Catalyst components for the polymerization of olefins

Abstract

A solid catalyst component for the polymerization of olefins comprises Mg, Ti and an electron donor of formula (I) wherein R 1 groups and R 9 groups, equal to or different from each other, are selected from C1-C 15 hydrocarbon groups, R 2 groups are selected from hydrogen or C1-C 10 hydrocarbon groups, R 3 groups up to R 8 groups are independently selected from hydrogen or C1-C 15 hydrocarbon groups, which can be fused together to form one or more rings. The catalyst system based on the solid catalyst component has high activity and stereospecificity.

Description

Technical Field

[0001] This disclosure relates to catalyst components for the polymerization of olefins (particularly propylene), the catalyst component comprising a magnesium dihalide-based support on which Ti atoms are supported and an electron donor compound containing ester and urethane functional groups. This disclosure also relates to catalysts obtained from said components 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 are used, which typically comprise a solid catalyst component consisting of magnesium dihalide supported on a titanium compound and an internal electron donor compound, used in combination with an alkylaluminum compound. However, often, when higher polymer crystallinity is desired, an external donor (e.g., an alkoxysilane) is also required to achieve higher isotactic regularity. Phthalic acid esters, particularly diisobutyl phthalate, are used as internal donors in catalyst preparation. Phthalic acid esters are used as internal donors in combination with alkylalkoxysilanes as external donors. This catalyst system exhibits good performance in terms of activity, isotactic regularity, and xylene insolubility.

[0003] One of the issues associated with using this catalyst system is that phthalates have recently attracted some attention, leading to some compounds in this category being classified as sources of serious health problems.

[0004] Therefore, the research activity is dedicated to discovering alternative classes of internal donors for preparing catalyst components for propylene polymerization.

[0005] Some of the tested catalysts contain donor structures that simultaneously possess both carbamate and ester groups. PCT Publication WO2018 / 091375 describes a 1,3-amino ester derivative comprising a carbamate group and a free ester functional group. The performance of these catalysts in balancing activity / stereotropic properties is not entirely satisfactory, particularly regarding stereotropic properties, which require improvement. Summary of the Invention

[0006] Surprisingly, the applicant discovered that a class of donors containing both carbamate and ester functional groups within specific structures derived from amino acids produced catalysts exhibiting a good balance of activity and stereodirection.

[0007] Therefore, the object of this disclosure is to provide a catalyst composition for olefin polymerization comprising Mg, Ti and an electron donor of formula (I).

[0008]

[0009] Where R 1 Groups and R 9 The groups may be the same or different from each other, and are selected from C1-C. 15 hydrocarbon group, R 2 The radical is selected from hydrogen or C1-C. 10 hydrocarbon group, R 3 group to R 8 The groups are independently selected from hydrogen or C1-C. 15 Hydrocarbon groups, which can fuse together to form one or more rings. Detailed Implementation

[0010] In addition to carbon and hydrogen, the group R as defined above 1 To R 9 It may contain heteroatoms selected from halogens, P, S, N, O and Si.

[0011] Preferably, R 1 and R 9 Independently for C1-C 10 Alkyl, more preferably C1-C8 alkyl. More preferably, the alkyl is a primary alkyl.

[0012] Preferably, R 2 Selected from C1-C 10 Alkyl groups, more preferably selected from C2-C 10 Alkyl groups, and especially those selected from C2-C 10 Primary alkyl group.

[0013] Preferably, R 3 and R 4 Independently selected from hydrogen or C1-C 10 Alkyl, more preferably hydrogen or C1-C8 alkyl, and especially selected from hydrogen or straight-chain C1-C8 alkyl. According to one specific embodiment, R 3 and R 4 Both are hydrogen.

[0014] Preferably, R 5 To R 8 Independently selected from hydrogen or C1-C 20 Hydrocarbon group, more preferably hydrogen or C1-C 15 Hydrocarbon group, and especially selected from hydrogen or C1-C 10 Hydrocarbon group.

[0015] According to a specific implementation plan, R 6 and R 7 The atoms are linked together to form a ring structure, which has 3 to 10 ring-forming carbon atoms. Preferably, the ring structure has 5 to 6 ring-forming carbon atoms. The ring structure may have one or more carbon atoms selected from C1-C on the ring. 10Hydrocarbon group, and preferably selected from C1-C 10 Alkyl groups, more preferably substituents selected from C1-C8 alkyl groups.

[0016] When R 6 and R 7 When a ring structure is formed, R 5 and R 8 Hydrogen is preferred.

[0017] The structure belonging to formula (II) is particularly preferred.

[0018]

[0019]

[0020] Where R 1 To R 4 and R 9 It has the same meaning as disclosed above, and R 10 Independently selected from hydrogen or halogen or C1-C 10 Alkyl, more preferably hydrogen, halogen or C1-C8 alkyl.

[0021] The preferred structures of formula (II) are those that have the following characteristics: R 1 and R 9 Independently for C1-C 10 Primary alkyl group, R 2 Selected from C1-C 10 Straight-chain or branched alkyl groups, R 3 and R 4 Selected from hydrogen or C1-C 10 Alkyl, and R 10 It is independently selected from hydrogen, C1-C8 alkyl or halogen, provided that at least two of them are hydrogen.

[0022] Preferably, the final amount of the electron donor compound in the solid catalyst component is 1 to 25% by weight, preferably in the range of 3 to 20% by weight.

[0023] Non-restrictive examples of the structures of equations (I) and (II) are as follows:

[0024] 4-((methoxycarbonyl)amino)butyrate methyl ester, 4-((methoxycarbonyl)(methyl)amino)3-methylbutyrate methyl ester, 4-((cyclohexylmethyl)(methoxycarbonyl)amino)3-methylbutyrate methyl ester, 4-(hexyl(methoxycarbonyl)amino)-3-methylpentanoate methyl ester, 4-(benzyl(methoxycarbonyl)amino)-3-methylpentanoate methyl ester, 4-(butyl(methoxycarbonyl)amino)-2,3-dimethylpentanoate methyl ester, 2-isopropyl-4-((methoxycarbonyl)(methyl)amino)-5-methylhexanoate methyl ester, 2-isopropyl-4-(hexyl(methoxycarbonyl)amino)-5-methylhexanoate methyl ester, 2-isopropyl-4-((cyclohexylmethyl)(methoxycarbonyl)amino)-5-methylhexanoate pentanoate, 3-benzyl- Methyl 4-(isopropyl(methoxycarbonyl)amino)butyrate, methyl 4-((methoxycarbonyl)(propyl)amino)-2-methyl-5-phenylpentanoate, methyl 4-((cyclohexylmethyl)(methoxycarbonyl)amino)-2-methyl-5-phenylpentanoate, ethyl 4-((methoxycarbonyl)amino)butyrate, ethyl 2-(((ethoxycarbonyl)(ethyl)amino)methyl)benzoate, ethyl 4-(hexyl(methoxycarbonyl)amino)butyrate, propyl 4-(hexyl(methoxycarbonyl)amino)3-methylbutyrate, ethyl 4-((methoxycarbonyl)amino)-3-methylpentanoate, ethyl 4-(isopropyl(methoxycarbonyl)amino)-3-methylpentanoate, hexyl 4-((methoxycarbonyl)amino)-2,3-dimethylpentanoate, hexyl 4-(isopropyl)amino)-2,3-dimethylpentanoate, methyl ... Ethyl (methoxycarbonyl)amino)-2,3-dimethylvalerate, 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)butyrate, ethyl 3-benzyl-4-(benzyl(methoxycarbonyl)amino)butyrate, decyl 4-((ethoxycarbonyl)(methyl)amino)butyrate, ethyl 4-(cyclohexyl(ethoxycarbonyl)amino)butyrate, ethyl 4-(ethoxycarbonyl)amino)-3-methylbutyrate, ethyl 4-((cyclohexylmethyl)(ethoxycarbonyl)amino)-3-methylbutyrate Ethyl ester, 4-(cyclohexyl(ethoxycarbonyl)amino)-3-methylvalerate, 4-(ethyl(ethoxycarbonyl)amino)-2,3-dimethylvalerate, 4-(butyl(ethoxycarbonyl)amino)-2,3-dimethylvalerate, 4-(benzyl(ethoxycarbonyl)amino)-2,3-dimethylvalerate, 2-isopropyl-4-((2-ethylhexyl)(ethoxycarbonyl)amino)-5-methylhexanoate, 3-benzyl-4-((ethoxycarbonyl)amino)butyrate, 4-(isobutyl(ethoxycarbonyl)amino)-2-methyl-5-phenylvalerate, 4-(hexyl(ethoxycarbonyl)amino)butyrate isobutyl ester, 4-((2-ethylhexyl)(ethoxycarbonyl)amino)-3-methylbutyrate isobutyl ester,2-((hexyl(isobutoxycarbonyl)amino)methyl)benzoate isobutyl ester, 4-((ethoxycarbonyl)(propyl)amino)-3-methylvalerate isobutyl ester, 4-((ethoxycarbonyl)amino)-2,3-dimethylvalerate isobutyl ester, 2-isopropyl-4-(cyclohexyl(ethoxycarbonyl)amino)-5-methylhexanoate isobutyl ester, 3-benzyl-4-(benzyl(ethoxycarbonyl)amino)butyrate isobutyl ester, 4-((cyclohexylmethyl)(ethoxycarbonyl)amino)-2-methyl-5-phenylvalerate isobutyl ester, 4-((isobutoxycarbonyl)amino)butyrate propyl ester, 4-((isobutoxycarbonyl)(methyl)amino)-3-methylbutyrate propyl ester, 4-(ethyl(isobutoxycarbonyl)amino)-3-methylvalerate propyl ester, 4-((isobutoxycarbonyl)amino)-3-methylvalerate isobutyl ester, 4-((isobutoxycarbonyl)amino)-2-methyl-5-phenylvalerate isobutyl ester, 4-((isobutoxycarbonyl)amino)-3-methyl ... propyl(propyl)amino)-2,3-dimethylvalerate, propyl 2-isopropyl-4-(butyl(isobutyryloxycarbonyl)amino)-5-methylhexanoate, propyl 3-benzyl-4-(cyclohexyl(isobutyryloxycarbonyl)amino)butanoate, propyl 4-((2-ethylhexyl)(isobutyryloxycarbonyl)amino)-2-methyl-5-phenylvalerate, propyl 4-((cyclohexylmethyl)(isobutyryloxycarbonyl)amino)-2-methyl-5-phenylvalerate, propyl 4-(ethyl(isobutyryloxycarbonyl)amino)butanoate, isobutyl 4-((2-ethylhexyl)(isobutyryloxycarbonyl)amino)-3-methylbutanoate, isobutyl 4-(benzyl(isobutyryloxycarbonyl)amino)-3-methylvalerate, propyl 4-((cyclohexylmethyl)(isobutyryloxycarbonyl)amino)-2, Isobutyl 3-dimethylvalerate, 2-isopropyl-4-((isobutoxycarbonyl)amino)-5-methylhexanoate, 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate, 3-benzyl-4-(butyl(isobutoxycarbonyl)amino)butanoate, 4-(hexyl(isobutoxycarbonyl)amino)-2-methyl-5-phenylvalerate, 2-ethylhexyl-4-(ethyl(butoxycarbonyl)amino)butyrate, 2-ethylhexyl-4-(butyl(butoxycarbonyl)amino)-3-methylbutyrate, 2-ethylhexyl-4-(hexyl(butoxycarbonyl)amino)-3-methylvalerate, 2-ethylhexyl-4-(cyclohexyl(butoxycarbonyl)amino)-2,3-dimethylvalerate, 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-phenylvalerate, 4-((ethoxycarbonyl)amino)benzyl butyrate, 4-(ethyl(ethoxycarbonyl)amino)-3-methylbutyrate decyl ester, 4-(butyl(ethoxycarbonyl)amino)-3-methylvalerate benzyl ester, 4-(hexyl(ethoxycarbonyl)amino)-2,3-dimethylvalerate benzyl ester, 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate ethyl ester, 2-isopropyl-4-(benzyl(ethoxycarbonyl)amino)-5-methylhexanoate benzyl ester3-Benzyl-4-((2-ethylhexyl)(ethoxycarbonyl)amino)benzyl butyrate, 4-(isopropyl(ethoxycarbonyl)amino)-2-methyl-5-phenylpentanoate benzyl ester, 4-(cyclohexyl(ethoxycarbonyl)amino)-2-methyl-5-phenylpentanoate benzyl ester, 2-(((methoxycarbonyl)amino)methyl)benzoate methyl ester, 2-((butyl(methoxycarbonyl)amino)methyl)benzoate methyl ester, 2-(((cyclohexylmethyl)(methoxycarbonyl)amino)methyl)benzoate decyl ester, 2-(1-((methoxycarbonyl)(methyl)amino)ethyl)benzoate methyl ester, 2-(1-(isobutyl(methoxycarbonyl)amino)ethyl)benzoate methyl ester, 2-(1-benzyl(methoxycarbonyl)amino)ethyl)benzoate methyl ester, 2 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-ethylhexyl)(methoxycarbonyl)amino)(phenyl)methyl)-5-chlorobenzoate, methyl 5-(tert-butyl)-2-(((methoxycarbonyl)(propyl)amino)(phenyl)methyl)-3-methylbenzoate, methyl 5-(tert-butyl)-2-((isobutyl(methoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, heptyl 2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoate, ethyl 2-((hexyl(ethyl)... Ethyl benzoate, 2-(1-(ethyl(ethoxycarbonyl)amino)ethyl)benzoate, 2-(1-((cyclohexylmethyl)(ethoxycarbonyl)amino)ethyl)benzoate, 2-(((ethoxycarbonyl)amino)(phenyl)methyl)benzoate, 2-((isobutyl(ethoxycarbonyl)amino)(phenyl)methyl)benzoate, 2-((isopropyl(ethoxycarbonyl)amino)(4-chlorophenyl)methyl)decyl benzoate, 2-((butyl(ethoxycarbonyl)amino)(4-chlorophenyl)methyl)benzoate, 2-(((ethoxycarbonyl)amino)(phenyl)methyl)-5-chlorobenzoate, 2-((benzyl(ethoxycarbonyl)amino)(phenyl)methyl)-5-chlorobenzoate Ethyl benzoate, 5-(tert-butyl)-2-((butyl(ethoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, 5-(tert-butyl)-2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, 2-(((isobutoxycarbonyl)amino)methyl)benzoate, 2-(1-((isobutoxycarbonyl)(methyl)amino)ethyl)benzoate, 2-((ethyl(isobutoxycarbonyl)amino)(phenyl)methyl)benzoate, 2-(((isobutoxycarbonyl)(propyl)amino)(4-chlorophenyl)methyl)benzoate, 2-((isopropyl(isobutoxycarbonyl)amino)(phenyl)methyl)-5-chlorobenzoate,5-(tert-butyl)-2-((isobutyl(isobutoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, 2-ethylhexyl-2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoate, 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, 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate Isobutyl benzoate, 2-ethylhexyl-2-((cyclohexyl(ethoxycarbonyl)amino)(phenyl)methyl)benzoate, 2-(((ethoxycarbonyl)(propyl)amino)(4-chlorophenyl)methyl)benzoate, 2-ethylhexyl-2-(((2-ethylhexyl)(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, 2-((isobutyl(ethoxycarbonyl)amino)(phenyl)methyl) 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, 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoate, 2-Ethylhexyl-5-(tert-butyl)-2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, 2-(((isobutoxycarbonyl)amino)(4-fluorophenyl)methyl)benzoic acid Isobutyl ester, 2-((isopropyl(isobutyoxycarbonyl)amino)(4-fluorophenyl)methyl)benzoate sec-butyl ester, 2-((hexyl(isobutyoxycarbonyl)amino)(4-fluorophenyl)methyl)benzoate isobutyl ester, 2-ethylhexyl-2-((ethyl(ethoxycarbonyl)amino)(phenyl)methyl)-4-bromobenzoate, 2-(((2-ethylhexyl)(isobutyoxycarbonyl)amino)methyl)benzoate isobutyl ester, 2-ethylhexyl-2-((isobutyl(ethoxycarbonyl)amino)(phenyl)methyl)-4-bromobenzoate, 2-ethylhexyl-2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)(phenyl)methyl)-4-bromobenzoate, 2-(2-((methoxycarbonyl)(methyl)amino)phenyl)acetate methyl acetate,2-(2-(cyclohexyl(methoxycarbonyl)amino)phenyl)acetate methyl ester, 2-(2-((methoxycarbonyl)amino)phenyl)propionate methyl ester, 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoate ethyl ester, 2-(2-(hexyl(ethoxycarbonyl)amino)phenyl)-2-methylpropionate methyl ester, 2-(2-(cyclohexyl(methoxycarbonyl)amino)phenyl)-2-phenylacetate methyl ester, 2-(4-chlorophenyl)-2-(2-(ethyl(methoxycarbonyl)amino)phenyl)acetate methyl ester, 2-(5-(tert-butyl)-2-(ethyl(methoxycarbonyl)amino)-3-methylphenyl)-2-(4-chlorophenyl)acetate methyl ester, 2-(2-((ethoxycarbonyl)amino)phenyl)ethyl acetate, 2-(2- Benzyl (isobutyl(ethoxycarbonyl)amino)phenyl)propionate, 2-(2-(cyclohexyl(ethoxycarbonyl)amino)phenyl)-2-methylpropionate, ethyl 2-(2-((2-ethylhexyl)(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, 2-(2-((isobutyryl(methyl)amino)phenyl)acetate, 2-(2-(cyclohexyl(isobutyryl)amino)phenyl)acetate, 2-(2-(isopropyl(isobutyryl)amino)amino)phenyl)acetate Isobutyl 2-(2-(hexyl(isobutyoxycarbonyl)amino)phenyl)propionate, Isobutyl 2-(2-(hexyl(isobutyoxycarbonyl)amino)phenyl)-2-methylpropionate, Isobutyl 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate, Isobutyl 2-(2-((2-ethylhexyl)(isobutyoxycarbonyl)amino)phenyl)-2-methylpropionate, Isobutyl 2-(2-(benzyl(isobutyoxycarbonyl)amino)phenyl)-2-phenylacetic acid, Isobutyl 2-(2-((cyclohexylmethyl)(isobutyoxycarbonyl)amino)phenyl)-2-phenylacetic acid, Isobutyl 2-(4-chlorophenyl)-2-(2-(cyclohexyl(isobutyoxycarbonyl)amino)phenyl)acetic acid, Isobutyl 2- (5-(tert-butyl)-2-(isopropyl(isobutoxycarbonyl)amino)-3-methylphenyl)-2-(4-chlorophenyl)acetic acid isobutyl ester, 2-ethylhexyl-2-(2-((butoxycarbonyl)amino)phenyl)acetic acid ester, 2-ethylhexyl-2-(2-(benzyl(butoxycarbonyl)amino)phenyl)acetic acid ester, 2-ethylhexyl-2-(2-((butoxycarbonyl)(propyl)amino)phenyl)propionate, 2-ethylhexyl-2-(2-((2-ethylhexyl)(butoxycarbonyl)amino)phenyl)propionate, 2-ethylhexyl-2-(2-((2-ethylhexyl)(butoxycarbonyl)amino)phenyl)propionate, 2-ethylhexyl-2-(2-(butyl(butoxycarbonyl)amino)phenyl)-2-methylpropionate, 2-ethylhexyl-2-(2-((butoxycarbonyl)amino)phenyl)-2-phenylacetic acid ester2-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.

[0025] The compounds in formula (I) can usually be prepared using the following synthetic route.

[0026] Commercially available amino acids can be converted from alkyl chloroformates to ((alkoxy)carbonyl)amino acids, while the acid moiety is treated in a suitable alcohol under Fischer conditions to obtain the desired ester. When amino acids are unavailable, they can be prepared from their α-aldehyde or α-keto acid precursors by reductive amination using suitable primary amines and borohydride reducing agents.

[0027] In the solid catalyst composition disclosed herein, the amount of Ti atoms relative to the total weight of the catalyst composition is preferably greater than 2.5% wt, more preferably greater than 3.0%.

[0028] As explained above, in addition to the aforementioned electron donors, the catalyst component of this disclosure also comprises Ti, Mg, and halogens. Specifically, the catalyst component comprises a titanium compound having at least a Ti-halogen bond and the aforementioned electron donor compound supported on magnesium halide. The magnesium halide is preferably in the active form of MgCl2, which is widely known in patent literature as a support for Ziegler-Natta catalysts. Patents USP 4,298,718 and USP 4,495,338 first describe the use of these compounds in Ziegler-Natta catalysis. It is known from these patents that the active form of magnesium dihalides used as a support or co-support in the component of catalysts for olefin polymerization is characterized by X-ray spectroscopy in which the intensity of the strongest diffraction line appearing in the spectrum of the inactive halide decreases and is replaced by a halogen whose maximum intensity is shifted at a lower angle relative to a stronger linear direction.

[0029] Preferred titanium compounds used in the catalyst composition of this disclosure are TiCl4 and TiCl3; in addition, Ti(OR) can also be used. 11 ) m-y X y Ti-haloalcohols, where m is the valence of titanium, y is a number between 1 and m-1, X is a halogen, and R11 It is a hydrocarbon group having 1 to 10 carbon atoms.

[0030] The solid catalyst component can be prepared by several methods. One method involves reacting a magnesium alkoxide or a chloroalkoxide (particularly a chloroalkoxide prepared according to USP 4,220,554) with an excess of TiCl4 in the presence of an electron donor compound at a temperature of about 80 to 120 °C.

[0031] According to a preferred method, the solid catalyst component can be prepared by using the formula Ti(OR) 11 ) m-y X y (where m is the valence of titanium and y is a number between 1 and m, preferably TiCl4) titanium compounds derived from the formula MgCl2·pR 12 OH (where p is a number between 0.1 and 6, preferably 2 to 3.5, and R 12 The adduct is prepared by reacting magnesium chloride with an adduct having a hydrocarbon group having 1 to 18 carbon atoms. A spherical form of the adduct can be suitably prepared by mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, and operating under stirring at the melting temperature of the adduct (100 to 130 °C). The emulsion is then rapidly quenched, thereby solidifying the adduct into spherical particles. Examples of spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648. The adduct thus obtained can be reacted directly with a Ti compound, or it can be pre-treated with thermally controlled alcohol removal (80 to 130 °C) to obtain an adduct in which the molar number of alcohol is less than 3, preferably between 0.1 and 2.5. The reaction with the Ti compound can be carried out by suspending the adduct (alcoholized or as is) in cold TiCl4 (about 0 °C); the mixture is then heated to 80 to 130 °C and held at that temperature for 0.5 to 2 hours. Treatment with TiCl4 can be performed once or multiple times. The electron donor compound is preferably added during the TiCl4 treatment. For example, the preparation of spherical catalyst components is described in European patent applications EP-A-395083, EP-A-553805, EP-A-553806, EPA601525 and WO98 / 44009.

[0032] The solid catalyst components obtained by the above method show surface areas (by the BET method) ranging from 20 to 500 m². 2 Between / g, and preferably between 50 and 400m 2 The concentration is between [value] / g and the total porosity (by BET method) is greater than 0.2 cm³. 3 / g, preferably between 0.2 and 0.6cm 3 Between / g. From radius to most The porosity caused by the pores (mercury method) can range from 0.3 to 1.5 cm⁻¹. 3 / g, preferably from 0.45 to 1cm 3 / g.

[0033] The solid catalyst component has an average particle size ranging from 5 to 120 μm, and more preferably from 10 to 100 μm.

[0034] In any of these preparation methods, the desired electron donor compound may be added directly, or alternatively, it may be obtained in situ using a suitable precursor that can be converted into the desired electron donor compound by, for example, a usable chemical reaction.

[0035] Regardless of the preparation method used, the final amount of the electron donor compound disclosed herein is such that its molar ratio relative to Ti atoms is 0.01 to 2, preferably 0.05 to 1.5.

[0036] In addition to the donors mentioned above, the solid catalyst component may also contain additional donors. Although there are no restrictions on the type of additional donors, they may be selected from esters, ethers, carbamates, thioesters, amides, and ketones.

[0037] Of the above categories, 1,3-diethers of formula (IV) are particularly preferred.

[0038]

[0039]

[0040] Where R I and R II The same or different and composed of hydrogen or straight or branched C1-C chains that can form one or more cyclic structures. 18 hydrocarbon group; R III Groups, whether the same or different from each other, are hydrogen or C1-C. 18 hydrocarbon group; R IV The groups may be the same or different from each other, and have the same characteristics as R. III The same meaning, except they cannot be hydrogen; R I To R IV Each of the groups may contain heteroatoms selected from halogens, N, O, S, and Si.

[0041] Preferably, R IV Alkyl groups having 1 to 6 carbon atoms, more particularly methyl groups, while R III The group is preferably hydrogen. Furthermore, when R... I When R is methyl, ethyl, propyl, isopropyl, or isopentyl, IIIt can be ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, isopentyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl, or benzyl; when R I When it is hydrogen, R II It can be ethyl, butyl, sec-butyl, tert-butyl, 2-ethylhexyl, cyclohexylethyl, diphenylmethyl, p-chlorophenyl, 1-naphthyl, 1-decahydronaphthyl; R I and R II It can also be the same, and can be ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, phenyl, benzyl, cyclohexyl, or cyclopentyl.

[0042] Compounds of formula (V) are particularly preferred:

[0043]

[0044] Where R VI The functional groups may be the same or different, and are hydrogen; halogens, preferably Cl and F; straight-chain or branched C. l -C 20 Alkyl; C3-C 20 cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl and C7-C 20 Aryl group, optionally containing one or more heteroatoms selected from the group consisting of N, O, S, P, Si and halogens (especially Cl and F) as substituents for carbon or hydrogen atoms or both; group R III and R IV As defined in equation (IV) above.

[0045] The solid catalyst components according to this disclosure are converted into catalysts for olefin polymerization by reacting them with organoaluminum compounds according to available methods.

[0046] In particular, the purpose of this disclosure is to provide a catalyst for the polymerization of olefins CH2=CHR, wherein R is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, the catalyst comprising a product obtained by contacting the following substances:

[0047] (i) the solid catalyst components as disclosed above, and

[0048] (ii) Alkyl aluminum compounds, and optionally,

[0049] (iii) External electron donor compounds.

[0050] The alkyl-Al compound (ii) is preferably selected from trialkylaluminum compounds, such as, for example, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum. Alkylaluminum halides, alkylaluminum hydrides, or alkylaluminum sesquichlorides, such as AlEt2Cl and Al2Et3Cl3, may also be used (possibly in the form of mixtures with the above-mentioned trialkylaluminum compounds).

[0051] External electron donor compounds may include silicon compounds, ethers, esters, amines, and heterocyclic compounds.

[0052] Another preferred type of external donor compound is of formula (R) 13 ) a (R 14 ) b Si(OR 15 ) c A silicon compound, where a and b are integers from 0 to 2, c is an integer from 1 to 4, and the sum (a+b+c) is 4; R 13 R 14 and R 15 It is a group having 1 to 18 carbon atoms that optionally contains heteroatoms. Particularly preferred are silicon compounds in which a is 1, b is 1, c is 2, and R... 13 and R 14 At least one of them is selected from branched alkyl, cycloalkyl, or aryl groups having 3 to 10 carbon atoms, optionally containing heteroatoms, and R 15 It is C1-C 10 Alkyl groups, particularly methyl groups. Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C-donor), diphenyldimethoxysilane, methyl tert-butyldimethoxysilane, dicyclopentyldimethoxysilane (D-donor), diisopropyldimethoxysilane, (2-ethylpiperidinyl)-tert-butyldimethoxysilane, (2-ethylpiperidinyl)tert-hexyldimethylchlorosilane, (3,3,3-trifluoro-n-propyl)(2-ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane, and N,N-diethylaminotriethoxysilane. Furthermore, it is also preferred that a is 0, c is 3, and R... 14 It is optionally a branched alkyl or cycloalkyl group containing heteroatoms and R 15 These are methyl silicon compounds. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, and tert-hexyltrimethoxysilane.

[0053] The amount of electron donor compound (iii) is such that the molar ratio between the organoaluminum compound and the electron donor compound (iii) is from 0.1 to 500, preferably from 1 to 300, and more preferably from 3 to 100.

[0054] As explained, the catalyst components of this disclosure, particularly when used in conjunction with alkylaluminum compounds and alkylalkoxysilanes for propylene polymerization, 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 xylene insolubility at 25°C greater than 96.0% wt, preferably greater than 96.5% wt, and more preferably greater than 97.0% wt.

[0055] Therefore, another object of this disclosure is: a method for the (co)polymerization of olefins CH2=CHR, wherein R is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, the method being carried out in the presence of a catalyst comprising the reaction products between the following substances:

[0056] (i) The solid catalyst components of this disclosure;

[0057] (ii) Alkyl aluminum compounds, and

[0058] (iii) Optional electron donor compound (external donor).

[0059] The polymerization method can be carried out according to available technologies, such as slurry polymerization using inert hydrocarbon solvents as diluents, or bulk polymerization using liquid monomers (e.g., propylene) as the reaction medium. Alternatively, polymerization methods can be carried out in the gas phase in one or more fluidized bed or mechanically stirred bed reactors.

[0060] Polymerization can be carried out at temperatures ranging from 20 to 120°C, preferably from 40 to 80°C. When polymerization is carried out in the gas phase, the operating pressure can be between 0.5 and 5 MPa, preferably between 1 and 4 MPa. In bulk polymerization, the operating pressure is between 1 and 8 MPa, preferably between 1.5 and 5 MPa.

[0061] The following embodiments are provided to further illustrate this disclosure and are not intended to limit this disclosure.

[0062] Characterization

[0063] Measurement of XI

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

[0065] Determination of the donor.

[0066] The electron donor content was determined by gas chromatography. The solid component was dissolved in acidic water. The solution was extracted with ethyl acetate, an internal standard was added, and the organic phase of the sample was analyzed in a gas chromatograph to determine the amount of donor present at the starting catalyst compound.

[0067] Melt flow rate (MFR)

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

[0069] Example

[0070] Procedure for preparing spherical adducts

[0071] The initial amount of MgCl2·2.8C2H5OH adduct was prepared according to the method described in Example 2 of WO98 / 44009, but on a larger scale.

[0072] General procedure for propylene polymerization

[0073] A 4-liter steel autoclave equipped with a stirrer, pressure gauge, thermometer, catalyst feed system, monomer feed line, and thermostatic jacket was purged with a nitrogen stream at 70°C for 1 hour. Then, at 30°C, under a propylene stream, 75 mL of anhydrous hexane, 0.76 g of AlEt3, dicyclopentyldimethoxysilane as an external electron donor (to achieve an Al / donor molar ratio of 20), and 0.006 ÷ 0.010 g of solid catalyst components were added sequentially. The autoclave was shut off; subsequently, 2.0 L of hydrogen was added. Then, under stirring, 1.2 kg of liquid propylene was added. The temperature was raised to 70°C within 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 vacuum dried 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.

[0074] General procedures for preparing internal donors

[0075] Example 1 of the invention: Ethyl 2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoate

[0076] Step 1: Synthesis of 2-((methylamino)methyl)benzoic acid

[0077] 250cm equipped with a magnetic stirrer 3 In a round-bottom flask, dissolve 5.0 g (33 mmol) of commercially available 2-formylbenzoic acid in a 50 cm³ solution. 3In methanol, 5.8 cm of solution was added dropwise at room temperature. 3 (66 mmol, 2 equivalents) of methylamine aqueous solution (40% wt). After 1 hour, 0.7 g (18 mmol, 0.6 equivalents) of sodium borohydride was added in small portions at 0 °C, and the reaction was then allowed to proceed at room temperature for 3 hours. At this point, the solvent was removed under vacuum, yielding a viscous oily substance, which was ground with acetone to give a white solid product. Yield 100%. 1 HNMR(400MHz,D2O):2.98(s,3H,CH3),4.20(s,2H,CH2),7.2-7.7(m,4H,arom.).

[0078] Step 2: Synthesis of 2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoic acid

[0079] 250cm equipped with a magnetic stirrer 3 In a round-bottom flask, 5.5 g (33 mmol) of 2-((methylamino)methyl)benzoic acid was dissolved in a 20 cm³ solution. 3 The mixture was prepared in an aqueous NaOH solution (3 equivalents relative to the amino acid). Then, 5.5 g (50 mmol, 1.5 equivalents) of ethyl chloroformate was added dropwise, and the 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 twice its volume of water and then evaporated to give the final product as a colorless oil. Yield: 67%. 1 HNMR(400MHz,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,arom.),7.8(m,1H,arom.).

[0080] Step 3: Synthesis of ethyl 2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoate

[0081] 250cm equipped with a magnetic stirrer 3 In a round-bottom flask, 5.2 g (0.22 mmol) of 2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoic acid was added to a 1 cm... 3 Dissolve together with sulfuric acid in 50cm 3 The mixture was refluxed in ethanol for 5 hours, and then the solvent was removed. The crude product was dissolved in ethyl acetate and washed with an aqueous sodium bicarbonate solution. The solvent was then removed to give the final product as a colorless oil. Yield: 80%, Purity: 95% (GC). 1HNMR(400MHz,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,arom.),7.9(m,1H,arom.).

[0082] Example 2 of the invention: Ethyl 2-(((ethoxycarbonyl)(ethyl)amino)methyl)benzoate

[0083] Step 1: Synthesis of 2-((ethylamino)methyl)benzoic acid

[0084] This derivative was prepared according to the synthesis described in step 1 of Example 1 of the invention, using 2M ethylamine in THF instead of an aqueous solution of methylamine. Yield: 90%. 1 HNMR(400MHz,D2O):1.0(t,3H,CH3),2.6(q,2H,CH2),3.9(s,2H,CH2),7.2(m,3H,arom.),7.7(m,1H,arom.).

[0085] Step 2: Synthesis of 2-(((ethoxycarbonyl)(ethyl)amino)methyl)benzoic acid

[0086] This derivative was prepared according to the synthesis described in step 2 of Example 1 of the invention, using 2-((ethylamino)methyl)benzoic acid as the starting material. The yield was 72%. 1 HNMR(400MHz,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,arom.),8.0(m,1H,arom.).

[0087] Step 3: Ethyl 2-(((ethoxycarbonyl)(ethyl)amino)methyl)benzoate

[0088] This derivative was synthesized according to the method described in steps 1-3 of the present invention, using 2-(((ethoxycarbonyl)(ethyl)amino)methyl)benzoic acid as the starting material. The yield was 90%, and the purity was 99% (GC). 1HNMR(400MHz,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,arom.),7.9(m,1H,arom.).

[0089] Example 3 of the Invention: Ethyl 2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoate

[0090] Step 1: Synthesis of 2-((propylamino)methyl)benzoic acid

[0091] This derivative was prepared according to the synthesis described in step 1 of Example 1 of the invention, using n-propylamine instead of aqueous methylamine. Yield: 85%. 1 HNMR(400MHz,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,arom.).

[0092] Step 2: Synthesis of 2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoic acid

[0093] This derivative was prepared according to the synthesis described in step 2 of Example 1 of the invention, using 2-((propylamino)methyl)benzoic acid as the starting material. The yield was 74%. 1 HNMR(400MHz,CDCl3):0.8(t,3H,CH3),1.1(m,3H,CH3),1.5(m,2H,CH2),3.2(m,2H ,CH2),4.1(q,2H,CH2),4.9(s,2H,CH2),7.3-7.5(m,3H,arom.),8.0(m,1H,arom.).

[0094] Step 3: Synthesize ethyl 2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoate

[0095] This derivative was prepared according to the synthesis described in steps 1-3 of the invention, using 2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoic acid as the starting material. The yield was 84%, and the purity was 96% (GC). 1HNMR(400MHz,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 ,CH2),4.1(m,2H,CH2),4.3(q,2H,CH2),4.8(s,2H,CH2),7.2-7.5(m,3H,arom.),7.9(m,1H,arom.).

[0096] Example 4 of the Invention: Ethyl 2-((Butyl(ethoxycarbonyl)amino)methyl)benzoate

[0097] Step 1: Synthesis of 2-((butylamino)methyl)benzoic acid

[0098] This derivative was prepared according to the synthesis described in step 1 of Example 1 of the invention, using n-butylamine instead of aqueous methylamine. Yield: 100%. 1 HNMR(400MHz,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,arom.),7.7(m,1H,arom.).

[0099] Step 2: Synthesis of 2-((butyl(ethoxycarbonyl)amino)methyl)benzoic acid

[0100] This derivative was prepared according to the synthesis described in step 2 of Example 1 of the invention, using 2-((butylamino)methyl)benzoic acid as the starting material. The yield was 81%. 1 HNMR(400MHz, 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,arom.),8.0(m,1H,arom.).

[0101] Step 3: Synthesis of ethyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate

[0102] This derivative was synthesized according to the method described in steps 1-3 of the present invention, using 2-((butyl(ethoxycarbonyl)amino)methyl)benzoic acid as the starting material. The yield was 89%, and the purity was 95% (GC). 1HNMR(400MHz, 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,arom.),7.9(m,1H,arom.).

[0103] Invention Example 5: Isobutyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate

[0104] Synthesis of 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate isobutyl ester

[0105] This derivative was prepared using isobutanol as a solvent according to the synthesis described in step 3 of Example 4 of the invention. Yield: 90%, purity: 97% (GC). 1 HNMR(400MHz, CDCl3):0.8(t,3H,CH3),0.9(d,6H,2CH3),1.0-1.5(m,7H,CH3(CH2)2),2.1(m,1H,C H),3.2(m,2H,CH2),4.2(m,4H,2CH2),4.8(s,2H,CH2),7.2-7.5(m,3H,arom.),8.0(m,1H,arom.).

[0106] Example 6 of the Invention: 2-Ethylhexyl-2-((Butyl(ethoxycarbonyl)amino)methyl)benzoate

[0107] Synthesis of 2-ethylhexyl-2-((butyl(ethoxycarbonyl)amino)methyl)benzoate

[0108] This derivative was prepared according to the synthesis described in step 3 of Example 4 of the invention, using 2-(2-ethylhexyloxy)ethanol as a solvent. Yield: 78%, purity: 98% (GC). 1 HNMR(400MHz, CDCl3):0.8(m,9H,3CH3),1.1-1.7(m,16H,CH3(CH2)2+(CH2)3CHCH2),3.2( m,2H,CH2),4.1(m,4H,2CH2),4.8(s,2H,CH2),7.2-7.5(m,3H,arom.),7.9(m,1H,arom.).

[0109] Example 7 of the Invention: Ethyl 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoate

[0110] Step 1: Synthesis of 2-((isobutylamino)methyl)benzoic acid

[0111] This derivative was prepared according to the synthesis described in step 1 of Example 1 of the invention, using isobutylamine instead of aqueous methylamine. Yield: 100%. 1 HNMR(400MHz,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,arom.),7.7(m,1H,arom.).

[0112] Step 2: Synthesis of 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoic acid

[0113] This derivative was prepared according to the synthesis described in step 2 of Example 1 of the invention, using 2-((isobutylamino)methyl)benzoic acid as the starting material. The yield was 81%. 1 HNMR(400MHz,CDCl3):0.8(d,3H,2CH3),1.1(m,3H,CH3),1.9(m,1H,CH),3.1(d,2H ,CH2),4.1(m,2H,CH2),4.8(s,2H,CH2),7.3-7.5(m,3H,arom.),8.0(m,1H,arom.).

[0114] Step 3: Synthesis of ethyl 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoate

[0115] This derivative was synthesized according to the method described in steps 1-3 of the present invention, using 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoic acid as the starting material. The yield was 87%, and the purity was 95% (GC). 1 HNMR(400MHz, CDCl3):0.8(d,6H,2CH3),1.0-1.3(m,6H,CH3+CH3),1.9(m,1H,CH),3.0(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,arom.),7.9(m,1H,arom.).

[0116] Example 8 of the Invention: Ethyl 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate

[0117] Step 1: Synthesis of 2-((hexamethylene)methyl)benzoic acid

[0118] This derivative was prepared according to the synthesis described in step 1 of Example 1 of the invention, using n-hexylamine instead of aqueous methylamine. Yield: 73%. 1 HNMR(400MHz,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,arom.),7.8(m,1H,arom.).

[0119] Step 2: Synthesis of 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoic acid

[0120] This derivative was prepared according to the synthesis described in step 2 of Example 1 of the invention, using 2-((hexylamino)methyl)benzoic acid as the starting material. The yield was 80%. 1 HNMR(400MHz,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,arom.),8.1(m,1H,arom.).

[0121] Step 3: Synthesize ethyl 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate

[0122] This derivative was synthesized according to the method described in steps 1-3 of the present invention, using 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoic acid as the starting material. The yield was 94%, and the purity was 99% (GC). 1 HNMR(400MHz, 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,arom.),7.9(m,1H,arom.).

[0123] Invention Example 9: Isobutyl 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate

[0124] Synthesis of 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate isobutyl ester

[0125] This derivative was synthesized according to the method described in step 3 of Example 8 of the invention, using 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoic acid as the starting material and isobutanol as the solvent. The yield was 83%, and the purity was 94% (GC). 1 HNMR(400MHz, 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,arom.),7.9(m,1H,arom.).

[0126] Invention Example 10: Isobutyl-2-((hexyl(isobutyryloxycarbonyl)amino)methyl)

[0127] Step 1: Synthesis of 2-((hexyl(isobutyryloxycarbonyl)amino)methyl)benzoic acid

[0128] This derivative was synthesized according to the method described in step 2 of Example 8 of the invention, using 2-((hexamethylene)methyl)benzoic acid as the starting material and isobutyl chloroformate as the alkylating agent. The yield was 60%. 1 HNMR(400MHz, 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,arom.),8.0(m,1H,arom.).

[0129] Step 2: Synthesis of 2-((hexyl(isobutyryloxycarbonyl)amino)methyl)benzoate isobutyl ester

[0130] This derivative was prepared using 2-((hexyl(isobutyryloxycarbonyl)amino)methyl)benzoic acid as a starting material according to the synthetic method described in Example 9 of the invention. The yield was 93%, and the purity was 97% (GC). 1 HNMR(400MHz, 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,arom.),7.9(m,1H,arom.).

[0131] Example 11 of the Invention: Ethyl 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate

[0132] Step 1: Synthesis of 2-(((2-ethylhexyl)amino)methyl)benzoic acid

[0133] This derivative was prepared according to the synthesis described in step 1 of Example 1 of the invention, using (2-ethylhexylamine instead of an aqueous solution of methylamine. Yield: 50%. 1 HNMR(400MHz,D2O):0.6-0.9(m,6H,CH3+CH3),1.0-1.4(m,7H,CH(CH2)3),1.5(m,2 H,CH2),2.7(m,2H,CH2),4.1(m,2H,CH2),7.0-7.4(m,3H,arom.),8(m,1H,arom.).

[0134] Step 2: Synthesis of 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoic acid

[0135] This derivative was synthesized according to the method described in step 2 of Example 1 of the invention, using 2-(((2-ethylhexyl)amino)methyl)benzoic acid as the starting material. The yield was 75%. 1 HNMR(400MHz, 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,arom.),8.0(m,1H,arom.).

[0136] Step 3: Synthesis of ethyl 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate

[0137] This derivative was synthesized according to the method described in steps 1-3 of the present invention, using 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoic acid as the starting material. The yield was 90%, and the purity was 99% (GC). 1 HNMR(400MHz, 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,arom.),7.9(m,1H,arom.).

[0138] Example 12 of the Invention: Isobutyl 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate

[0139] Synthesis of 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate isobutyl ester

[0140] This derivative was prepared using isobutanol as a solvent according to the synthesis described in step 3 of Example 11 of the invention. Yield: 92%, purity: 98% (GC). 1 HNMR(400MHz, CDCl3):0.7(m,6H,CH3+CH3),0.9(d,6H,(CH3)2),1.0-1.6(m,12H,(CH2)3CHCH2CH3),2.0( m,1H,CH),3.1(m,2H,CH2),4.1(m,4H,2CH2),4.9(m,2H,CH2),7.1-7.4(m,3H,arom.),7.9(m,1H,arom.).

[0141] Example 13 of the Invention: Isobutyl 2-(((2-ethylhexyl)(isobutyryloxycarbonyl)amino)methyl)benzoate

[0142] Step 1: Synthesis of 2-(((2-ethylhexyl)(isobutyryloxycarbonyl)amino)methyl)benzoic acid

[0143] This derivative was prepared according to the synthesis described in step 1 of Example 10 of the invention, using 2-(((2-ethylhexyl)amino)methyl)benzoic acid as the starting material. The yield was 84%. 1 HNMR(400MHz, 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,arom.),8.0(m,1H,arom.).

[0144] Step 3: Synthesis of 2-(((2-ethylhexyl)(isobutyryloxycarbonyl)amino)methyl)benzoate isobutyl ester

[0145] This derivative was prepared using 2-(((2-ethylhexyl)(isobutyryloxycarbonyl)amino)methyl)benzoic acid as a starting material, according to the synthetic method described in Example 12 of the invention. The yield was 95%, and the purity was 97% (GC). 1HNMR(400MHz, 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,2H,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,arom.),7.9(m,1H,arom.).

[0146] Example 14 of the Invention: Ethyl 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoate

[0147] Step 1: Synthesis of 2-(((cyclohexylmethyl)amino)methyl)benzoic acid

[0148] This derivative was prepared according to the synthesis described in step 1 of Example 1 of the invention, using N-methylcyclohexylamine instead of aqueous methylamine. Yield: 100%. 1 HNMR(400MHz,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,arom.),8(m,1H,arom.).

[0149] Step 2: Synthesis of 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoic acid

[0150] This derivative was synthesized according to the method described in step 2 of Example 1 of the invention, using 22-(((cyclohexylmethyl)amino)methyl)benzoic acid as the starting material. The yield was 80%. 1 HNMR(400MHz, 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,arom.),7.9(m,1H,arom.).

[0151] Step 3: Synthesis of ethyl 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoate

[0152] This derivative was prepared according to the synthesis described in steps 1-3 of Examples of the Invention, using 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoic acid as the starting material. The final starting material was purified by gel permeation chromatography. Yield: 40%, purity: 95% (GC). 1 HNMR(400MHz, 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,arom.),7.9(m,1H,arom.).

[0153] Comparative Example 1: 2-((ethoxycarbonyl)(methyl)amino)ethyl benzoate

[0154] Step 1: Synthesis of ethyl 2-((ethoxycarbonyl)amino)benzoate

[0155] 250cm equipped with a magnetic stirrer 3 In a round-bottom flask, 5.0 g (30 mmol) of commercially available ethyl 2-aminobenzoate was added to a 5.1 cm flask. 3 Dissolve (36 mmol, 1.2 equivalents) of triethylamine together in 50 cm 3 In tetrahydrofuran. Then, 3.5 cm³ of the solution was added dropwise at 0°C. 3 (36 mmol, 1.2 equivalents) ethyl chloroformate was reacted, and the reaction was allowed to proceed 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 twice its volume of water and then evaporated to give the final product as a colorless oil. Yield: 90%. 1 HNMR(400MHz,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,arom.),7.6(m,2H,arom.),8.1(m,1H,arom.).

[0156] Step 2: Synthesis of ethyl 2-((ethoxycarbonyl)(methyl)amino)benzoate

[0157] 250cm 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 dissolved in a 50 cm³ solution. 3Add 0.8 g (30 mmol, 1.2 equivalents) of sodium hydride (powder, 90%) to tetrahydrofuran in small portions. Set the mixture to 30°C and add the sodium hydride dropwise at 1.9 cm⁻¹. 3 (30 mmol, 1.2 equivalents) of iodomethane was added and the mixture was stirred at 40 °C for 3 h. The mixture was then acidified with 1 M HCl and the product was extracted with ethyl acetate. The organic fraction was washed with twice its volume of water and then evaporated to give the final product as a colorless oil. Yield: 85%, Purity: 98%. 1 HNMR(400MHz,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,arom.),7.8-8.2(m,3H,arom.).

[0158] General procedure for preparing solid catalyst components

[0159] 250 cm under nitrogen atmosphere at room temperature 3 TiCl4 was introduced into a 500 cm³ container equipped with a mechanical stirrer, cooler, and thermometer. 3 In a round-bottom flask, after cooling to 0°C, while stirring, the internal donors listed in Table 1 and 10.0 g of the spherical adduct were added sequentially. The amount of internal donor added was such that the Mg / donor molar ratio was 6. The temperature was raised to 100°C and held for 2 hours. Afterward, 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 again to restore the initial liquid volume. The mixture was then heated at 120°C and held at that temperature for 1 hour. Stirring was stopped again, the solid was allowed to settle, and the supernatant was siphoned off. The solid was washed six times (6 times, 100 cm³ each time) with anhydrous hexane in a temperature gradient down to 60°C. 3 ), and wash once at room temperature (100cm). 3 The obtained solid was then dried under vacuum. Using the above procedure, the composition of the solid catalyst thus obtained was tested in propylene polymerization. The results are listed in Table 1.

[0160] Embodiments 1 to 14 of the Invention and Comparative Example 1

[0161] Preparation and polymerization of solid catalyst components

[0162] The general procedure for preparing solid catalyst components was performed using the donors reported in Table 1 as internal donors. The solid catalyst components thus obtained were tested in propylene polymerization using the above procedure. The results are listed in Table 1.

[0163] Table 1

[0164]

[0165]

[0166]

[0167] nd: Not determined

Claims

1. A catalyst component for olefin polymerization, said catalyst component comprising Mg, Ti and an electron donor of formula (II). (II) Where R 1 Groups and R 9 The groups may be the same or different from each other, and are selected from C1-C. 15 hydrocarbon group, R 2 The radical is selected from hydrogen or C1-C. 10 hydrocarbon group, R 3 and R 4 The groups are independently selected from hydrogen or C1-C. 15 Hydrocarbon groups, which can fuse together to form one or more rings; and R 10 They are independently selected from hydrogen, halogens, or C1-C. 10 alkyl.

2. The catalyst component according to claim 1, wherein R as defined above 1 To R 9 It may contain heteroatoms selected from halogens, P, S, N, O and Si.

3. The catalyst component according to claim 1, wherein R 1 and R 9 Independently for C1-C 10 alkyl.

4. The catalyst component according to claim 1, wherein R 1 and R 9 It is independently a C1-C8 alkyl group.

5. The catalyst component according to claim 1, wherein R 2 Selected from C1-C 10 alkyl.

6. The catalyst component according to claim 1, wherein R 2 Selected from C2-C 10 alkyl.

7. The catalyst component according to claim 1, wherein R 2 Selected from C2-C 10 Primary alkyl group.

8. The catalyst component according to claim 1, wherein R 3 and R 4 Independently selected from hydrogen or C1-C 10 alkyl.

9. The catalyst component according to claim 1, wherein R 3 and R 4 It is independently selected from hydrogen or C1-C8 alkyl.

10. The catalyst component according to claim 1, wherein R 3 and R 4 It is independently selected from hydrogen or straight-chain C1-C8 alkyl groups.

11. The catalyst component according to claim 9, wherein R 3 and R 4 Both are hydrogen.

12. The catalyst component according to claim 1, wherein R 5 To R 8 Independently selected from hydrogen or C1-C 20 Hydrocarbon group.

13. The catalyst component according to claim 12, wherein R 5 To R 8 Independently selected from hydrogen or C1-C 15 Hydrocarbon group.

14. The catalyst component according to claim 12, wherein R 5 To R 8 Independently selected from hydrogen or C1-C 10 Hydrocarbon group.

15. The catalyst component according to claim 12, wherein R 6 and R 7 They are connected together to form a ring structure, the ring structure having 3 to 10 carbon atoms forming the ring.

16. The catalyst component according to claim 15, wherein R 5 and R 8 Both are hydrogen.

17. The catalyst component according to claim 1, wherein R 10 It is independently selected from hydrogen, halogen, or C1-C8 alkyl.

18. The catalyst component according to claim 17, wherein R 1 and R 9 Independently for C1-C 10 Primary alkyl group, R 2 Selected from C2-C 10 Straight-chain alkyl, R 3 and R 4 Selected from hydrogen or C1-C 10 Alkyl, and R 10 The groups are independently selected from hydrogen, C1-C8 alkyl or halogen, provided that at least two of them are hydrogen.

19. A catalyst system for olefin polymerization, said catalyst system comprising reaction products between the following substances: (i) the catalyst component according to claim 1, and (ii) Alkyl aluminum compounds.

20. The catalyst system according to claim 19, wherein the catalyst system further comprises an external electron donor compound.

21. A method for the polymerization of olefins CH2=CHR, wherein R is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, said method being carried out in the presence of a catalyst system according to claim 19.

22. The method of claim 21, wherein the method for olefin polymerization is a method for olefin copolymerization.

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