Olefin polymerization catalyst components

Abstract

A solid catalyst component for olefin polymerization, comprising Mg, Ti, and an electron donor of formula (I), [Formula 1] JPEG2026506029000010.jpg3348 (I) During the ceremony, R1 and R 9 The groups may be the same or different and are C-C 15 R is selected from hydrocarbon groups; 2 The group is hydrogen or C1-C 10 R is selected from hydrocarbon groups; 3 ~R 8 The groups are independently hydrogen or C-C groups which can be fused together to form one or more rings. 15 The hydrocarbon group is selected from the group consisting of: Catalyst systems based on solid catalyst components have high activity and stereospecificity.

Description

[Technical Field]

[0001] The present disclosure relates to a catalyst component for the polymerization of olefins, particularly propylene, comprising a Mg dihalide support on which Ti atoms are supported and an electron donor compound containing ester and carbamate functional groups. The disclosure also relates to catalysts obtained from the component and their use in olefin, particularly propylene, polymerization processes. [Background technology]

[0002] Catalyst components for the stereospecific polymerization of olefins have been disclosed in the art. For propylene polymerization, Ziegler-Natta catalysts, typically containing a solid catalyst component composed of a magnesium dihalide supported on a titanium compound and an internal electron donor compound, are used in combination with an alkylaluminum compound. However, traditionally, if higher crystallinity of the polymer is desired, an external donor (e.g., an alkoxysilane) is also required to achieve higher isotacticity. Phthalate esters, particularly diisobutyl phthalate, are used as internal donors in catalyst preparation. This catalyst system, in which phthalate esters are used as internal donors in combination with alkylalkoxysilanes as external donors, exhibits superior performance in terms of activity, isotacticity, and xylene insolubility.

[0003] One of the problems associated with the use of this catalyst system is that phthalates have recently generated some concern, with some compounds belonging to this class being classified as causing serious health problems.

[0004] As a result, research efforts have been devoted to discovering alternative classes of internal donors in the preparation of catalyst components for propylene polymerization.

[0005] Some of the tested catalysts contain donor structures that simultaneously contain both a carbamate group and an ester group. PCT Publication WO 2018 / 091375 describes 1,3-aminoester derivatives containing one carbamate group and one free ester function. In terms of the activity / stereospecificity balance, the performance of these catalysts is not entirely satisfactory, and improvements are needed, especially in terms of stereospecificity. Summary of the Invention

[0006] Surprisingly, applicants have discovered that a class of donors containing both carbamate and ester functionalities in specific structures derived from amino acids yields catalysts that exhibit a good balance of activity and stereospecificity.

[0007] Therefore, an object of the present disclosure is to provide a catalyst component for olefin polymerization comprising Mg, Ti and an electron donor of formula (I), [ka] (I) In the formula, R 1 and R 9 The groups may be the same or different and are C-C 15 R is selected from hydrocarbon groups; 2 The group is hydrogen or C1-C 10 R is selected from hydrocarbon groups; 3 ~R 8 The groups are independently hydrogen or C-C groups which can be fused together to form one or more rings. 15 The hydrocarbon group is selected from the group consisting of: DETAILED DESCRIPTION OF THE INVENTION

[0008] In addition to carbon and hydrogen, the group R defined above 1 ~R 9 may contain heteroatoms selected from halogen, P, S, N, O, and Si.

[0009] Preferably, R 1 and R9 are independent, C1-C 10ア More preferably, the alkyl group is a C1-C8 alkyl group. More preferably, the alkyl group is a primary alkyl group.

[0010] Preferably, R 2 is C1-C 10 alkyl groups, more preferably C-C 10 Alkyl groups, and in particular C2-C 10 The alkyl groups are selected from primary alkyl groups.

[0011] Preferably, R 3 and R 4 are independently hydrogen or C1-C 10ア According to a particular embodiment, R is selected from alkyl groups, more preferably from hydrogen or C1-C8 alkyl groups, and in particular from hydrogen or straight-chain C1-C8 alkyl groups. 3 and R 4 are both hydrogen.

[0012] Preferably, R 5 ~R 8 are independently hydrogen or C1-C 20 Hydrocarbon groups, more preferably hydrogen or C1-C 15 Hydrocarbon groups, and in particular hydrogen or C1-C 10 The hydrocarbon group is selected from the group consisting of:

[0013] According to a particular embodiment, R 6 and R 7 are bonded to each other to form a cyclic structure having 3 to 10 carbon atoms forming the ring. Preferably, the cyclic structure has 5 to 6 carbon atoms forming the ring. The cyclic structure is 10 is selected from hydrocarbon groups, preferably C1-C 10 The ring may have one or more substituents selected from alkyl groups, more preferably C1-C8 alkyl groups.

[0014] R 6 and R 7 When forms a ring structure, R5 and R 8 is preferably hydrogen.

[0015] Particularly preferred is a structure belonging to the following formula (II): [ka] (II) In the formula, R 1 ~R 4 and R 9 has the same meaning as disclosed above, and R 10 are independently hydrogen or halogen or C1-C 10 It is more preferably selected from an alkyl group, a hydrogen, a halogen, or a C1-C8 alkyl group.

[0016] In the preferred structure of formula (II), R 1 and R 9 independently, C1-C 10 is a primary alkyl group, and R 2 But C1-C 10 is a straight-chain or branched alkyl group, R 3 and R 4 is hydrogen or C1-C 10 alkyl groups, and R 10 are independently selected from hydrogen, a C1-C8 alkyl group, or halogen, provided that at least two of them are hydrogen.

[0017] Preferably, the final content of the electron donor compound in the solid catalyst component is in the range of 1 to 25% by weight, preferably in the range of 3 to 20% by weight.

[0018] Non-limiting examples of structures of formula (I) and / or (II) include the following: Methyl 4-((methoxycarbonyl)amino)butanoate, methyl 4-((methoxycarbonyl)(methyl)amino)-3-methylbutanoate, methyl 4-((cyclohexylmethyl)(methoxycarbonyl)amino)-3-methylbutanoate, methyl 4-(hexyl(methoxycarbonyl)amino)-3-methylpentanoate, methyl 4-(benzyl(methoxycarbonyl)amino)-3-methylpentanoate, methyl 4-(butyl(methoxycarbonyl)amino)-2,3-dimethylpentanoate, methyl 2-isopropyl-4-((methoxy)amino) methyl 2-isopropyl-4-((cyclohexylmethyl)(methoxycarbonyl)amino)-5-methylhexanoate, methyl 2-isopropyl-4-(hexyl(methoxycarbonyl)amino)-5-methylhexanoate, pentyl 2-isopropyl-4-((cyclohexylmethyl)(methoxycarbonyl)amino)-5-methylhexanoate, methyl 3-benzyl-4-(isopropyl(methoxycarbonyl)amino)butanoate, methyl 4-((methoxycarbonyl)(propyl)amino)-2-methyl-5-phenylpentanoate, methyl 4-((cyclohexylmethyl)(methoxycarbonyl)amino) ethyl 4-((methoxycarbonyl)amino)-2-methyl-5-phenylpentanoate, ethyl 4-((methoxycarbonyl)amino)butanoate, ethyl 2-(((ethoxycarbonyl)(ethyl)amino)methyl)benzoate, ethyl 4-(hexyl(methoxycarbonyl)amino)butanoate, propyl 4-(hexyl(methoxycarbonyl)amino)3-methylbutanoate, ethyl 4-((methoxycarbonyl)amino)-3-methylpentanoate, ethyl 4-(isopropyl(methoxycarbonyl)amino)-3-methylpentanoate, hexyl 4-((meth ethyl 2-isopropyl-4-(butyl(methoxycarbonyl)amino)-5-methylhexanoate, ethyl 2-isopropyl-4-(isobutyl(methoxycarbonyl)amino)-5-methylhexanoate, ethyl 2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoate, ethyl 3-benzyl-4-(cyclohexyl(methoxycarbonyl)amino)butanoate,Ethyl 3-benzyl-4-(benzyl(methoxycarbonyl)amino)butanoate, decyl 4-((ethoxycarbonyl)(methyl)amino)butanoate, ethyl 4-(cyclohexyl(ethoxycarbonyl)amino)butanoate, ethyl 4-((ethoxycarbonyl)amino)3-methylbutanoate, ethyl 4-((cyclohexylmethyl)(ethoxycarbonyl)amino)3-methylbutanoate, ethyl 4-(cyclohexyl(ethoxycarbonyl)amino)-3-methylpentanoate, ethyl 4-(ethyl(ethoxycarbonyl)amino) ethyl 4-(butyl(ethoxycarbonyl)amino)-2,3-dimethylpentanoate, ethyl 4-(benzyl(ethoxycarbonyl)amino)-2,3-dimethylpentanoate, ethyl 2-isopropyl-4-((2-ethylhexyl)(ethoxycarbonyl)amino)-5-methylhexanoate, ethyl 3-benzyl-4-((ethoxycarbonyl)amino)butanoate, ethyl 4-(isobutyl(ethoxycarbonyl)amino)-2-methyl-5-furan isobutyl 4-(hexyl(ethoxycarbonyl)amino)butanoate, isobutyl 4-((2-ethylhexyl)(ethoxycarbonyl)amino)3-methylbutanoate, isobutyl 2-((hexyl(isobutoxycarbonyl)amino)methyl)benzoate, isobutyl 4-((ethoxycarbonyl)(propyl)amino)-3-methylpentanoate, isobutyl 4-((ethoxycarbonyl)amino)-2,3-dimethylpentanoate, isobutyl 2-isopropyl-4-(cyclohexyl (ethoxycarbonyl)amino)-5-methylhexanoate, isobutyl 3-benzyl-4-(benzyl(ethoxycarbonyl)amino)butanoate, isobutyl 4-((cyclohexylmethyl)(ethoxycarbonyl)amino)-2-methyl-5-phenylpentanoate, propyl 4-((isobutoxycarbonyl)amino)butanoate, propyl 4-((isobutoxycarbonyl)(methyl)amino)3-methylbutanoate, propyl 4-(ethyl(isobutoxycarbonyl)amino)-3-methylpentanoate,Propyl 4-((isobutoxycarbonyl)(propyl)amino)-2,3-dimethylpentanoate, Propyl 2-isopropyl-4-(butyl(isobutoxycarbonyl)amino)-5-methylhexanoate, Propyl 3-benzyl-4-(cyclohexyl(isobutoxycarbonyl)amino)butanoate, Propyl 4-((2-ethylhexyl)(isobutoxycarbonyl)amino)-2-methyl-5-phenylpentanoate, Propyl 4-((cyclohexylmethyl)(isobutoxycarbonyl)amino)-2-methyl-5-phenyl isobutyl 4-(ethyl(isobutoxycarbonyl)amino)butanoate, isobutyl 4-((2-ethylhexyl)(isobutoxycarbonyl)amino)3-methylbutanoate, isobutyl 4-(benzyl(isobutoxycarbonyl)amino)-3-methylpentanoate, isopentyl 4-((cyclohexylmethyl)(isobutoxycarbonyl)amino)-2,3-dimethylpentanoate, isobutyl 2-isopropyl-4-((isobutoxycarbonyl)amino)-5-methylhexanoate, isobutyl 2-( (butyl(ethoxycarbonyl)amino)methyl)benzoate, isobutyl 3-benzyl-4-(butyl(isobutoxycarbonyl)amino)butanoate, isobutyl 4-(hexyl(isobutoxycarbonyl)amino)-2-methyl-5-phenylpentanoate, 2-ethylhexyl 4-(ethyl(butoxycarbonyl)amino)butanoate, 2-ethylhexyl 4-(butyl(butoxycarbonyl)amino)3-methylbutanoate, 2-ethylhexyl 4-(hexyl(butoxycarbonyl)amino)-3-methylpentanoate, 2-ethylhexyl 4-(cyclohexyl(butoxycarbonyl)amino)-2,3-dimethylpentanoate, 2-ethylhexyl 2-isopropyl-4-((2-ethylhexyl)(butoxycarbonyl)amino)-5-methylhexanoate, 2-ethylhexyl 3-benzyl-4-(benzyl(butoxycarbonyl)amino)butanoate, 2-ethylhexyl 4-((cyclohexylmethyl)(butoxycarbonyl)amino)-2-methyl-5-phenylpentanoate, benzyl 4-((ethoxycarbonyl)amino)butanoate,Decyl 4-(ethyl(ethoxycarbonyl)amino)3-methylbutanoate, benzyl 4-(butyl(ethoxycarbonyl)amino)-3-methylpentanoate, benzyl 4-(hexyl(ethoxycarbonyl)amino)-2,3-dimethylpentanoate, ethyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate, benzyl 2-isopropyl-4-(benzyl(ethoxycarbonyl)amino)-5-methylhexanoate, benzyl 3-benzyl-4-((2-ethylhexyl)(ethoxycarbonyl)amino)butanoate noate, benzyl 4-(isopropyl(ethoxycarbonyl)amino)-2-methyl-5-phenylpentanoate, benzyl 4-(cyclohexyl(ethoxycarbonyl)amino)-2-methyl-5-phenylpentanoate, methyl 2-(((methoxycarbonyl)amino)methyl)benzoate, methyl 2-((butyl(methoxycarbonyl)amino)methyl)benzoate, decyl 2-(((cyclohexylmethyl)(methoxycarbonyl)amino)methyl)benzoate, methyl 2-(1-((methoxycarbonyl)(methyl)amino) methyl 2-(1-(isobutyl(methoxycarbonyl)amino)ethyl)benzoate, methyl 2-(1-(benzyl(methoxycarbonyl)amino)ethyl)benzoate, methyl 2-((ethyl(methoxycarbonyl)amino)(phenyl)methyl)benzoate, methyl 2-((ethyl(methoxycarbonyl)amino)(4-chlorophenyl)methyl)benzoate, methyl 2-((cyclohexyl(methoxycarbonyl)amino)(4-chlorophenyl)methyl)benzoate, methyl 2-(((2-ethyl hexyl)(methoxycarbonyl)amino)(phenyl)methyl)-5-chlorobenzoate, methyl 5-(tert-butyl)-2-(((methoxycarbonyl)(propyl)amino)(phenyl)methyl)-3-methylbenzoate, heptyl 5-(tert-butyl)-2-((isobutyl(methoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, ethyl 2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoate, ethyl 2-((hexyl(ethoxycarbonyl)amino)methyl)benzoate,Ethyl 2-(1-(ethyl(ethoxycarbonyl)amino)ethyl)benzoate, Ethyl 2-(1-((cyclohexylmethyl)(ethoxycarbonyl)amino)ethyl)benzoate, Ethyl 2-(((ethoxycarbonyl)amino)(phenyl)methyl)benzoate, Ethyl 2-((isobutyl(ethoxycarbonyl)amino)(phenyl)methyl)benzoate, Decyl 2-((isopropyl(ethoxycarbonyl)amino)(4-chlorophenyl)methyl)benzoate, Ethyl 2-((butyl(ethoxycarbonyl)amino )(4-chlorophenyl)methyl)benzoate, ethyl 2-(((ethoxycarbonyl)amino)(phenyl)methyl)-5-chlorobenzoate, ethyl 2-((benzyl(ethoxycarbonyl)amino)(phenyl)methyl)-5-chlorobenzoate, ethyl 5-(tert-butyl)-2-((butyl(ethoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, ethyl 5-(tert-butyl)-2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate Isobutoxycarbonyl, isobutyl 2-(((isobutoxycarbonyl)amino)methyl)benzoate, isobutyl 2-(1-((isobutoxycarbonyl)(methyl)amino)ethyl)benzoate, isobutyl 2-((ethyl(isobutoxycarbonyl)amino)(phenyl)methyl)benzoate, isobutyl 2-(((isobutoxycarbonyl)(propyl)amino)(4-chlorophenyl)methyl)benzoate, isobutyl 2-((isopropyl(isobutoxycarbonyl)amino)(phenyl)methyl)-5-chlorobenzoate, iso Butyl 5-(tert-butyl)-2-((isobutyl(isobutoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, 2-ethylhexyl 2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoate, ethyl 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate, 2-ethylhexyl 2-((hexyl(ethoxycarbonyl)amino)methyl)benzoate, 2-ethylhexyl 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoate,2-Ethylhexyl 2-(1-(ethyl(ethoxycarbonyl)amino)ethyl)benzoate, 2-ethylhexyl 2-(((ethoxycarbonyl)amino)(phenyl)methyl)benzoate, isobutyl 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate, 2-ethylhexyl 2-((cyclohexyl(ethoxycarbonyl)amino)(phenyl)methyl)benzoate, isopentyl 2-(((ethoxycarbonyl)(propyl)amino)(4-chlorophenyl)methyl), Benzoate, 2-ethylhexyl 2-((isopropyl(ethoxycarbonyl)amino)(4-chlorophenyl)methyl)benzoate, 2-ethylhexyl 2-(((2-ethylhexyl)(ethoxycarbonyl)amino)(4-chlorophenyl)methyl)benzoate, 2-ethylhexyl 2-(((ethoxycarbonyl)(methyl)amino)(phenyl)methyl)-5-chlorobenzoate, 2-ethylhexyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate, Octyl 2-((isobutyl(ethoxycarbonyl)amino) (phenyl)methyl)-5-chlorobenzoate, 2-ethylhexyl 2-((benzyl(ethoxycarbonyl)amino)(phenyl)methyl)-5-chlorobenzoate, 2-ethylhexyl 5-(tert-butyl)-2-(((ethoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, 2-ethylhexyl 5-(tert-butyl)-2-((hexyl(ethoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, ethyl 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoate benzoate, 2-ethylhexyl 5-(tert-butyl)-2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, isobutyl 2-(((isobutoxycarbonyl)amino)(4-fluorophenyl)methyl)benzoate, sec-butyl 2-((isopropyl(isobutoxycarbonyl)amino)(4-fluorophenyl)methyl)benzoate, isobutyl 2-((hexyl(isobutoxycarbonyl)amino)(4-fluorophenyl)methyl)benzoate, 2-ethylhexyl 2 -((ethyl(ethoxycarbonyl)amino)(phenyl)methyl)-4-bromobenzoate, isobutyl 2-(((2-ethylhexyl)(isobutoxycarbonyl)amino)methyl)benzoate, 2-ethylhexyl 2-((isobutyl(ethoxycarbonyl)amino)(phenyl)methyl)-4-bromobenzoate, 2-ethylhexyl 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)(phenyl)methyl)-4-bromobenzoate, methyl 2-(2-((methoxycarbonyl)(methyl)amino)phenyl)acetate,Methyl 2-(2-(cyclohexyl(methoxycarbonyl)amino)phenyl)acetate, methyl 2-(2-((methoxycarbonyl)amino)phenyl)propanoate, ethyl 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoate, methyl 2-(2-(hexyl(ethoxycarbonyl)amino)phenyl)-2-methylpropanoate, methyl 2-(2-(cyclohexyl(methoxycarbonyl)amino)phenyl)-2-phenylacetate, methyl 2-(4-chlorophenyl)-2-(2-(ethyl(methoxycarbonyl)amino)phenyl) 2-(2-(2-(ethoxycarbonyl)amino)phenyl)acetate, methyl 2-(5-(tert-butyl)-2-(ethyl(methoxycarbonyl)amino)-3-methylphenyl)-2-(4-chlorophenyl)acetate, ethyl 2-(2-((ethoxycarbonyl)amino)phenyl)acetate, benzyl 2-(2-(isobutyl(ethoxycarbonyl)amino)phenyl)propanoate, pentyl 2-(2-(cyclohexyl(ethoxycarbonyl)amino)phenyl)-2-methylpropanoate, ethyl 2-(2-((2-ethylhexyl)(ethoxycarbonyl)amino)phenyl) 2-(4-chlorophenyl)-2-(2-(benzyl(ethoxycarbonyl)amino)phenyl)-2-phenylacetate, ethyl 2-(4-chlorophenyl)-2-(2-(benzyl(ethoxycarbonyl)amino)phenyl)acetate, ethyl 2-(5-(tert-butyl)-2-((cyclohexylmethyl)(ethoxycarbonyl)amino)-3-methylphenyl)-2-(4-chlorophenyl)acetate, isobutyl 2-(2-((isobutoxycarbonyl)(methyl)amino)phenyl)acetate, isobutyl 2-(2-(cyclohexyl(isobutoxycarbonyl)amino)phenyl)acetate , isobutyl 2-(2-(isopropyl(isobutoxycarbonyl)amino)phenyl)propanoate, isobutyl 2-(2-(hexyl(isobutoxycarbonyl)amino)phenyl)propanoate, isobutyl 2-(2-(hexyl(isobutoxycarbonyl)amino)phenyl)-2-methylpropanoate, isobutyl 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate, isobutyl 2-(2-((2-ethylhexyl)(isobutoxycarbonyl)amino)phenyl)-2-methylpropanoate,Isobutyl 2-(2-(benzyl(isobutoxycarbonyl)amino)phenyl)-2-phenylacetate, Isobutyl 2-(2-((cyclohexylmethyl)(isobutoxycarbonyl)amino)phenyl)-2-phenylacetate, Isobutyl 2-(4-chlorophenyl)-2-(2-(cyclohexyl(isobutoxycarbonyl)amino)phenyl)acetate, Isobutyl 2-(5-(tert-butyl)-2-(isopropyl(isobutoxycarbonyl)amino)-3-methyl 2-ethylhexyl 2-(2-((butoxycarbonyl)amino)phenyl)acetate, 2-ethylhexyl 2-(2-(benzyl(butoxycarbonyl)amino)phenyl)acetate, 2-ethylhexyl 2-(2-((butoxycarbonyl)(propyl)amino)phenyl)propanoate, 2-ethylhexyl 2-(2-((2-ethylhexyl)(butoxycarbonyl)amino)phenyl)propanoate, 2-ethyl Hexyl 2-(2-(butyl(butoxycarbonyl)amino)phenyl)-2-methylpropanoate, 2-ethylhexyl 2-(2-((butoxycarbonyl)amino)phenyl)-2-phenylacetate, 2-ethylhexyl 2-(2-(isobutyl(butoxycarbonyl)amino)phenyl)-2-phenylacetate, 2-ethylhexyl 2-(4-chlorophenyl)-2-(2-(isopropyl(butoxycarbonyl)amino)phenyl)acetate, 2-ethylhexyl 2- (4-chlorophenyl)-2-(2-((2-ethylhexyl)(butoxycarbonyl)amino)phenyl)acetate, 2-ethylhexyl 2-(5-(tert-butyl)-2-((butoxycarbonyl)(propyl)amino)-3-methylphenyl)-2-(4-chlorophenyl)acetate, 2-ethylhexyl 2-(5-(tert-butyl)-2-((cyclohexylmethyl)(butoxycarbonyl)amino)-3-methylphenyl)-2-(4-chlorophenyl)acetate.

[0019] Compounds falling within formula (I) may generally be prepared using the following synthetic routes.

[0020] Commercially available amino acids can be converted to ((alkyloxy)carbonyl)amino acids with alkyl chloroformates, followed by treatment of the acid moiety in an appropriate alcohol under Fisher conditions to give the desired esters. If the amino acid is not available, it can be prepared from its α-aldehyde acid or α-keto acid precursor by reductive amination with an appropriate primary amine and a boron hydride reducing agent.

[0021] In the solid catalyst component of the present disclosure, the amount of Ti atoms is preferably greater than 2.5 wt. %, more preferably greater than 3.0 wt. %, based on the total weight of said catalyst component.

[0022] As explained above, the catalyst component of the present disclosure contains, in addition to the electron donor, Ti, Mg, and a halogen. In particular, the catalyst component includes a titanium compound containing at least one Ti-halogen bond and the aforementioned electron donor compound supported on a magnesium halide. The magnesium halide is preferably MgCl2 in its active form, which is widely known in the patent literature as a support for Ziegler-Natta catalysts. U.S. Pat. Nos. 4,298,718 and 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysts. From these patents, it is known that activated magnesium dihalides used as supports or co-supports in catalyst components for olefin polymerization can be characterized by X-ray spectroscopy. In this X-ray spectrum, the intensity of inactive halides decreases, and the maximum intensity is replaced by a halo shifted to lower angles relative to the intensity of the more intense lines.

[0023] Preferred titanium compounds for use in the catalyst components of the present disclosure are TiCl4 and TiCl3, and further represented by the formula Ti(OR 11 ) m-y X y Also usable are haloalcohol salts of the formula: where m is the valence of titanium, y is a number from 1 to m-1, X is a halogen, R 11 is a hydrocarbon group having 1 to 10 carbon atoms.

[0024] The preparation of the solid catalyst component can be carried out according to several methods: One method involves reacting magnesium alcoholate or chloroalcoholate (particularly chloroalcoholate prepared according to U.S. Patent No. 4,220,554) with excess TiCl4 in the presence of an electron donor compound at a temperature of about 80-120°C.

[0025] According to a preferred method, the solid catalyst component has the formula Ti(OR 11 ) m-y X y (wherein m is the valence of titanium and y is a number from 1 to m), preferably TiCl4, is reacted with a titanium compound of the formula MgCl2·pR 12 OH (wherein p is a number of 0.1 to 6, preferably 2 to 3.5); R 12The adduct can be prepared by reacting magnesium chloride derived from an adduct of (wherein is a hydrocarbon radical having 1 to 18 carbon atoms) with an alcohol. The adduct can be conveniently prepared in spherical form by mixing the alcohol with magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct and operating under stirring at the melting point of the adduct (100-130°C). The emulsion is then rapidly quenched, thereby solidifying the adduct in the form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in U.S. Pat. Nos. 4,399,054 and 4,469,648. The adduct thus obtained can be reacted directly with a Ti compound or subjected to a prior thermally controlled dealcoholization (80-130°C) to obtain an adduct having an alcohol mole number of less than 3, preferably 0.1-2.5. The reaction with a Ti compound can be carried out by suspending the adduct (dealcoholized or neat) in cold TiCl4 (approximately 0°C) and heating the mixture to 80-130°C and maintaining it at this temperature for 0.5-2 hours. The treatment with TiCl4 can be carried out one or more times. The electron donor compound is preferably added during the treatment with TiCl4. The preparation of spherical catalyst components is described, for example, in European Patent Applications EP-A-395083, EP-A-553805, EP-A-553806, EPA601525, and WO98 / 44009.

[0026] The solid catalyst component obtained according to the above method has a surface area of ​​20 to 500 m by the BTE method. 2 / g, preferably 50 to 400m 2 / g, and the total porosity by BTE method is 0.2 cm 3 / g or larger, preferably 0.2 to 0.6 cm 3 Porosity (Hg method) is typically 0.3-1.5 cm / g, with pores up to 10,000 Å in radius. 3 / g, preferably 0.45 to 0.1 cm 3 / g.

[0027] The average particle size of the catalyst component is 5 to 120 μm, and more preferably 10 to 100 μm.

[0028] In any of these preparation methods, the desired electron donor compound can be added as such or, alternatively, can be generated in situ using a suitable precursor, which can be converted into the desired electron donor compound, for example, by available chemical reactions.

[0029] Regardless of the preparation method used, the final content of the electron donor compound of the present disclosure is such that its molar ratio to Ti atoms is 0.01 to 2, preferably 0.05 to 1.5.

[0030] In addition to the above-mentioned donors, the solid catalyst component may also contain additional donors, which may be selected from esters, ethers, carbamates, thioesters, amides, and ketones, without any limitation on the type of additional donors.

[0031] Of the above class, the 1,3-diethers of formula (IV) are particularly preferred.

[0032] [ka] (IV) In the formula, R I and R II are the same or different and are hydrogen or straight or branched C-C alkyl groups which may also form one or more cyclic structures. 18 R are hydrocarbon groups, and may be equal or different from each other. III The group is hydrogen or C1-C 18 R are hydrocarbon groups, and may be equal or different from each other. IV The R group can be any group except that it cannot be hydrogen. III has the same meaning as R I ~R IV Each of the groups may contain heteroatoms selected from halogen, N, O, S, and Si.

[0033] Preferably, R IV is an alkyl radical of 1 to 6 carbon atoms, more specifically, methyl, while R III The radical is preferably hydrogen. I is methyl, ethyl, propyl, isopropyl, or isopentyl, R II R can be ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, isopentyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl, or benzyl. I is hydrogen, R II R can be ethyl, butyl, sec-butyl, tert-butyl, 2-ethylhexyl, cyclohexylethyl, diphenylmethyl, p-chlorophenyl, 1-naphthyl, 1-decahydronaphthyl. I and R II may be the same and may be ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, phenyl, benzyl, cyclohexyl, cyclopentyl.

[0034] Particularly preferred are compounds of formula (V) [ka] (V) In the formula, R VI The radicals may be equal or different and may be hydrogen; halogen, preferably Cl and F; linear or branched C-C 20 Alkyl radical; C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkylaryl and C7-C 20 arylalkyl radicals, optionally containing, as substituents on carbon or hydrogen atoms or on both, one or more heteroatoms selected from the group consisting of N, O, S, P, Si, and halogens, in particular Cl and F, and the radical R III and R IVis as defined above in formula (IV).

[0035] The solid catalyst components according to the present disclosure are converted into catalysts for olefin polymerization by reacting them with organoaluminum compounds according to available methods.

[0036] In particular, the object of the present disclosure is to provide a catalyst for the polymerization of olefins CH═CHR, where R is hydrogen or a hydrocarbyl radical having from 1 to 12 carbon atoms, comprising: (i) a solid catalyst component as disclosed above; (ii) an alkylaluminum compound, and optionally (iii) a catalyst comprising a product obtained by contacting an external electron donor compound with

[0037] The alkyl-Al compound (ii) is preferably selected from trialkylaluminum compounds such as triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, etc. It is also possible to use alkylaluminum halides, alkylaluminum hydrides, or alkylaluminum sesquichlorides (e.g., AlEt2Cl and Al2Et3Cl3), which may be used in combination with the trialkylaluminums listed above.

[0038] External electron donor compounds can include silicon compounds, ethers, esters, amines, and heterocyclic compounds.

[0039] Another class of preferred external donor compounds is represented by the formula (R 13 ) a (R 14 ) b Si(OR 15 ) c In the formula, 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. 13 , R 14 , and R 15is a radical having 1 to 18 carbon atoms, optionally containing a heteroatom. Particularly preferred is when a is 1, b is 1, c is 2, and R 13 and R 14 at least one of R is selected from a branched alkyl, cycloalkyl, or aryl group having 3 to 10 carbon atoms, optionally containing heteroatoms; 15 is C1-C 10 The silicon compound is an alkyl group, particularly a methyl group. Examples of such a preferred silicon compound include methylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), diisopropyldimethoxysilane, (2-ethylpiperidinyl)t-butyldimethoxysilane, (2-ethylpiperidinyl)thexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2-ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane, and N,N-diethylaminotriethoxysilane. Furthermore, when a is 0, c is 3, and R 14 is a branched alkyl or cycloalkyl group optionally containing heteroatoms, and R 15 Also preferred are silicon compounds in which R is a methyl group. Examples of such preferred silicon compounds include cyclohexyltrimethoxysilane, t-butyltrimethoxysilane, and thexyltrimethoxysilane.

[0040] The amount of the electron donor compound (iii) used is such that the molar ratio of the organoaluminum compound to the electron donor compound (iii) is 0.1-500, preferably 1-300, more preferably 3-100.

[0041] As explained, the catalyst components of the present disclosure, particularly when used in combination with an alkylaluminum compound and an alkylalkoxysilane in the polymerization of propylene, are capable of producing polypropylene under the polymerization conditions described in the Experimental Section with an activity greater than 50 kg / gcat, preferably greater than 55 kg / gcat, and a xylene insolubility at 25°C greater than 96.0 wt%, preferably greater than 96.5 wt%, more preferably greater than 97.0 wt%.

[0042] Therefore, a further object of the present disclosure is a process for the (co)polymerization of olefins CH═CHR, where R is hydrogen or a hydrocarbyl radical having 1 to 12 carbon atoms, comprising: (i) a solid catalyst component of the present disclosure; and (ii) an alkylaluminum compound; (iii) optionally with an electron donor compound (external donor), in the presence of a catalyst comprising the product of the reaction of

[0043] The polymerization process can be carried out according to available techniques, such as slurry polymerization using an inert hydrocarbon solvent as diluent, or bulk polymerization using a liquid monomer (e.g., propylene) as the reaction medium. Furthermore, it is also possible to carry out the polymerization process in the gas phase, operating in one or more fluidized bed or mechanically agitated bed reactors.

[0044] The polymerization can be carried out at a temperature of 20°C to 120°C, preferably 40°C to 80°C. When the polymerization is carried out in the gas phase, the operating pressure can be in the range of 0.5 to 5 MPa, preferably 1 to 4 MPa. In bulk polymerization, the operating pressure is generally in the range of 1 to 8 MPa, preferably 1.5 to 5 MPa.

[0045] The following examples are not intended to be limiting but are provided to further illustrate the present disclosure. Characterization Measurement of XI

[0046] 2.5 g of polymer and 250 ml of orthoxylene were placed in a round-bottom flask equipped with a condenser and a reflux condenser and kept under nitrogen gas. The resulting mixture was heated to 135°C and stirred for approximately 60 minutes. The final solution was cooled to 25°C with continuous stirring, and the insoluble polymer was filtered. The filtrate was then evaporated to constant weight at 140°C in a nitrogen stream. The content of the xylene-soluble fraction was expressed as a percentage of the original 2.5 grams, and then expressed by difference as XI%. Donor measurement

[0047] The electron donor content was determined by gas chromatography. The solid component was dissolved in acidified water. The solution was extracted with ethyl acetate, an internal standard was added, and a sample of the organic phase was analyzed by gas chromatography to determine the amount of donor present in the starting catalyst compound. Melt Flow Rate (MFR)

[0048] The melt flow rate MIL of the polymer was measured according to ISO 1133 (230°C, 2.16 Kg). Example Preparation procedure of spherical adducts

[0049] An initial amount of microspherical MgCl2·2.8C2H5OH was prepared according to the method described in Example 2 of WO98 / 44009, but operated on a larger scale. General Procedure for Propylene Polymerization

[0050] A 4-liter steel autoclave equipped with a stirrer, pressure gauge, thermometer, catalyst supply system, monomer supply line, and thermostat jacket was purged with a nitrogen stream at 70 °C for 1 hour. Then, under a propylene flow at 30 °C, 75 mL of anhydrous hexane, 0.76 g of AlEt3, dicyclopentyldimethoxysilane as an external electron donor in an amount to give an Al / donor molar ratio of 20, and 0.006 ÷ 0.010 g of the solid catalyst component were sequentially added. After closing the autoclave, 2.0 mL of hydrogen was added. Then, 1.2 kg of liquid propylene was added with stirring. The temperature was raised to 70 °C over 5 minutes, and the 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 under vacuum at 70 °C for 3 hours. The polymer was then weighed and fractionated with o-xylene to determine the amount of xylene-insoluble (XI) fraction. General procedure for preparing internal donor formulations Inventive Example 1: Ethyl 2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoate

[0051] Step 1: Synthesis of 2-((methylamino)methyl)benzoic acid 250cm equipped with a magnetic stirrer 3 In a 50 cm round-bottom flask, 5.0 g (33 mmol) of commercially available 2-formylbenzoic acid was added to 3 Dissolved in methanol, 5.8 cm 3 (66 mmol, 2 eq) aqueous methylamine (40 wt%) was added dropwise at room temperature. After 1 hour, 0.7 g (18 mmol, 0.6 eq) sodium borohydride was added portionwise at 0°C, and the reaction was then allowed to stand at room temperature for 3 hours. At this point, the solvent was removed under vacuum to give a viscous oil, which was triturated with acetone to give the product as a white solid. Yield 100%, 1 HNMR(400 MHz,D2O):2.98(s,3H,CH3),4.20(s,2H,CH2),7.2-7.7(m,4H,aromatic.).

[0052] Step 2: Synthesis of 2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoic acid 250cm equipped with a magnetic stirrer 3 In a 20 cm round-bottom flask, 5.5 g (33 mmol) of 2-((methylamino)methyl)benzoic acid was added to 3 The residue was dissolved in an aqueous NaOH solution (3 equivalents relative to the amino acid). 5.5 g (50 mmol, 1.5 equivalents) of ethyl chloroformate was then added dropwise, and the reaction was stirred at room temperature for 3 hours. The mixture was subsequently acidified with 1 M HCl, and the product was extracted with ethyl acetate. The organic fraction was washed with 2 volumes of water and then evaporated to give the final product as a colorless oil. Yield: 67%. 1 HNMR (400 MHz, CDCl3): 1.2(t,3H,CH3),2.9(s,3H,CH3),4.1(q,2H,CH2),4.9(s,2H,CH2),7.3-7.5(m,3H,aromatic.),7.8(m,1H,aromatic.).

[0053] Step 3: Synthesis of ethyl 2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoate 250cm equipped with a magnetic stirrer 3 In a 1 cm round-bottom flask, 5.2 g (0.22 mmol) of 2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoic acid was added to 1 cm 3 of sulfuric acid in 50 cm 3 The crude product was dissolved in ethanol. The mixture was refluxed for 5 hours, after which the solvent was removed. The crude product was dissolved in ethyl acetate and washed with aqueous sodium bicarbonate. The final product was then obtained after solvent removal as a colorless oil. Yield 80%, purity 95% (GC). 1 HNMR(400 MHz, CDCl3):1.1(t,3H,CH3),1.2(t,3H,CH3),2.8(s,3H,CH3),4.1(q,2H,CH2 ),4.3(q,2H,CH2),4.8(s,2H,CH2),7.3-7.5(m,3H,a aromatic.),7.9(m,1H,aromatic.). Inventive Example 2: Ethyl 2-(((ethoxycarbonyl)(ethyl)amino)methyl)benzoate

[0054] Step 1: Synthesis of 2-((ethylamino)methyl)benzoic acid This derivative was prepared according to the synthesis described in step 1 of Inventive Example 1, using ethylamine (2M in THF) instead of aqueous methylamine. Yield 90%. 1 HNMR (400 MHz,D2O): 1.0(t,3H,CH3),2.6(q,2H,CH2),3.9(s,2H,CH2),7.2(m,3H,aromatic.),7.7(m,1H,aromatic.).

[0055] Step 2: Synthesis of 2-(((ethoxycarbonyl)(ethyl)amino)methyl)benzoic acid This derivative was prepared according to the synthesis described in step 2 of Inventive Example 1 using 2-((ethylamino)methyl)benzoic acid as the starting material. Yield 72%. 1 HNMR (400 MHz, CDCl3): 1.1(m,6H,CH3+CH3),3.3(q,2H,CH2),4.1(q,2H,CH2),4.8(s,2H,CH2),7.3-7.5(m,3H,aromatic.),8.0(m,1H,aromatic.).

[0056] Step 3: Ethyl 2-(((ethoxycarbonyl)(ethyl)amino)methyl)benzoate This derivative was prepared according to the synthesis described in step 3 of Inventive Example 1 using 2-(((ethoxycarbonyl)(ethyl)amino)methyl)benzoic acid as the starting material. Yield 90%, purity 99% (GC). 1 HNMR(400 MHz, CDCl3):1.1(m,6H,CH3+CH3),1.3(m,6H,CH3),3.2(q,2H,CH2),4.1(q,2H, CH2),4.3(q,2H,CH2),4.8(s,2H,CH2),7.3-7.5(m,3H,aromatic.),7.9(m,1H,aromatic.). Inventive Example 3: Ethyl 2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoate

[0057] Step 1: Synthesis of 2-((propylamino)methyl)benzoic acid This derivative was prepared according to the synthesis described in step 1 of Inventive Example 1, using n-propylamine instead of aqueous methylamine. Yield 85%. 1 HNMR (400 MHz,D2O): 0.8(t,3H,CH3),1.5(m,2H,CH2),3.3(m,2H,CH2),3.9(s,2H,CH2),7.2-7.7(m,4H,aromatic.).

[0058] Step 2: Synthesis of 2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoic acid This derivative was prepared according to the synthesis described in step 2 of Inventive Example 1 using 2-((propylamino)methyl)benzoic acid as the starting material. Yield 74%. 1 HNMR(400 MHz, CDCl3):0.8(t,3H,CH3),1.1(m,3H,CH3),1.5(m,2H,CH2),3.2(m,2H,CH 2),4.1(q,2H,CH2),4.9(s,2H,CH2),7.3-7.5(m,3H,aromatic.),8.0(m,1H,aromatic.).

[0059] Step 3: Synthesis of ethyl 2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoate This derivative was prepared according to the synthesis described in step 3 of Inventive Example 1 using 2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoic acid as the starting material. Yield 84%, purity 96% (GC). 1 HNMR(400 MHz, CDCl3):0.8(t,3H,CH3),1.1(m,3H,CH3),1.3(t,3H,CH3),1.5(m,2H,CH2),3.1(m,2H,CH 2),4.1(m,2H,CH2),4.3(q,2H,CH2),4.8(s,2H,CH2),7.2-7.5(m,3H,aromatic.),7.9(m,1H,aromatic.). Inventive Example 4: Ethyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate

[0060] Step 1: Synthesis of 2-((butylamino)methyl)benzoic acid This derivative was prepared according to the synthesis described in step 1 of Inventive Example 1, using butylamine instead of aqueous methylamine. Yield 100%. 1 HNMR (400 MHz,D2O):0.8(t,3H,CH3),1.3(m,2H,CH2),1.5(m,2H,CH2),2.6(m,2H,CH2),3.9(s,2H,CH2),7.3(m,3H,aromatic.),7.7(m,1H,aromatic.).

[0061] Step 2: Synthesis of 2-((butyl(ethoxycarbonyl)amino)methyl)benzoic acid This derivative was prepared according to the synthesis described in step 2 of Inventive Example 1 using 2-((butylamino)methyl)benzoic acid as the starting material. Yield 81%. 1 HNMR(400 MHz, CDCl3):0.8(t,3H,CH3),1.3(m,5H,CH2+CH3),1.5(m,2H,CH2),3.2(m,2H, CH2),4.1(m,2H,CH2),4.9(s,2H,CH2),7.3-7.5(m,3H,aromatic.),8.0(m,1H,aromatic.).

[0062] Step 3: Synthesis of ethyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate This derivative was prepared according to the synthesis described in step 3 of Inventive Example 1 using 2-((butyl(ethoxycarbonyl)amino)methyl)benzoic acid as the starting material. Yield 89%, purity 95% (GC). 1 HNMR(400 MHz, CDCl3):0.8(t,3H,CH3),1.0-1.5(m,10H,2CH3+2CH2),3.1(m,2H,CH2),4.1(m, 2H,CH2),4.3(q,2H,CH2),4.8(s,2H,CH2),7.2-7.5(m,3H,aromatic.),7.9(m,1H,aromatic.). Inventive Example 5: Isobutyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate

[0063] Synthesis of isobutyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate This derivative was prepared according to the synthesis described in step 3 of Inventive Example 4, using isobutanol as the solvent. Yield 90%, purity 97% (GC). 1 HNMR(400 MHz, CDCl3):0.8(t,3H,CH3),0.9(d,6H,2CH3),1.0-1.5(m,7H,CH3(CH2)2),2.1(m,1H,CH), 3.2(m,2H,CH2),4.2(m,4H,2CH2),4.8(s,2H,CH2),7.2-7.5(m,3H,aromatic.),8.0(m,1H,aromatic.). Inventive Example 6: 2-Ethylhexyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate

[0064] Synthesis of 2-ethylhexyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate This derivative was prepared according to the synthesis described in step 3 of Inventive Example 4 using 2-(2-ethylhexyloxy)ethanol as the solvent. Yield 78%, purity 98% (GC). 1 HNMR(400 MHz, CDCl3):0.8(m,9H,3CH3),1.1-1.7(m,16H,CH3(CH2)2+(CH2)3CHCH2),3.2(m,2 H,CH2),4.1(m,4H,2CH2),4.8(s,2H,CH2),7.2-7.5(m,3H,aromatic.),7.9(m,1H,aromatic.). Inventive Example 7: Ethyl 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoate

[0065] Step 1: Synthesis of 2-((isobutylamino)methyl)benzoic acid This derivative was prepared according to the synthesis described in Step 1 of Inventive Example 1, using isobutylamine instead of aqueous methylamine. Yield 100%. 1HNMR (400 MHz,D2O): 0.8(d,6H,2CH3),1.7(m,1H,CH),2.4(d,2H,CH2),2.6(m,2H,CH2),3.8(s,2H,CH2),7.3(m,3H,aromatic.),7.7(m,1H,aromatic.).

[0066] Step 2: Synthesis of 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoic acid This derivative was prepared according to the synthesis described in step 2 of Inventive Example 1 using 2-((isobutylamino)methyl)benzoic acid as the starting material. Yield 81%. 1 HNMR(400 MHz, CDCl3):0.8(d,3H,2CH3),1.1(m,3H,CH3),1.9(m,1H,CH),3.1(d,2H,CH 2),4.1(m,2H,CH2),4.8(s,2H,CH2),7.3-7.5(m,3H,aromatic.),8.0(m,1H,aromatic.).

[0067] Step 3: Synthesis of ethyl 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoate This derivative was prepared according to the synthesis described in Step 3 of Inventive Example 1 using 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoic acid as the starting material. Yield 87%, purity 95% (GC). 1 HNMR(400 MHz, CDCl3):0.8(d,6H,2CH3),1.0-1.3(m,6H,CH3+CH3),1.9(m,1H,CH),3.0(m,2H,CH2), 4.1(m,2H,CH2),4.3(q,2H,CH2),4.8(s,2H,CH2),7.2-7.5(m,3H,aromatic.),7.9(m,1H,aromatic.). Inventive Example 8: Ethyl 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate

[0068] Step 1: Synthesis of 2-((hexylamino)methyl)benzoic acid This derivative was prepared according to the synthesis described in Step 1 of Inventive Example 1, using n-hexylamine instead of aqueous methylamine. Yield 73%. 1 HNMR(400 MHz,D2O):0.7(t,3H,CH3),1.0-1.5(m,8H,(CH2)4),2.5(m,2H,CH2),4.0(s,2H,CH2),7.0-7.3(m,3H,aromatic.),7.8(m,1H,aromatic.).

[0069] Step 2: Synthesis of 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoic acid This derivative was prepared according to the synthesis described in step 2 of Inventive Example 1 using 2-((hexylamino)methyl)benzoic acid as the starting material. Yield 80%. 1 HNMR(400 MHz, CDCl3):0.8(t,3H,CH3),1.3(m,9H,(CH2)3+CH3),1.6(m,2H,CH2),3.3(m,2H ,CH2),4.2(m,2H,CH2),4.9(s,2H,CH2),7.3-7.6(m,3H,aromatic.),8.1(m,1H,aromatic.).

[0070] Step 3: Synthesis of ethyl 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate This derivative was prepared according to the synthesis described in Step 3 of Inventive Example 1 using 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoic acid as the starting material. Yield 94%, purity 99% (GC). 1 HNMR(400 MHz, CDCl3):0.8(t,3H,CH3),1.0-1.6(m,14H,2CH3+(CH2)4),3.1(m,2H,CH2),4.1(m ,2H,CH2),4.3(q,2H,CH2),4.8(s,2H,CH2),7.2-7.5(m,3H,aromatic.),7.9(m,1H,aromatic.). Inventive Example 9: Isobutyl 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate

[0071] Synthesis of isobutyl 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate This derivative was prepared according to the synthesis described in step 3 of Inventive Example 8 using 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoic acid as the starting material. Yield 83%, purity 94% (GC). 1 HNMR(400 MHz, CDCl3):0.8(t,3H,CH3),0.9(d,6H,2CH3),1.0-1.5(m,8H,(CH2)4),2.0(m,1H,CH),3 .1(m,2H,CH2),4.2(m,4H,2CH2),4.8(s,2H,CH2),7.2-7.5(m,3H,aromatic.),7.9(m,1H,aromatic.). Inventive Example 10: Isobutyl 2-((hexyl(isobutoxycarbonyl)amino)methyl)

[0072] Step 1: Synthesis of 2-((hexyl(isobutoxycarbonyl)amino)methyl)benzoic acid This derivative was prepared according to the synthesis described in step 2 of Inventive Example 8, using 2-((hexylamino)methyl)benzoic acid as the starting material and isobutyl chloroformate as the alkylating agent. Yield: 60%. 1 HNMR(400 MHz, CDCl3):0.8-0.9(m,9H,CH3+2CH3),1.2-1.6(m,8H,(CH2)4),1.9(m,1H,CH),3.1( m,2H,CH2),4.2(m,2H,CH2),4.9(s,2H,CH2),7.3-7.6(m,3H,aromatic.),8.0(m,1H,aromatic.).

[0073] Step 2: Synthesis of isobutyl 2-((hexyl(isobutoxycarbonyl)amino)methyl)benzoate This derivative was prepared according to the synthesis described in Inventive Example 9 using 2-((hexyl(isobutoxycarbonyl)amino)methyl)benzoic acid as the starting material. Yield 93%, purity 97% (GC). 1HNMR(400 MHz, CDCl3):0.7-1.0(m,12H,2CH3+2CH3),1.1-1.6(m,8H,(CH2)4),1.8(m,1H,CH),2.0(m,1H,CH),3.1 (m,2H,CH2),3.8(m,2H,CH2),4.0(d,2H,CH2),4.8(s,2H,CH2),7.2-7.5(m,3H,aromatic.),7.9(m,1H,aromatic.). Inventive Example 11: Ethyl 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate

[0074] Step 1: Synthesis of 2-(((2-ethylhexyl)amino)methyl)benzoic acid This derivative was prepared according to the synthesis described in Step 1 of Inventive Example 1, using (2-ethyl)hexylamine instead of aqueous methylamine. Yield 50%. 1 HNMR(400 MHz,D2O):0.6-0.9(m,6H,CH3+CH3),1.0-1.4(m,7H,CH(CH2)3),1.5(m,2H,C H2),2.7(m,2H,CH2),4.1(m,2H,CH2),7.0-7.4(m,3H,aromatic.),8(m,1H,aromatic.).

[0075] Step 2: Synthesis of 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoic acid This derivative was prepared according to the synthesis described in step 2 of Inventive Example 1 using 2-(((2-ethylhexyl)amino)methyl)benzoic acid as the starting material. Yield 75%. 1 HNMR(400 MHz, CDCl3):0.7(m,6H,CH3+CH3),1.0-1.4(m,10H,CH(CH2)3+CH3),1.6(m,2H,CH2),3. 2(m,2H,CH2),4.1(m,2H,CH2),4.8(s,2H,CH2),7.2-7.5(m,3H,aromatic.),8.0(m,1H,aromatic.).

[0076] Step 3: Synthesis of ethyl 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate This derivative was prepared according to the synthesis described in step 3 of Inventive Example 1 using 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoic acid as the starting material. Yield 90%, purity 99% (GC). 1 HNMR(400 MHz, CDCl3):0.7(m,6H,CH3+CH3),1.0-1.4(m,13H,CH(CH2)3+2CH3),1.6(m,2H,CH2),3.1(m,2H, CH2),4.1(m,2H,CH2),4.3(q,2H,CH2),4.9(s,2H,CH2),7.1-7.4(m,3H,aromatic.),7.9(m,1H,aromatic.). Inventive Example 12: Isobutyl 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate

[0077] Synthesis of isobutyl 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate This derivative was prepared according to the synthesis described in Step 3 of Inventive Example 11 using isobutanol as the solvent. Yield: 92%, purity: 98% (GC). 1 HNMR(400 MHz, CDCl3):0.7(m,6H,CH3+CH3),0.9(d,6H,(CH3)2),1.0-1.6(m,12H,(CH2)3CHCH2CH3),2.0(m,1 H,CH),3.1(m,2H,CH2),4.1(m,4H,2CH2),4.9(m,2H,CH2),7.1-7.4(m,3H,aromatic.),7.9(m,1H,aromatic.). Inventive Example 13: Isobutyl 2-(((2-ethylhexyl)(isobutoxycarbonyl)amino)methyl)benzoate

[0078] Step 1: Synthesis of 2-(((2-ethylhexyl)(isobutoxycarbonyl)amino)methyl)benzoic acid This derivative was prepared according to the synthesis described in step 1 of Inventive Example 10 using 2-(((2-ethylhexyl)amino)methyl)benzoic acid as the starting material. Yield 84%. 1HNMR(400 MHz, CDCl3):0.8-1.0(m,9H,CH3+(CH3)2),1.0-1.6(m,12H,(CH2)3CHCH2CH3),3.1(m ,2H,CH2),3.8(m,2H,CH2),4.8(s,2H,CH2),7.2-7.5(m,3H,aromatic.),8.0(m,1H,aromatic.).

[0079] Step 3: Synthesis of isobutyl 2-(((2-ethylhexyl)(isobutoxycarbonyl)amino)methyl)benzoate This derivative was prepared according to the synthesis described in Inventive Example 12 using 2-(((2-ethylhexyl)(isobutoxycarbonyl)amino)methyl)benzoic acid as the starting material. Yield: 95%, purity: 97% (GC). 1 HNMR(400 MHz, CDCl3):0.6(m,3H,CH3),0.7(m,6H,(CH3)2),0.9(m,6H,(CH3)2),1.0-1.7(m,12H,(CH2)3CHCH2CH3),2.0(m,2 H,2CH),3.1(m,2H,CH2),3.8(m,2H,CH2),4.1(m,2H,CH2),4.9(m,2H,CH2),7.2-7.5(m,3H,aromatic.),7.9(m,1H,aromatic.). Inventive Example 14: Ethyl 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoate

[0080] Step 1: Synthesis of 2-(((cyclohexylmethyl)amino)methyl)benzoic acid This derivative was prepared according to the synthesis described in Step 1 of Inventive Example 1, using N-methylcyclohexylamine instead of aqueous methylamine. Yield 100%. 1 HNMR(400 MHz,D2O):0.8-1.4(m,5H,cyclohexyl),1.6(m,5H,cyclohexyl),2.2(m,1H,CH),3.1(d,2H,CH2),4.2(m,2H,CH2),7.0-7.4(m,3H,aromatic.),8(m,1H,aromatic.).

[0081] Step 2: Synthesis of 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoic acid This derivative was prepared according to the synthesis described in step 2 of Inventive Example 1 using 22-(((cyclohexylmethyl)amino)methyl)benzoic acid as the starting material. Yield 80%. 1 HNMR(400 MHz, CDCl3):0.8-1.4(m,8H,cyclohexyl+CH3),1.6(m,5H,cyclohexyl),2.1(m,1H,CH),3 .2(d,2H,CH2),4.0(m,2H,CH2),4.9(s,2H,CH2),7.2-7.5(m,3H,aromatic.),7.9(m,1H,aromatic.).

[0082] Step 3: Synthesis of ethyl 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoate This derivative was prepared according to the synthesis described in step 3 of Inventive Example 1 using 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoic acid as the starting material. The final material was subjected to purification by gel chromatography. Yield 40%, purity 95% (GC). 1 HNMR(400 MHz, CDCl3):0.7-1.4(m,8H,cyclohexyl+CH3),1.6(m,H,cyclohexyl+CH3),1.9(m,1H,CH),3.0(m, 2H,CH2),4.0(m,2H,CH2),4.3(q,2H,CH2),4.9(s,2H,CH2),7.2-7.5(m,3H,aromatic.),7.9(m,1H,aromatic.). Comparative Example 1: Ethyl 2-((ethoxycarbonyl)(methyl)amino)benzoate

[0083] Step 1: Synthesis of ethyl 2-((ethoxycarbonyl)amino)benzoate 250cm equipped with a magnetic stirrer 3 In a 5.1 cm round-bottom flask, 5.0 g (30 mmol) of commercially available ethyl 2-aminobenzoate was added to a 5.1 cm 3(36 mmol, 1.2 equiv.) of triethylamine, 50 cm 3 The mixture was dissolved in 3.5 cm of tetrahydrofuran. 3 Ethyl chloroformate (36 mmol, 1.2 eq) was added dropwise at 0°C, and the reaction was then allowed to stand at room temperature for 3 hours. The mixture was then acidified with 1 M HCl, and the product was extracted with ethyl acetate. The organic fraction was washed with two volumes of water and then evaporated to give the final product as a colorless oil. Yield 90%. 1 HNMR (400 MHz, CDCl3): 1.2(t,3H,CH3),1.3(t,3H,CH3),4.1(q,2H,CH2),4.3(q,2H,CH3),7.3(m,1H,aromatic.),7.6(m,2H,arom.),8.1(m,1H,aromatic.).

[0084] Step 2: Synthesis of ethyl 2-((ethoxycarbonyl)(methyl)amino)benzoate 250cm equipped with a magnetic stirrer 3 In a 50 cm round-bottom flask under nitrogen, 6.0 g (25 mmol) of ethyl 2-((ethoxycarbonyl)amino)benzoate was added to 3 of tetrahydrofuran and 0.8 g (30 mmol, 1.2 eq) of sodium hydride (powder, 90%) were added in portions. The mixture was set to 30° C. and 1.9 cm 3 Methyl iodide (30 mmol, 1.2 equiv.) was added dropwise and the reaction was stirred at 40° C. for 3 h. Subsequently, the mixture was acidified with 1 M HCl and the product was extracted with ethyl acetate. The organic fraction was washed with 2 volumes of water and then evaporated to give the final product as a colorless oil. Yield 85%, purity 98%. 1 HNMR (400 MHz, CDCl3): 1.2(t,3H,CH3),1.3(t,3H,CH3),3.3(s,3H,CH3),4.1(q,2H,CH2),4.3(q,2H,CH3),7.3(m,1H,aromatic.),7.8-8.2(m,3H,aromatic.). General procedure for preparing the solid catalyst component

[0085] A 500cm2 reactor equipped with a mechanical stirrer, a condenser, and a thermometer 3 In a round-bottom flask, 250 cm 3 of TiCl4 was introduced at room temperature under a nitrogen atmosphere. After cooling to 0°C, the internal donor listed in Table 1 and 10.0 g of the spherical adduct were added successively to the flask under stirring. The amount of internal donor charged was such that the Mg / donor molar ratio was 6. The temperature was raised to 100°C and maintained for 2 hours. After that, stirring was stopped, the solid product was allowed to settle, and the supernatant was siphoned off at 100°C. After removing the supernatant, fresh TiCl4 was added to restore the initial volume. The mixture was then heated to 120°C and maintained at this temperature for 1 hour. Again, stirring was stopped, the solid was allowed to settle, and the supernatant was siphoned off. The solid was then washed six times with anhydrous hexane at a temperature gradient of 60°C (6 × 100 cm). 3 ), and once at room temperature (100 cm 3 ) and washed. The solid obtained was then dried under vacuum. The solid catalyst component thus obtained was tested in the polymerization of propylene using the procedure described above. The results are listed in Table 1. Inventive Examples 1 to 14 and Comparative Example 1 Preparation of solid catalyst components and polymerization

[0086] The general procedure for preparing the solid catalyst component was carried out using the donors reported in Table 1 as internal donors. The solid catalyst component thus obtained was tested in the polymerization of propylene using the procedure described above. The results are listed in Table 1. Table 1 [Table 1-1] [Table 1-2]

[0087] nd: Not measured

Claims

1. Mg, Ti, and an electron donor of formula (I), 【Chemistry 1】 (I) In the formula, R １ and R ９ The groups may be the same or different, and １ -C １５ R is selected from hydrocarbon groups; ２ The group is hydrogen or C １ -C １０ R is selected from hydrocarbon groups; ３ ~R ８ The groups are independently hydrogen or C groups which can be fused together to form one or more rings. １ -C １５ A catalyst component for olefin polymerization selected from hydrocarbon groups.

2. R as defined above １ ~R ９ 10. The catalyst component of claim 1, wherein may contain heteroatoms selected from halogens, P, S, N, O, and Si.

3. R １ ~R ９ is independently C １ -C １０ is an alkyl group, more preferably C １ -C ８ Catalyst component according to any one of the preceding claims, which is an alkyl group.

4. R ２ is C １ -C １０ alkyl group, more preferably C ２ -C １０ Alkyl groups, and in particular C ２ -C １０ Catalyst component according to any one of the preceding claims, wherein the alkyl groups are selected from primary alkyl groups.

5. R ３ and R ４ are independently hydrogen or C １ -C １０ alkyl group, more preferably hydrogen or C １ -C ８ Alkyl groups, and in particular hydrogen or straight chain C １ -C ８ Catalyst component according to any one of the preceding claims, wherein the alkyl group is selected from the group consisting of:

6. R ３ and R ４ 6. The catalyst component of claim 5, wherein both of are hydrogen.

7. R ５ ~R ８ are independently hydrogen or C １ -C ２０ Catalyst component according to any one of the preceding claims, selected from hydrocarbon groups.

8. R ５ ~R ８ are independently hydrogen or C １ -C １５ Hydrocarbon groups, and in particular hydrogen or C １ -C １０ 8. The catalyst component of claim 7, wherein the group is selected from hydrocarbon groups.

9. R ６ and R ７ The catalyst component of claim 7, wherein: are linked together to form a cyclic structure having from 3 to 10 carbon atoms forming the ring.

10. R ５ and R ８ 10. The catalyst component of claim 9, wherein both are hydrogen.

11. The electron donor is selected from those belonging to formula (II): 【Chemistry 2】 (II) In the formula, R １ ~R ４ and R ９ has the same meaning as disclosed above, and R １０ are independently hydrogen or halogen or C １ -C １０ alkyl group, more preferably hydrogen, halogen, or C １ -C ８ Catalyst component according to any one of the preceding claims, wherein the alkyl group is selected from the group consisting of:

12. R １ and R ９ is independent, C １ -C １０ is a primary alkyl group, and R ２ is C ２ -C １０ straight chain alkyl groups, R ３ and R ４ is hydrogen or C １ -C １０ alkyl groups, R １０ The groups are independently hydrogen, C １ -C ８ 12. The catalyst component of claim 11, wherein the alkyl groups are selected from alkyl groups, or halogens, provided that at least two of them are hydrogen.

13. (i) a solid catalyst component according to any one of the preceding claims; (ii) a catalyst system for the polymerization of olefins, comprising the product of the reaction of

14. 14. The catalyst of claim 13 further comprising an external electron donor compound.

15. 10. A process for the (co)polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbyl radical having 1 to 12 carbon atoms, which is carried out in the presence of a catalyst system according to any one of the preceding claims.

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