyl-3-cyclopentylsuccinate, 2,3-bis(trimethylsilyl)succinate, 2,2-sec-butyl-3-methylsuccinate, 2-(3,3,3-trifluoropropyl)-3-methylsuccinate, 2,3-bis(2-ethyl-butyl)succinate, 2,3-diethyl-2-isopropylsuccinate, 2,3-diisopropyl-2-methylsuccinate, 2,3-dicyclohexyl-2-methylsuccinate, 2,3-dibenzylsuccinate, 2,Dipentyl 3-diisopropylsuccinate, dipentyl 2,3-bis(cyclohexylmethyl)succinate, dipentyl 2,3-di-tert-butylsuccinate, dipentyl 2,3-diisobutylsuccinate, dipentyl 2,3-dipentylsuccinate, dipentyl 2,3-diisopentylsuccinate, dipentyl 2,3-(1-trifluoromethyl-ethyl)succinate, dipentyl 2,3-tetradecylsuccinate Dipentyl ester, dipentyl 2,3-fluorenylsuccinate, dipentyl 2-isopropyl-3-isobutylsuccinate, dipentyl 2-tert-butyl-3-isopropylsuccinate, dipentyl 2-isopropyl-3-cyclohexylsuccinate, dipentyl 2-isopentyl-3-cyclohexylsuccinate, dipentyl 2-tetradecyl-3-cyclohexylmethylsuccinate, dipentyl 2-cyclohexyl-3-cyclopentylsuccinate.

[0041] Another preferred subclass of succinates may be selected from those of formula (IIIa):

[0042]

[0043] (IIIa)

[0044] The free radicals R1 and R2, which may be identical or different from each other, are C1-C radicals that optionally contain heteroatoms. 20 Straight-chain or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups; and free radicals R3 and R4, which are identical or different from each other, are C1-C. 20 Alkyl, C3-C 20 cycloalkyl, C5-C 20 The compound is an aryl, arylalkyl, or alkylaryl group, provided that at least one of them is a branched alkyl group; the compound is a (S,R) or (R,S) stereoisomer relative to the two asymmetric carbon atoms identified in the structure of formula (IIIa).

[0045] R1 and R2 are preferably C1-C8 alkyl, cycloalkyl, aryl, arylalkyl, and alkylaryl groups. Particularly preferred are compounds in which R1 and R2 are selected from primary alkyl groups, especially branched primary alkyl groups. Examples of suitable R1 and R2 groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, and 2-ethylhexyl. Particularly preferred are ethyl, isobutyl, and neopentyl.

[0046] Particularly preferred are compounds in which the R3 and / or R4 radicals are secondary alkyl groups (such as isopropyl, sec-butyl, 2-pentyl, 3-pentyl) or cycloalkyl groups (such as cyclohexyl, cyclopentyl and cyclohexylmethyl).

[0047] Examples of the above compounds are the following in pure (S,R) form or mixtures thereof, optionally in racemic form: diethyl 2,3-bis(trimethylsilyl)succinate, diethyl 2,3-bis(2-ethylbutyl)succinate, diethyl 2,3-dibenzylsuccinate, diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diethyl 2,3-bis(cyclohexylmethyl)succinate, diethyl 2,3-diisobutylsuccinate, diethyl 2,3-dineopentylsuccinate, diethyl 2,3-dicyclopentylsuccinate, and diethyl 2,3-dicyclohexylsuccinate.

[0048] Preferred malonates are those of formula (IV):

[0049]

[0050] Where R1 is H or Cl-C 20 Straight-chain or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups, where R2 is C1-C 20 Straight-chain or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups, with R3 and R4 being the same or different from each other and being C1-C2. 20 Straight-chain or branched alkyl groups or C3-C 20 Cycloalkyl groups.

[0051] Preferably, R3 and R4 are linear or branched C1-C chains. 20 Alkyl groups, more preferably, are primary branched C4-C groups. 20 Alkyl groups, such as isobutyl or neopentyl groups.

[0052] In particular, when R1 is H, R2 is preferably a straight-chain or branched C3-C. 20 Alkyl, cycloalkyl, or arylalkyl groups; more preferably, R2 is C3-C 20 Secondary alkyl, cycloalkyl, or arylalkyl groups.

[0053] Preferred examples of monosubstituted malonic acid ester compounds are: dipentyl 2-isopropylmalonate, diisobutyl 2-isopropylmalonate, di-n-butyl 2-isopropylmalonate, diethyl 2-dodecylmalonate, diethyl 2-tert-butylmalonate, diethyl 2-(2-pentyl)malonate, diethyl 2-cyclohexylmalonate, dipentyl 2-tert-butylmalonate, dipentyl 2-isobutylmalonate, dipentyl 2-cyclohexylmethylmalonate, and dimethyl 2-cyclohexylmethylmalonate.

[0054] Preferred examples of disubstituted malonate compounds are: diethyl 2,2-dibenzylmalonate, diethyl 2-isobutyl-2-cyclohexylmalonate, dimethyl 2-n-butyl-2-isobutylmalonate, diethyl 2-n-butyl-2-isobutylmalonate, diethyl 2-isopropyl-2-n-butylmalonate, diethyl 2-methyl-2-isopropylmalonate, diethyl 2-isopropyl-2-isobutylmalonate, diethyl 2-methyl-2-isobutylmalonate, diethyl 2-isobutyl-2-benzylmalonate, diethyl 2,2-diisobutylmalonate, and diethyl 2-isopentyl-2-cyclohexylmalonate.

[0055] Preferably, when the molar ratio between the sum of ID1 and ID2 (ID1+ID2) and Ti atoms in the final solid catalyst component ((ID1+ID2) / Ti) is in the range of 0.45 to 0.70, the molar ratio ID2 / ID1 is in the range of 0.8:1 to less than 1.0:1, more preferably 0.85:1 to less than 1.0:1, and especially 0.90:1 to less than 1.0:1.

[0056] In a more preferred embodiment, when ((ID1+ID2) / Ti) is in the range of 0.45 to 0.70 and ID2 / ID1 is in the range of 0.8:1 to 1.0:1, the ID2 / Ti molar ratio is in the range of 0.15:1 to 0.50:1.

[0057] Preferably, when ((ID1+ID2) / Ti) is in the range of 0.80:1 to 1.70:1, and particularly in the range of 1.0:1 to 1.70:1, the molar ratio ID2 / ID1 is in the range of 0.5:1 to 1:0:1.

[0058] Preferably, the molar ratio of Mg atoms to ID1 in the final solid catalyst component is in the range of 10:1 to 40:1, preferably 15:1 to 35:1, and more preferably 18:1 to 30:1.

[0059] Preferably, the solid catalyst component has a particle size of at least 0.20 cm⁻¹ as determined by the mercury method. 3 The porosity is defined as per g, 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⁻². 3 / g, and especially above 0.40 cm 3 / g.

[0060] Preferably, the catalyst component has an average particle size ranging from 20 to 150 µm, and more preferably from 40 to 100 µm.

[0061] As explained above, in addition to the electron donors, the catalyst composition of the present invention also includes a titanium compound having at least one Ti-halogen bond and magnesium halide. Preferred titanium compounds used in the catalyst composition of the present invention are TiCl4 and TiCl3; furthermore, Ti(OR) can also be used. 5 ) n-y X y Ti-halools, where n is the valence of titanium, y is a number between 1 and n-1, X is a halogen, and R 5 It is a hydrocarbon radical with 1 to 10 carbon atoms.

[0062] The preparation of solid catalyst components can be carried out according to several methods. According to a preferred method, the solid catalyst components can be prepared by using the formula Ti(OR) 5 ) m-y X y Titanium compounds (where m is the valence of titanium and y is a number between 1 and m, preferably TiCl4) and those derived from the formula MgCl2 • pR 6 OH (where p is between 0.1 and 6, preferably a number from 2 to 3.5, and R) 6 The adduct is prepared by reacting magnesium chloride with an adduct of a hydrocarbon radical having 1 to 18 carbon atoms. By mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, and operating under stirring at the melting temperature of the adduct (100 to 130 °C), a spherical form of the adduct can be suitably prepared. The emulsion is then rapidly quenched, thereby solidifying the adduct into 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 pre-treated with thermally controlled alcohol removal (80 to 130 °C) to obtain an adduct in which the molar number of alcohol is less than 3, preferably between 0.1 and 2.5, and even more preferably between 0.5 and 2.3.

[0063] 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 (de-alcoholized or as is) adduct in cold TiCl4, typically at 0°C. Preferably, the adduct is used in an amount such that it has a concentration in the range of 20 to 100 g / L, and more preferably 30 to 90 g / L. According to a preferred embodiment, ID2 is added to the system at the beginning of this reaction stage and preferably when the temperature of the mixture is in the range of 10°C to 60°C. ID2 is fed in an amount such that it satisfies the desired molar ratio in the final catalyst. In embodiments, the Mg / ID2 molar ratio can be in the range of 5:1 to 50:1, preferably 10:1 to 45:1, more preferably 15:1 to 40:1, and especially 20:1 to 40:1. The temperature is then gradually increased until it reaches a temperature in the range of 90 to 130°C, and is maintained at this temperature for 0.5 to 3 hours.

[0064] After the reaction time is complete, 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 in the range of 70 to 130°C. Preferably, ID1 is added in this stage. ID1 is preferably fed in an amount such that the Mg / ID1 molar ratio is in the range of 4:1 to 35:1, preferably 6:1 to 30:1, more preferably 7:1 to 25:1. After the reaction time is complete, stirring is stopped, the slurry is allowed to settle, and the liquid phase is removed. Although not required, an additional reaction stage can be carried out under the same conditions described above, and in the absence of an electron donor, using a titanium compound, and preferably TiCl4. The solid thus obtained can then be washed with liquid hydrocarbons under mild conditions and then dried.

[0065] 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 of the periodic table (IUPAC version), preferably groups 11 to 15.

[0066] Most preferably, the compound, which does not contain metal-carbon bonds, comprises an element selected from Cu, Zn, and Bi. Preferred compounds are oxides, carbonates, alkoxylates, carboxylates, and halides of the metal. Among these, ZnO, ZnCl2, CuO, CuCl2 and Cu diacetate, BiCl3, Bi carbonates, and Bi carboxylates are preferred. 3、 Bi carbonates and Bi carboxylates are particularly preferred.

[0067] The compounds can be added during the preparation of the aforementioned magnesium-alcohol adducts, or they can be introduced into the catalyst by dispersing them in liquid form of titanium compounds and then reacting them with the adducts.

[0068] Regardless of the method used, the final amount of the metal entering the final catalyst component is in the range of 0.1 to 10% by weight, preferably from 0.3 to 8% by weight, and most preferably from 0.5 to 5% by weight, relative to the total weight of the solid catalyst component.

[0069] 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.

[0070] In particular, the object of the present invention is a catalyst for the polymerization of olefins CH2=CHR, wherein R is hydrogen or a hydrocarbon radical having 1 to 12 carbon atoms, the catalyst comprising a product obtained by contacting the following substances:

[0071] (i) the solid catalyst composition as disclosed above and

[0072] (ii) Alkyl aluminum compounds, and optionally

[0073] (iii) External electron donor compounds.

[0074] The alkyl-Al compound (ii) is preferably selected from trialkylaluminum compounds, such as, for example, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum. Alkylaluminum halides, alkylaluminum hydrides, or alkylaluminum sesquichlorides, such as AlEt2Cl and Al2Et3Cl3, may also be used, possibly in combination with the above-mentioned trialkylaluminum compounds.

[0075] 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.

[0076] Another preferred type of external donor compound is of formula (R) 7 ) a (R 8 ) b Si(OR 9 ) c A silicon compound, where a and b are integers from 0 to 2, c is an integer from 1 to 4, and the sum (a+b+c) is 4; R 7 R 8 and R 9 It may optionally contain a heteroatom, such as an alkyl, cycloalkyl, or aryl radical having 1 to 18 carbon atoms. Particularly preferred are silicon compounds in which a is 1, b is 1, c is 2, and R... 7 and R 8 At least one of them is selected from branched alkyl, cycloalkyl, or aryl groups having 3 to 10 carbon atoms, optionally containing heteroatoms, and R 9It is C1-C 10 Alkyl groups, particularly 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, and methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane. Furthermore, silicon compounds in which a is 0, c is 3, and R... 8 It may optionally contain a branched alkyl or cycloalkyl group with heteroatoms, and R 9 It is methyl. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, and tert-hexyltrimethoxysilane.

[0077] The amount of external electron donor compound (iii) is such that the molar ratio between the organoaluminum compound and the electron donor compound (iii) is 0.1:1 to 500:1, preferably 1:1 to 300:1, and more preferably 3:1 to 100:1.

[0078] The catalyst of this disclosure (where the ((ID1+ID2) / Ti) molar ratio is in the range of 0.45 to 0.70) provides medium / highly stereoregular polypropylene and is particularly suitable for BOPP grades. It should be noted that the catalyst of this disclosure can meet the requirements with a much lower amount of ID1 compared to a catalyst in which ID1 is the only donor.

[0079] The same applies to catalysts where ((ID1+ID2) / Ti) is in the range of 0.80:1 to 1.70:1, which provides a very high level of stereoregularity. Moreover, in this case, the requirements can be met using a fairly low level of ID1.

[0080] Therefore, this constitutes another object of the present invention: a process for the (co)polymerization of olefins CH2=CHR, wherein R is hydrogen or a hydrocarbon radical having 1 to 12 carbon atoms, the process being carried out in the presence of a catalyst comprising the reaction products between the following substances:

[0081] (i) The solid catalyst components of the present invention;

[0082] (ii) Alkyl aluminum compounds, and

[0083] (iii) Optional electron donor compound (external donor).

[0084] The polymerization process can be carried out using known techniques, such as slurry polymerization using inert hydrocarbon solvents as diluents, or bulk polymerization using liquid monomers (e.g., propylene) as the reaction medium. Additionally, polymerization methods can be performed in the gas phase within one or more fluidized bed or mechanically stirred bed reactors.

[0085] The catalyst of the present invention can be used as is in a polymerization process by directly introducing it into the reactor. In a preferred embodiment, the catalyst may be prepolymerized before being introduced into the first polymerization reactor. As used in the art, the term "prepolymerized" means that the catalyst has already undergone a polymerization step at a low conversion level. According to the present invention, the catalyst is considered prepolymerized when the amount of polymer produced is from about 0.1 to at most about 1000 g / gram of solid catalyst component.

[0086] Prepolymerization can be carried out with α-olefins selected from the same olefin group disclosed above. In particular, it is especially preferred to prepolymerize ethylene or mixtures thereof with one or more α-olefins in an amount of up to 20 mol%. Preferably, the conversion rate of the prepolymerization catalyst component is from about 0.2 g to up to about 500 g / g solid catalyst component.

[0087] The prepolymerization step can be carried out in the liquid or gas phase at a temperature ranging from 0°C to 80°C, preferably from 5°C to 50°C. The prepolymerization step can be carried out online as part of a continuous polymerization process or separately in a batch process. It is particularly preferred that the catalyst of the present invention undergoes batch prepolymerization with ethylene to produce a polymer amount ranging from 0.5 to 20 g / gram of catalyst component.

[0088] Polymerization is typically carried out at temperatures ranging from 20 to 120°C, preferably from 40 to 80°C. When polymerization is carried out in the gas phase, the operating pressure is typically between 0.5 and 5 MPa, preferably between 1 and 4 MPa. In bulk polymerization, the operating pressure is typically between 1 and 8 MPa, preferably between 1.5 and 5 MPa.

[0089] Preferred α-olefins for (co)polymerization are ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene. In particular, the above-described catalysts can be used for (co)polymerization of propylene and ethylene to prepare various kinds of products, especially propylene homopolymers and copolymers. Considering their high activity and stereospecificity, the catalysts disclosed herein can be advantageously used to prepare propylene / ethylene copolymers with low xylene-soluble content and high-purity polypropylene polymers with very low contents of halogens (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% by weight of the total weight of propylene and ethylene, the catalysts disclosed herein can provide copolymers with low amounts of xylene-soluble material.

[0090] 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% by weight in some applications) of (B) a low-crystallinity, highly xylene-soluble propylene-vinyl copolymer.

[0091] Such polymer compositions are preferably prepared using a multi-step process comprising at least two distinct polymerization stages carried out in different reactors. Typically, the first step in preparing the crystalline propylene homopolymer or copolymer can be carried out in either the gas 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, one operating under rapid fluidization conditions and the other in which the polymer flows under gravity. Liquid-phase processes can be slurries, solutions, or bulk (liquid monomers). The latter technique is most preferred and can be carried out in various types of reactors, such as continuous stirred tank reactors, circulating reactors, or plug flow reactors. Preferably, the first step is carried out in the gas phase. In this stage and / or the continuous stage, hydrogen can be used as a molecular weight regulator.

[0092] 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 polymerizing materials and catalyst system from the aforementioned polymerization steps.

[0093] The polymer produced in this stage may contain 15 to 75% by weight of ethylene, optionally a smaller proportion of diene, and the polymer may have a solubility of at least 60% by weight in xylene at 25°C.

[0094] The following examples are given for illustrative purposes and not for limiting the invention itself.

[0095] Characterization

[0096] Porosity determination.

[0097] Mercury porosity and surface area: Measurements were performed using a Pascal 140-240 series porosity meter manufactured by Carlo Erba.

[0098] Porosity was determined by the intrusion of mercury under pressure. For this determination, a calibrated dilatometer (capillary diameter 3 mm) CD3P (manufactured by Carlo Erba) connected to a mercury reservoir and a high-vacuum pump was used. A weighed sample was placed in the dilatometer. The apparatus was then placed under high vacuum and maintained under these conditions for approximately 20 minutes. The dilatometer was then connected to the mercury reservoir, and mercury was allowed to slowly fill the dilatometer until it reached the level marked at a height of 10 cm on the dilatometer. The valve connecting the dilatometer to the vacuum pump was closed, and the mercury pressure was gradually increased to 100 kPa using nitrogen. Subsequently, the calibrated dilatometer was transferred to an autoclave with high-pressure oil to reach a pressure value of up to 200 MPa. Under pressure, mercury entered the pores of the particles, and the mercury level decreased accordingly.

[0099] Porosity (cm) 3 The porosity ( / g), pore size distribution curve, and average pore diameter are calculated directly from the integrated pore size distribution curve, which is a function of both the volume reduction of mercury and the applied pressure. All these data are provided and detailed by a computer associated with the porosity meter, equipped with dedicated software supplied by Carlo Erba. Following the calculation, the average pore radius is given as a weighted average of the individual average pore radius contributions for each porosity interval.

[0100] Measurement of XI

[0101] Approximately 2.5 g of polymer and 250 ml of o-xylene were placed in a round-bottom flask equipped with a cooler and a reflux condenser and kept under nitrogen atmosphere. The resulting mixture was heated to 135 °C and maintained with stirring for approximately 60 minutes. The final solution was allowed to cool to 25 °C with continuous stirring, and then the insoluble polymer was filtered off. The filtrate was then evaporated at 140 °C under a nitrogen stream to constant weight. The content of the xylene-soluble fraction is expressed as a percentage of the original 2.5 g and then expressed as XI by the difference.

[0102] Determination of the donor.

[0103] The content of electron donors was determined by gas chromatography.

[0104] Determination of melt flow rate (MFR).

[0105] The melt flow rate (MIL) of the polymer was determined according to ISO 1133 (230°C, 2.16 kg).

[0106] Determination of comonomers.

[0107] The content of comonomer (ethylene) was determined by NMR spectroscopy.

[0108] Determination of Tm

[0109] The determination was performed using differential scanning calorimetry (DSC). 6 ± 1 mg of sample was weighed and heated to 220 ± 1 °C at a rate of 20 °C / min in a nitrogen stream, held at 220 ± 1 °C for 2 minutes, and then cooled to 40 ± 2 °C at a rate of 20 °C / min, held at that temperature for 2 minutes to allow crystallization. The sample was then heated to 220 ± 1 °C at a rate of 20 °C / min to remelt the sample. Melt scans were recorded to obtain thermograms, from which the melting and crystallization temperatures were read.

[0110] Determination of intrinsic viscosity (IV)

[0111] The intrinsic viscosity was measured based on the xylene soluble fraction. The sample was dissolved in tetrahydronaphthalene at 135°C and then poured into a capillary viscometer. The viscometer tube (Ubbelohde type) was surrounded by a cylindrical glass jacket; this setup allows for temperature control using a circulating, constant-temperature liquid. The downward passage of the meniscus was timed by a photoelectric device.

[0112] The passage of the meniscus in front of the upper lamp activates a counter with a quartz crystal oscillator. When the meniscus passes the lower lamp, it stops the counter, and the outflow time is recorded: this is converted to an intrinsic viscosity value using the Huggins equation (Huggins, ML, *Journal of the American Chemical Society*, 1942, 64, 2716), provided that the flow time of the pure solvent is known under the same experimental conditions (same viscometer and same temperature). [η] is determined using a single polymer solution.

[0113] Determination of flexural modulus

[0114] Flexural modulus is measured according to ISO 178 and ISO 1873-2.

[0115] Determination of tensile modulus

[0116] Tensile modulus measured according to ISO 527 and ISO 1873-2

[0117] Charpy's measurement

[0118] Charpy impact test according to ISO 179-1eA and ISO 1873-2

[0119] Determination of 13C NMR spectrum of propylene / ethylene copolymer

[0120] Multiphase copolymers and their XI and XS fractions 13C10 NMR spectra were acquired on a Bruker AV-600 spectrometer equipped with a cryoprobe, operated at 160.91 MHz in Fourier transform mode at 120 °C.

[0121] S ββ Carbon (according to "through") 13 The monomer sequence distribution in ethylene-propylene rubber was measured by 13C NMR. The peak at 29.9 ppm was used as an internal reference. The sample was dissolved in 1,1,2,2-tetrachloroethane-d2 at 120 °C with a concentration of 8 wt% / volume. Each spectrum was acquired as 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 9000 Hz spectral window. (See "Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Mode" by CJ Carman, RA Harrington, and CE Wilkes, *Macromolecules*, 1977, 10, 536).

[0122] The spectral assignment, triplet state distribution, and composition assessment were 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:

[0123] PPP = 100 T ββ / S PPE = 100 T βδ / SEPE = 100 T δδ / S

[0124] PEP = 100 S ββ / S PEE = 100 S βδ / S EEE = 100 (0.25 S δ + 0.5 S δδ ) / S

[0125] S = T ββ + T βδ + T δδ + S ββ + S βδ + 0.25 S δ + 0.5 S δδ

[0126] The molar percentage of ethylene content was evaluated using the following equation:

[0127] E moles% = 100 × [PEP + PEE + EEE]

[0128] The weight percentage of ethylene content is assessed using the following equation:

[0129] E %wt = 100 × MW E × E% mol / (MW E × E% mol + MW P × P% mol)

[0130] Where P% mol is the molar percentage of propylene content, and MW E and MW P These are the molecular weights of ethylene and propylene, respectively.

[0131] Example

[0132] General procedure for preparing MgCl2*pEtOH adducts.

[0133] The initial amount of microspheres of MgCl2*2.8EtOH was prepared according to the method described in Example 2 of USP 4,399,054, but at 3,000 rpm instead of 10,000 rpm. A portion of the adduct thus obtained was then thermally deethanolinated in a nitrogen stream at increasing temperatures from 30 to 130 °C until the molar alcohol content per mole of Mg was 2.1.

[0134] Preparation of electron donors

[0135] Synthesis of 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane

[0136] Step 1: Synthesis of diethyl 2-cyclohexylmalonate

[0137] Ethanol (400 mL) and potassium tert-butoxide (50 g, 0.4 mol) were added to a 1 L round-bottom flask equipped with a mechanical stirrer, thermometer, and condenser. Then, 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. The mixture was refluxed for 40 hours, then the solvent was removed under vacuum, and the slurry was recovered with ethyl acetate (200 mL). The organic phase was washed with water (2 × 100 mL) and 10% NaHCO3, and then evaporated to give 26 g of diethyl 2-cyclohexylmalonate as a pale yellow oil, 99% (GC) pure, in 27% yield. 1 HNMR (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).

[0138] Step 2: Synthesis of diethyl 2-cyclohexyl-2-isopentylmalonate

[0139] 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, thermometer, and condenser. The temperature was raised to 40 °C, and gas formation was observed. After 1 hour, the gas escaped and disappeared, and then isopentyl bromide (20 g, 130 mmol) was added over 30 minutes. The mixture was placed under reflux for 25 hours and then diluted with 300 mL of 1 M HCl. The organic phase was diluted with diethyl ether (200 mL), washed with water (2 × 100 mL), and then evaporated to give 23 g of diethyl 2-cyclohexyl-2-isopentylmalonate as a pale yellow oil with a purity of 95% (GC) and a yield of 67%. 1 ¹H NMR (δ, 400 MHz, CDCl₃): 4.1 (q, 4H, OCH₂), 1.7 (m, 3H, CHcyclohexyl + α-CH₂isopentyl), 1.6–1.3 (m, 8H, cyclohexyl), 1.2 (m, 7H, OCH₂CH₃ + γ-CHisopentyl), 1.0 (m, 4H, cyclohexyl + β-CH₂isopentyl), 0.8 (d, 6H, (CH₃)₂isopentyl).

[0140] Step 3: Synthesis of 2-cyclohexyl-2-isopentyl-1,3-propanediol

[0141] 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, thermometer, and condenser. The mixture was refluxed for 16 hours and then diluted with 200 mL of 1 M HCl. The organic phase was extracted with diethyl ether (200 mL), washed with water (2 × 100 mL), and 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%. 1 ¹H NMR (δ, 400 MHz, CDCl₃): 4.9–4.6 (dd, 4H, OCH₂), 2.2 (s, 2H, OH), 1.9–1.1 (m, 16H, cyclohexyl + isopentyl), 0.9 (d, 6H, (CH₃)₂isopentyl).

[0142] Step 4: Synthesis of 2-cyclohexyl-2-isopentyl-1,3-dimethoxypropane

[0143] 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, thermometer, and condenser. The temperature was raised to 40 °C (gas escape), and methyl iodine (20 g, 141 mmol) was added dropwise over 1 hour. The slurry was then allowed to stand at 40 °C for 8 hours and diluted with 200 mL of 1 M HCl. The organic phase was diluted with diethyl ether (100 mL), washed with water (2 × 50 mL), and then evaporated to give 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).

[0144] Preparation of solid catalyst components - general procedure.

[0145] At 0 °C, 500 mL of TiCl4 was introduced into a 1000 mL four-necked round-bottom flask purged with nitrogen. While stirring, 25 g of microspheres of MgCl2∙2.1EtOH adduct (prepared as described above) was added. Then, a certain amount of BiCl3 was added at -3 °C to have a Mg / BiCl3 molar ratio of 60, and subsequently, a certain amount of ID2 was added at 40 °C to achieve the Mg / donor ratio reported in Table 1.

[0146] The temperature was raised to 100 °C and maintained at that value for 60 minutes. Afterward, stirring was stopped, the liquid was siphoned off, and the treatment with TiCl4 was repeated at 120 °C for 30 minutes, with the amount of ID1 reported in Table 1 added at the start. Following precipitation and siphoning, the solid was washed with anhydrous heptane (6 × 100 ml) while the temperature was lowered from 90 °C to RT, and dried to obtain a free-flowing powder. The characterization of the components of the solid catalyst thus obtained is reported in Table 1.

[0147] General procedure for bulk homopolymerization of propylene

[0148] 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 nitrogen stream at 70°C for one hour. Then, at 30°C, under a propylene flow, the following were added sequentially: 14 ml of anhydrous hexane (containing 0.6 g of AlEt3), approximately 6 mg of solid catalyst component, and, if used, an external donor (type and amount reported in the table). The autoclave was shut off, and then hydrogen was added in the amounts indicated in Table 2. Then, under stirring, 1.2 kg of liquid propylene was fed. The temperature was raised to 70°C over ten minutes, and polymerization was carried out at this temperature for two hours. At the end of polymerization, unreacted propylene was removed; the polymer was recovered and dried in an oven at 80°C.

[0149] Examples 1 to 11 and Comparative Examples 12 to 13: Polymerization of propylene.

[0150] The catalysts of Examples 1 to 4 and Comparative Example 5 were prepared according to the general procedure described above, except that BiCl3 was not used in Example 1, and in Example 8, the first treatment with TiCl4 was carried out at 110°C. The types and amounts of donors are described in Table 1. The results of the bulk polymerization of propylene are reported in Table 2.

[0151] Table 1.

[0152]

[0153] ID1 = 2-Cyclohexyl-2-isopentyl-1,3-dimethoxypropane

[0154] DEDIPS = Diethyl 2,3-Diisopropylsuccinate

[0155] DECIM = Diethyl 2-cyclohexyl-2-isopentylmalonate

[0156] Table 2

[0157]

[0158]

[0159] TEAL / external donor molar ratio 20

[0160] Comparisons between E3 and C12 (similar levels of ID1 / Ti) and between E11 and C13 (similar total donor / Ti ratios, with lower levels of ID1 / Ti in E11) suggest that using significantly less ID1 can maintain good performance, or even improve catalyst performance at the same level of ID1.

Claims

1. A solid catalyst component for olefin polymerization, said solid catalyst component comprising magnesium halide, a titanium compound having at least a Ti-halogen bond, and at least two electron donor compounds, wherein one of the at least two electron donor compounds (ID1) is selected from 1,3-diethers of formula (I): （I） Where R 1 and R 2 Independently, it is a C1-C5 alkyl group, where X is Si or C, and R is... 3 and R 4 The groups are independently selected from hydrogen, C1-C. 20 Hydrocarbon groups and halogens, provided there are at least two R groups. 3 It is not hydrogen, and the other electron donor compound (ID2) is selected from organic compounds with two ester groups. The solid catalyst component is further characterized by the fact that the molar ratio between ID2 and ID1 (ID2 / ID1) is in the range of 0.5:1 to less than 1.0:1, and the molar ratio between the sum of ID1 and ID2 (ID1+ID2) and Ti atoms in the final solid catalyst component ((ID1+ID2) / Ti) is in the range of 0.45:1 to 1.70:1, provided that: i) When ((ID1+ID2) / Ti) is in the range of 0.45 to 0.70, the molar ratio ID2 / ID1 is in the range of 0.70:1 to less than 1.0:1; and ii) When ((ID1+ID2) / Ti) is in the range of 0.80 to 1.70, the molar ratio ID2 / Ti is in the range of 0.30:1 and 0.70:

1.

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

3. The solid catalyst component according to claim 1, wherein all R 4 All the radicals are hydrogen.

4. The solid catalyst component according to any one of the preceding claims, wherein when R 3 When it is a hydrocarbon group, it is selected from C1-C4 straight-chain or branched alkyl groups and groups linked together to form a C6 saturated ring that may be optionally replaced by a C1-C4 straight-chain alkyl group.

5. The solid catalyst component according to any one of claims 1 to 4, wherein X is carbon.

6. The solid catalyst component according to any one of the preceding claims, wherein the ID2 is selected from the esters of aliphatic dicarboxylic acids, the esters of the aliphatic dicarboxylic acids being selected from the group consisting of: malonic acid esters, maleic acid esters, citrate esters, succinate esters, glutaric acid esters and adipate esters.

7. The solid catalyst component according to claim 6, wherein the succinate is one of those of formula (III): The free radicals R1 and R2, which may be identical or different from each other, are C1-C radicals that optionally contain heteroatoms. 20 Straight-chain or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups; free radicals R3 to R6 that are the same as or different from each other, and are hydrogen or optionally contain heteroatoms in a C1-C group. 20 Straight-chain or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl groups, and radicals R3 to R6 that are attached to the same carbon atom of the succinate chain, can link together to form a ring.

8. The solid catalyst component according to any one of the preceding claims, wherein when the molar ratio between the sum of ID1 and ID2 (ID1+ID2) in the final solid catalyst component and Ti atoms ((ID1+ID2) / Ti) is in the range of 0.45 to 0.70, the molar ratio ID2 / ID1 is in the range of 0.80:1 to 1.0:1, more preferably 0.85:1 to 1.0:1, and especially 0.90:1 to 1.0:

1.

9. The solid catalyst composition according to claim 8, wherein the ID2 / Ti molar ratio is in the range of 0.15:1 to 0.50:

1.

10. The solid catalyst component according to any one of the preceding claims, wherein the molar ratio ID2 / ID1 is in the range of 0.5:1 to 1:0:1 when ((ID1+ID2) / Ti) is in the range of 0.80:1 to 1.70:1, and particularly 1.0:1 to 1.70:

1.

11. The solid catalyst component according to any one of the preceding claims, wherein the molar ratio of Mg atoms to ID1 in the final solid catalyst component is in the range of 10:1 to 40:1, preferably 15:1 to 35:1, and more preferably 18:1 to 30:

1.

12. The solid catalyst component according to any one of the preceding claims, wherein the solid catalyst component comprises an additional metal compound, the additional metal compound being free of metal-carbon bonds and comprising an element selected from Cu, Zn and Bi.

13. The solid catalyst component according to claim 12, wherein the metal compound is selected from BiCl3, Bi carbonates and Bi carboxylates.

14. 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 the following substances: (i) the solid catalyst component according to any one of the preceding claims, and (ii) Alkyl aluminum compounds, and optionally (iii) External donor compounds.

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, said process being carried out in the presence of the catalyst according to claim 14.

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