Catalyst components for olefin polymerization

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] This disclosure relates to catalyst components for the polymerization of olefins, particularly propylene, the catalyst components comprising a Mg dihalide-based support on which Ti atoms are supported, and an electron-donating compound containing ester and carbamate functional groups. This disclosure further relates to catalysts obtained from the above components and their use in the polymerization process of olefins, particularly propylene. [Background technology]

[0002] Catalyst components for the stereospecific polymerization of olefins have been disclosed in the art. For the polymerization of propylene, Ziegler-Natta catalysts, which generally include a solid catalyst component composed of a titanium-supported magnesium dihalide and an internal electron donor compound, are used in combination with alkylaluminum compounds. However, conventionally, when a higher degree of crystallinity of the polymer is desired, an external donor (e.g., alkoxysilane) is also required to obtain higher isotacticity. 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 alkylalkoxysilane as an external donor, exhibits excellent performance in terms of activity, isotacticity, and xylene insolubility.

[0003] One of the problems associated with the use of this catalytic system is that phthalates have recently raised some concerns, and some compounds belonging to this class have been classified as causes of serious health problems.

[0004] As a result, research activities are being dedicated to discovering alternative classes of internal donors in the preparation of catalyst components for propylene polymerization.

[0005] Some of the tested catalysts contain a donor structure having both a carbamine group and an ester group at the same time. PCT Publication WO2018 / 091375 describes 1,3-amino ester derivatives containing one carbamate group and one free ester functional group. From the perspective of the balance of activity / stereospecificity, the performance of these catalysts is not entirely satisfactory, and improvement is particularly needed in terms of stereospecificity. Summary of the Invention

[0006] Surprisingly, the applicant has discovered that among specific structures derived from amino acids, there is a class of donors containing both a carbamate functional group and an ester functional group, which produce catalysts showing a good balance of activity and stereospecificity.

[0007] Therefore, the object of the present disclosure is a catalyst component for olefin polymerization containing Mg, Ti, and an electron donor of formula (I),

Chemical Formula

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

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

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

[0011] Preferably, R 3 and R 4 These are independently hydrogen or C1-C 10ア From a lukyl group, more preferably from hydrogen or a C1-C8 alkyl group, and in particular from hydrogen or a linear C1-C8 alkyl group. According to a particular embodiment, R 3 and R 4 Both are hydrogen.

[0012] Preferably, R 5 ~R 8 These are independently hydrogen or C1-C 20 hydrocarbon group, more preferably hydrogen or C1-C 15 hydrocarbon groups, and in particular hydrogen or C1-C 10 Selected from hydrocarbon groups.

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

[0014] R 6 and R 7 When R forms a ring structure,5 and R 8 Preferably, it is 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 This has the same meaning as disclosed above, and R 10 These are independently hydrogen, halogen, or C1-C 10 Alkyl alkyl groups, more preferably selected from hydrogen, halogens, or C1-C8 alkyl groups.

[0016] In the preferred structure of formula (II), R 1 and R 9 It became independent, C1-C 10 It is a primary alkyl group, R 2 However, C1-C 10 It is a linear or branched alkyl group, R 3 and R 4 However, hydrogen or C1-C 10 Selected from alkyl groups, R 10 Each of these elements is independently selected from hydrogen, a C1-C8 alkyl group, or a halogen, wherein at least two of these 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, and more preferably in the range of 3 to 20% by weight.

[0018] Non-restrictive examples of the structure of equations (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-((methyl (Cycarbonyl)(methyl)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)(methoxycarbon) (Isopropyl(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 Xycarbonyl)amino)-2,3-dimethylpentanoate, ethyl 4-(isopropyl(methoxycarbonyl)amino)-2,3-dimethylpentanoate, 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( Toxycarbonyl)amino)-2,3-dimethylpentanoate, 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- Phenylpentanoate, 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 (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-methylben Zoate, 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)benzyl Zoate, 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(methoxycarbon) (Isobutyl(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)(ethoxycarbon) Nyl)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-(4-chlorophenyl)acetate, 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 corresponding to formula (I) can generally be prepared using the following synthetic route.

[0020] Alkyl chloroformate can be used to convert commercially available amino acids into ((alkyloxy)carbonyl) amino acids, and the desired ester can be obtained by subsequently treating the acidic portion in a suitable alcohol under Fischer conditions. If amino acids are not available, they can be prepared from their α-aldehyde or α-keto acid precursors by reductive amination using a suitable primary amine and a borohydride reducing agent.

[0021] In the solid catalyst component of this disclosure, the amount of Ti atoms is preferably greater than 2.5% by weight and more preferably greater than 3.0% by weight, relative to the total weight of the catalyst component.

[0022] As described above, the catalyst components of this disclosure include Ti, Mg, and halogens in addition to the electron donor described above. In particular, the catalyst component is preferably an active form of MgCl2, widely known from the patent literature as a support for Ziegler-Natta catalysts, having a titanium compound containing at least one Ti-halogen bond and an electron donor compound supported on the aforementioned Mg halide. U.S. Patents 4,298,718 and 4,495,338 first described the use of these compounds in Ziegler-Natta catalysts. From these patents, it is known that active magnesium dihalides used as a support or co-support in components of olefin polymerization catalysts are characterized by their X-ray spectra. In these X-ray spectra, the intensity of inactive halides decreases, and the maximum intensity is replaced by a halo that shifts to a lower angle compared to the intensity of a stronger line.

[0023] Preferred titanium compounds used in the catalyst components of this disclosure are TiCl4 and TiCl3, and furthermore, the formula Ti(OR 11 ) m-y X y Haloaloolates can also be used, where m is the valence of titanium, y is the number from 1 to m-1, X is the halogen, R 11 It is a hydrocarbon group having 1 to 10 carbon atoms.

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

[0025] According to a preferred method, the solid catalyst component is given by formula Ti(OR 11 ) m-y X y A titanium compound of the formula (wherein m is the valence of titanium and y is the number from 1 to m), preferably TiCl4, is given by the formula MgCl2·pR 12 OH(wherein p is a number from 0.1 to 6, preferably from 2 to 3.5, R 12The adduct can be prepared by reacting magnesium chloride derived from an adduct of a hydrocarbon group having 1 to 18 carbon atoms. The adduct can be appropriately prepared into a spherical shape by mixing the alcohol and magnesium chloride in the presence of an inert hydrocarbon that is immiscible with the adduct and operating under stirring conditions at the melting point of the adduct (100 to 130°C). The emulsion is then rapidly quenched, thereby solidifying the adduct in the form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in U.S. Patents 4,399,054 and 4,469,648. The adduct thus obtained can be reacted directly with a Ti compound or subjected to pre-heat-controlled de-alcoholization (80 to 130°C) to obtain an adduct with less than 3 moles of alcohol, preferably 0.1 to 2.5. The reaction with the Ti compound can be carried out by suspending the adduct (de-alcoholized or in its as-is) in low-temperature TiCl4 (about 0°C), heating the mixture to 80 to 130°C, and maintaining this temperature for 0.5 to 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. Preparation of the spherical catalyst component 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 components obtained according to the above method have a surface area of ​​20-500 m² as determined by the BTE method. 2 / g, preferably 50-400m 2 / g, and total porosity by BTE method is 0.2 cm 3 Larger than / g, preferably 0.2-0.6cm 3 It can be / g. The porosity (Hg method) due to pores up to a radius of 10,000 Å is generally 0.3 to 1.5 cm. 3 / g, preferably 0.45~0.1cm 3 It could be in the range of / 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 in this manner, or, as an alternative, can be generated in situ using a suitable precursor, in which case the precursor can be converted to the desired electron donor compound, for example, by an available chemical reaction.

[0029] Regardless of the preparation method used, the final content of the electron donor compound of this 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 donors described above, the solid catalyst component may also contain additional donors. While there are no restrictions on the type of additional donors, they can be selected from esters, ethers, carbamates, thioesters, amides, and ketones.

[0031] Among the above classes, the 1,3-diether of formula (IV) is particularly preferred.

[0032] [ka] (IV) In the formula, R I and R II These are C1-C atoms that are the same or different, and may also form hydrogen or one or more cyclic structures, in a straight or branched chain. 18 Hydrocarbon groups, which are equal to or different from each other. III The group is hydrogen or C1-C 18 Hydrocarbon groups, which are equal to or different from each other. IV The group is R, except that it cannot be hydrogen. III It has the same meaning as R I ~R IV Each group may contain a heteroatom selected from halogens, N, O, S, and Si.

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

[0034] Compounds of formula (V) are particularly preferred, [ka] (V) In the formula, R VI Radicals are equal to or different from hydrogen; halogens, preferably Cl and F; and linear or branched C1-C. 20 Alkyl radical; C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkylaryls, and C7-C 20 The arylalkyl radical is optionally comprising one or more heteroatoms selected from the group consisting of N, O, S, P, Si, and halogens, particularly Cl and F, as substituents on a carbon atom, a hydrogen atom, or both, and the radical R III and R IVis as defined above by formula (IV).

[0035] The solid catalyst component according to the present disclosure is converted into a catalyst for olefin polymerization by reacting with an organoaluminum compound according to available methods.

[0036] In particular, the object of the present disclosure is a catalyst for the polymerization of an olefin CH2=CHR, where R is hydrogen or a hydrocarbyl radical having 1 to 12 carbon atoms, (i) the solid catalyst component disclosed above, (ii) an alkylaluminum compound, and optionally, (iii) an external electron donor compound, and is a catalyst containing a product obtained by contacting them.

[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), and these may be used in combination with the trialkylaluminums listed above.

[0038] Examples of the external electron donor compound include silicon compounds, ethers, esters, amines, and heterocyclic compounds.

[0039] Another class of preferred external donor compounds is a silicon compound of the formula (R 13 )<000009l>(R 14 ) b Si(OR 15 ) c 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 13 , R 14 [[ID=4Z]]and R 15It is a radical having 1 to 18 carbon atoms and optionally containing heteroatoms. Particularly preferred is when a is 1, b is 1, c is 2, and R 13 and R 14 At least one of them is optionally selected from branched alkyl, cycloalkyl, or aryl groups having 3 to 10 carbon atoms including a heteroatom, R 15 C1-C 10 The silicon compound is an alkyl group, particularly a methyl group. Examples of such preferred silicon compounds include methylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), diisopropyldimethoxysilane, (2-ethylpiperidinyl)t-butyldimethoxysilane, (2-ethylpiperidinyl)texyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2-ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane, and N,N-diethylaminotriethoxysilane. Furthermore, a is 0, c is 3, and R 14 is optionally a branched alkyl or cycloalkyl group containing a heteroatom, and R 15 Silicon compounds in which the group is a methyl group are also preferred. Examples of such preferred silicon compounds include cyclohexyltrimethoxysilane, t-butyltrimethoxysilane, and texyltrimethoxysilane.

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

[0041] As described above, when the catalyst components of this disclosure are used in combination with alkylaluminum compounds and alkylalkoxysilanes for the polymerization of propylene, under the polymerization conditions described in the experimental section, it is possible to produce polypropylene with activity greater than 50 kg / gcat, preferably greater than 55 kg / gcat, and xylene insolubility greater than 96.0% by weight, preferably greater than 96.5% by weight, more preferably greater than 97.0% by weight at 25°C.

[0042] Therefore, a further object of this disclosure is a (co)polymerization process of olefin CH2=CHR (wherein R is hydrogen or a hydrocarbyl radical having 1 to 12 carbon atoms), (i) The solid catalyst component of the present disclosure and (ii) Alkyl aluminium compounds, (iii) The reaction is carried out in the presence of a catalyst containing the product of the reaction with an optional electron donor compound (external donor).

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

[0044] Polymerization can be carried out at temperatures of 20°C to 120°C, preferably 40°C to 80°C. When polymerization is carried out in the gas phase, the operating pressure may 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 embodiments are given for illustrative purposes only, and are not intended to limit the scope of this 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 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 out. The filtrate was then evaporated at 140°C under a nitrogen stream to a constant weight. The content of the xylene-soluble fraction was expressed as a percentage of the original 2.5 grams, and then expressed as 10% by the difference. Measurement of donors

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

[0048] The polymer melt flow rate (MIL) was measured according to ISO 1133 (230°C, 2.16 kg). Examples Procedure for preparing spherical adducts

[0049] The initial amount of microspherical MgCl2·2.8C2H5OH was prepared according to the method described in Example 2 of WO98 / 44009, but the operation was performed 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, 75 mL of anhydrous hexane, 0.76 g of AlEt3, dicyclopentyl dimethoxysilane as an external electron donor in an amount that resulted in an Al / donor molar ratio of 20, and 0.006 ÷ 0.010 g of solid catalyst components were sequentially added via a propylene flow at 30°C. After closing the autoclave, 2.0 NL of hydrogen was added. Then, 1.2 kg of liquid propylene was supplied with stirring. The temperature was raised to 70°C in 5 minutes, and polymerization was carried out at this temperature for 2 hours. At the end of polymerization, unreacted propylene was removed. The polymer was recovered and dried under vacuum at -70°C for 3 hours. Next, the polymer was weighed, fractionated with o-xylene, and the amount of the xylene-insoluble (XI) fraction was measured. General preparation procedure for internally donated products Invention Example 1: Ethyl 2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoate

[0051] Step 1: Synthesis of 2-((methylamino)methyl)benzoic acid A 250cm pipe equipped with a magnetic stirrer. 3 In a round-bottom flask, add 5.0 g (33 mmol) of commercially available 2-formylbenzoic acid to a 50 cm flask. 3 Dissolve in methanol and mix for 5.8 cm. 3 (66 mmol, 2 equivalents) of aqueous methylamine (40 wt%) was added dropwise at room temperature. After 1 hour, 0.7 g (18 mmol, 0.6 equivalents) of sodium boride was added gradually at 0°C, and the reaction mixture was allowed to stand at room temperature for 3 hours. At this point, the solvent was removed under vacuum to obtain a viscous oil, which was triturated with acetone to obtain 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 A 250cm pipe equipped with a magnetic stirrer. 3 In a round-bottom flask, 5.5 g (33 mmol) of 2-((methylamino)methyl)benzoic acid was added to a 20 cm flask. 3 The amino acid was dissolved in an aqueous solution of NaOH (3 equivalents relative to the amino acid). Then, 5.5 g (50 mmol, 1.5 equivalents) of ethyl chloroformate was added dropwise, and the reaction mixture was stirred at room temperature for 3 hours. 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 obtain 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 A 250cm pipe equipped with a magnetic stirrer. 3 In a round-bottom flask, add 5.2 g (0.22 mmol) of 2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoic acid to 1 cm 3 50cm containing sulfuric acid 3 The mixture was dissolved in ethanol. After refluxing the mixture for 5 hours, the solvent was removed. The product was then dissolved in ethyl acetate and washed with an aqueous sodium bicarbonate solution. After removing the solvent, the final product was obtained 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.). Invention Example 2: Ethyl 2-(((ethoxycarbonyl)(ethyl)amino)methyl)benzoate

[0054] Step 1: Synthesis of 2-((ethylamino)methyl)benzoic acid The derivative was prepared using ethylamine (2M in THF) instead of aqueous methylamine, according to the synthesis described in Step 1 of Invention Example 1. 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 The derivative was prepared using 2-((ethylamino)methyl)benzoic acid as a starting material, according to the synthesis described in step 2 of Invention Example 1. 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 The derivative was prepared using 2-(((ethoxycarbonyl)(ethyl)amino)methyl)benzoic acid as a starting material, according to the synthesis described in step 3 of Invention Example 1. 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.). Invention Example 3: Ethyl 2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoate

[0057] Step 1: Synthesis of 2-((propylamino)methyl)benzoic acid The derivative was prepared using n-propylamine instead of aqueous methylamine, according to the synthesis described in Step 1 of Invention Example 1. 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 The derivative was prepared using 2-((propylamino)methyl)benzoic acid as a starting material, according to the synthesis described in step 2 of Invention Example 1. 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 The derivative was prepared using 2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoic acid as a starting material, according to the synthesis described in step 3 of Invention Example 1. 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.). Invention Example 4: Ethyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate

[0060] Step 1: Synthesis of 2-((butylamino)methyl)benzoic acid The derivative was prepared using butylamine instead of aqueous methylamine, according to the synthesis described in Step 1 of Invention Example 1. 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 The derivative was prepared using 2-((butylamino)methyl)benzoic acid as a starting material, according to the synthesis described in step 2 of Invention Example 1. 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 The derivative was prepared using 2-((butyl(ethoxycarbonyl)amino)methyl)benzoic acid as a starting material, according to the synthesis described in step 3 of Invention Example 1. 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.). Invention Example 5: Isobutyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate

[0063] Synthesis of isobutyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate The derivative was prepared using isobutanol as a solvent, according to the synthesis described in step 3 of Invention Example 4. 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.). Invention Example 6: 2-Ethylhexyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate

[0064] Synthesis of 2-ethylhexyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate The derivative was prepared using 2-(2-ethylhexyloxy)ethanol as a solvent, according to the synthesis described in step 3 of Invention Example 4. 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.). Invention Example 7: Ethyl 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoate

[0065] Step 1: Synthesis of 2-((isobutylamino)methyl)benzoic acid The derivative was prepared using isobutylamine instead of aqueous methylamine, according to the synthesis described in Step 1 of Invention Example 1. 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 The derivative was prepared using 2-((isobutylamino)methyl)benzoic acid as a starting material, according to the synthesis described in step 2 of Invention Example 1. 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 ethylethyl 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoate The derivative was prepared using 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoic acid as a starting material, according to the synthesis described in step 3 of Invention Example 1. 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.). Invention Example 8: Ethyl 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate

[0068] Step 1: Synthesis of 2-((hexylamino)methyl)benzoic acid The derivative was prepared using n-hexylamine instead of aqueous methylamine, according to the synthesis described in Step 1 of Invention Example 1. 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 The derivative was prepared using 2-((hexylamino)methyl)benzoic acid as a starting material, according to the synthesis described in step 2 of Invention Example 1. 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 The derivative was prepared using 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoic acid as a starting material, according to the synthesis described in step 3 of Invention Example 1. 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.). Invention Example 9: Isobutyl 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate

[0071] Synthesis of isobutyl 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate The derivative was prepared using 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoic acid as a starting material, according to the synthesis described in step 3 of Invention Example 8. 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.). Invention Example 10: Isobutyl 2-((Hexyl(isobutoxycarbonyl)amino)methyl)

[0072] Step 1: Synthesis of 2-((hexyl(isobutoxycarbonyl)amino)methyl)benzoic acid The derivative was prepared using 2-((hexylamino)methyl)benzoic acid as a starting material and isobutyl chloroformate as an alkylating agent, according to the synthesis described in step 2 of Invention Example 8. 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 The derivative was prepared using 2-((hexyl(isobutoxycarbonyl)amino)methyl)benzoic acid as a starting material, according to the synthesis described in Invention Example 9. 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.). Invention Example 11: Ethyl 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate

[0074] Step 1: Synthesis of 2-(((2-ethylhexyl)amino)methyl)benzoic acid The derivative was prepared using (2-ethyl)hexylamine instead of aqueous methylamine, according to the synthesis described in Step 1 of Invention Example 1. 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 The derivative was prepared using 2-(((2-ethylhexyl)amino)methyl)benzoic acid as a starting material, according to the synthesis described in step 2 of Invention Example 1. 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 The derivative was prepared using 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoic acid as a starting material, according to the synthesis described in step 3 of Invention Example 1. 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.). Invention Example 12: Isobutyl 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate

[0077] Synthesis of isobutyl 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate The derivative was prepared using isobutanol as a solvent, according to the synthesis described in step 3 of Invention Example 11. 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.). Invention Example 13: Isobutyl 2-(((2-ethylhexyl)(isobutoxycarbonyl)amino)methyl)benzoate

[0078] Step 1: Synthesis of 2-(((2-ethylhexyl)(isobutoxycarbonyl)amino)methyl)benzoic acid The derivative was prepared using 2-(((2-ethylhexyl)amino)methyl)benzoic acid as a starting material, according to the synthesis described in Step 1 of Invention Example 10. 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 The derivative was prepared using 2-(((2-ethylhexyl)(isobutoxycarbonyl)amino)methyl)benzoic acid as a starting material, according to the synthesis described in Invention Example 12. 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.). Invention Example 14: Ethyl 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoate

[0080] Step 1: Synthesis of 2-(((cyclohexylmethyl)amino)methyl)benzoic acid The derivative was prepared using N-methylcyclohexylamine instead of aqueous methylamine, according to the synthesis described in Step 1 of Invention Example 1. 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 The derivative was prepared using 22-(((cyclohexylmethyl)amino)methyl)benzoic acid as a starting material, according to the synthesis described in step 2 of Invention Example 1. 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 The derivative was prepared using 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoic acid as a starting material, according to the synthesis described in step 3 of Invention Example 1. The final raw material was purified 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 A 250cm pipe equipped with a magnetic stirrer. 3 In a round-bottom flask, add 5.0 g (30 mmol) of commercially available ethyl 2-aminobenzoate to a 5.1 cm layer. 3(36 mmol, 1.2 equivalents) of triethylamine, along with 50 cm 3 It was dissolved in tetrahydrofuran. Then, 3.5 cm 3 (36 mmol, 1.2 equivalents) of ethyl chloroformate was added dropwise at 0°C, and the reaction mixture was 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 2 volumes of water and evaporated to obtain 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 A 250cm pipe equipped with a magnetic stirrer. 3 In a round-bottom flask under a nitrogen atmosphere, 6.0 g (25 mmol) of ethyl 2-((ethoxycarbonyl)amino)benzoate was added to 50 cm³. 3 Tetrahydrofuran and 0.8 g (30 mmol, 1.2 equivalents) of sodium hydride (powder, 90%) were added little by little. The mixture was set to 30°C and heated to 1.9 cm. 3 30 mmol (1.2 equivalents) of methyl iodide was added dropwise, and the reaction mixture was stirred at 40°C for 3 hours. 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 evaporated to obtain 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 preparation procedure for solid catalyst components

[0085] A 500cm² tank equipped with a mechanical stirrer, cooler, and thermometer. 3 In a round-bottom flask, 250 cm 3 TiCl4 was introduced at room temperature under a nitrogen atmosphere. After cooling to 0°C, the internal donors listed in Table 1 and 10.0 g of spherical adducts were sequentially added to the flask while stirring. The amount of internal donor packed was such that the Mg / donor molar ratio was 6. The temperature was raised to 100°C and maintained for 2 hours. Then, stirring was stopped, the solid product was allowed to precipitate, and the supernatant was collected by siphon at 100°C. After removing the supernatant, fresh TiCl4 was added to restore the initial volume. Next, the mixture was heated to 120°C and maintained at this temperature for 1 hour. Stirring was stopped again, the solid was allowed to precipitate, and the supernatant was collected by siphon. The solid was sterilized six times with anhydrous hexane at a temperature gradient of 60°C (6 × 100 cm²). 3 ), and once at room temperature (100cm 3 The solid was then washed. Next, the resulting solid was 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. Invention Examples 1-14 and Comparative Example 1 Preparation and polymerization of solid catalyst components

[0086] The general preparation procedure for the solid catalyst components was carried out using the donors reported in Table 1 as internal donors. The solid catalyst components thus obtained were 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. It includes Mg, Ti, and an electron donor of formula (II), (II) In the formula, R １ and R ９ groups may be the same as or different from each other, and are selected from C １ -C １５ hydrocarbon groups, R ２ group is selected from C １ -C １０ hydrocarbon groups, R ３ to R4 groups are independently selected from hydrogen or C １ -C １５ hydrocarbon groups that can condense with each other to form one or more rings, and R10 is independently selected from hydrogen or halogen or a C1-C10 alkyl group, a catalyst component for olefin polymerization.

2. R １ ~R 4 and R ９ C is independent １ -C １０ The catalyst component according to claim 1, wherein it is an alkyl group.

3. R ２ C １ -C １０ A catalyst component according to claim 1, selected from alkyl groups.

4. R ３ and R ４ These are, independently, hydrogen or C １ -C １０ A catalyst component according to claim 1, selected from alkyl groups.

5. The catalyst component according to Claim 1, A catalyst system for olefin polymerization, comprising a reaction product of an alkylaluminum compound.

6. Olefin CH ２ A (co)polymerization process of CHR (wherein R is hydrogen or a hydrocarbyl radical having 1 to 12 carbon atoms), the process being carried out in the presence of the catalyst system described in claim 5.

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