Catalyst components for polymerization of olefins

Abstract

A solid catalyst component for the polymerization of olefins comprises Mg, Ti and an electron donor of formula (I) wherein R1 and R9 groups, equal to or different from each other, are selected from C1-C15 hydrocarbyl groups, R2 groups are selected from hydrogen or C1-C10 hydrocarbyl groups, R3 to R8 groups are independently selected from hydrogen or C1-C15 hydrocarbyl groups, which groups can be fused together to form one or more rings. A catalyst system based on the solid catalyst component has high activity and stereospecificity.

Description

Technical Field

[0001] The present disclosure relates to a catalyst component for the polymerization of olefins, particularly propylene, comprising a magnesium dihalide-based support on which Ti atoms are supported and an electron donor compound containing ester and carbamate functional groups. The present disclosure also relates to a catalyst obtained from the component and its use in a process for the polymerization of olefins, particularly propylene. Background Art

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

[0003] One of the problems associated with the use of this catalyst system is that phthalates have recently attracted some attention, leading to some compounds in this class being classified as a source of serious health problems.

[0004] Therefore, research activities are directed towards finding alternative classes of internal donors for the preparation of catalyst components for propylene polymerization.

[0005] Some tested catalysts contain donor structures with both carbamate and ester groups. PCT Publication WO2018 / 091375 describes 1,3-aminoester derivatives containing a carbamate group and a free ester functional group. The performance of these catalysts in terms of activity / stereospecificity balance is not entirely satisfactory, with improvements in stereospecificity being particularly needed. Summary of the Invention

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

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

[0008]

[0009] where R 1 Group and R 9 The groups are the same or different from each other and are selected from C1-C 15 Hydrocarbon, R 2 The group is selected from hydrogen or C1-C 10 Hydrocarbon, R 3 Group to R 8 Groups are independently selected from hydrogen or C1-C 15 Hydrocarbyl groups, these groups may be fused together to form one or more rings. DETAILED DESCRIPTION

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

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

[0012] Preferably, R 2 Selected from C1-C 10 Alkyl, more preferably selected from C2-C 10 Alkyl, and in particular 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 linear C1-C8 alkyl. According to a 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 Hydrocarbyl, more preferably hydrogen or C1-C 15 Hydrocarbyl, and in particular selected from hydrogen or C1-C 10 Hydrocarbon group.

[0015] According to a specific embodiment, R 6 and R 7 The ring structure is connected together to form a ring structure, and the ring structure has 3 to 10 carbon atoms forming a ring. Preferably, the ring structure has 5 to 6 carbon atoms forming a ring. The ring structure may have one or more carbon atoms selected from C1-C 10Hydrocarbyl, and preferably selected from C1-C 10 The alkyl group is more preferably a substituent selected from a C1-C8 alkyl group.

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

[0017] Particularly preferred are structures belonging to the following formula (II)

[0018]

[0019]

[0020] where R 1 to R 4 and R 9 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] Preferred structures of formula (II) are those wherein R 1 and R 9 Independently C1-C 10 Primary alkyl, R 2 Selected from C1-C 10 Straight or branched alkyl, R 3 and R 4 Selected from hydrogen or C1-C 10 Alkyl, and R 10 are independently selected from hydrogen, C1-C8 alkyl or halogen, provided that at least two of them are hydrogen.

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

[0023] Non-limiting examples of structures of formula (I) and or (II) are as follows:

[0024] 4-((methoxycarbonyl)amino)butyric acid methyl ester, 4-((methoxycarbonyl)(methyl)amino)3-methylbutyric acid methyl ester, 4-((cyclohexylmethyl)(methoxycarbonyl)amino)3-methylbutyric acid methyl ester, 4-(hexyl(methoxycarbonyl)amino)-3-methylpentanoic acid methyl ester, 4-(benzyl(methoxycarbonyl)amino)-3-methylpentanoic acid methyl ester, 4-(butyl(methoxycarbonyl)amino)-2,3-dimethylpentanoic acid methyl ester, 2-isopropyl-4-((methoxycarbonyl)(methyl)amino)-5-methylhexanoic acid methyl ester, 2-isopropyl-4-((hexyl(methoxycarbonyl)amino)-5-methylhexanoic acid methyl ester, 2-isopropyl-4-((cyclohexylmethyl)(methoxycarbonyl)amino)-5-methylhexanoic acid pentyl ester, 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, 4-(isopropyl(methoxycarbonyl)amino) Ethyl (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)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 4-(cyclohexyl(ethoxycarbonyl)amino)-3-methylpentanoate, Ethyl 4-(ethyl(ethoxycarbonyl)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)butyrate, Ethyl 4-(isobutyl(ethoxycarbonyl)amino)-2-methyl-5-phenylpentanoate, Isobutyl 4-(hexyl(ethoxycarbonyl)amino)butyrate, Isobutyl 4-((2-ethylhexyl)(ethoxycarbonyl)amino)-3-methylbutyrate,Isobutyl 2-((hexyl(isobutoxycarbonyl)amino)methyl)benzoate, isobutyl 4-((ethoxycarbonyl)(propyl)amino)-3-methylvalerate, isobutyl 4-((ethoxycarbonyl)amino)-2,3-dimethylvalerate, isobutyl 2-isopropyl-4-(cyclohexyl(ethoxycarbonyl)amino)-5-methylhexanoate, isobutyl 3-benzyl-4-(benzyl(ethoxycarbonyl)amino)butyrate, isobutyl 4-((cyclohexylmethyl)(ethoxycarbonyl)amino)-2-methyl-5-phenylvalerate, propyl 4-((isobutoxycarbonyl)amino)butyrate, propyl 4-((isobutoxycarbonyl)(methyl)amino)3-methylbutyrate, propyl 4-(ethyl(isobutoxycarbonyl)amino)-3-methylvalerate, propyl 4-((isobutoxycarbonyl)amino) propyl 2-isopropyl-4-(butyl(isobutoxycarbonyl)amino)-5-methylhexanoate, propyl 3-benzyl-4-(cyclohexyl(isobutoxycarbonyl)amino)butyrate, propyl 4-((2-ethylhexyl)(isobutoxycarbonyl)amino)-2-methyl-5-phenylpentanoate, propyl 4-((cyclohexylmethyl)(isobutoxycarbonyl)amino)-2-methyl-5-phenylpentanoate, isobutyl 4-(ethyl(isobutoxycarbonyl)amino)butyrate, isobutyl 4-((2-ethylhexyl)(isobutoxycarbonyl)amino)3-methylbutyrate, isobutyl 4-(benzyl(isobutoxycarbonyl)amino)-3-methylpentanoate, isobutyl 4-((cyclohexylmethyl)(isobutoxycarbonyl)amino)-2, Isobutyl 3-dimethylvalerate, isobutyl 2-isopropyl-4-((isobutoxycarbonyl)amino)-5-methylhexanoate, isobutyl 2-((butyl(ethoxycarbonyl)amino)methyl)benzoate, isobutyl 3-benzyl-4-(butyl(isobutoxycarbonyl)amino)butyrate, isobutyl 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)butyrate, 2-ethylhexyl-4-((cyclohexylmethyl)(butoxycarbonyl)amino)-2-methyl-5-phenylpentanoate, benzyl 4-((ethoxycarbonyl)amino)butyrate, decyl 4-(ethyl(ethoxycarbonyl)amino)-3-methylbutyrate, 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)butyrate, 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)ethyl)benzoate, methyl 2-(1-(isobutyl(methoxycarbonyl)amino)ethyl)benzoate, methyl 2-(1-benzyl(methoxycarbonyl)amino)ethyl)benzoate, methyl-((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, heptyl-5-(tert-butyl)-2-((isobutyl(methoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, ethyl-2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoate, ethyl-2-((hexyl(ethoxycarbonyl)amino)(phenyl)methyl)benzoate benzoate, ethyl 2-(((ethoxycarbonyl)amino)(phenyl)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 benzoate, ethyl 5-(tert-butyl)-2-((butyl(ethoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, ethyl 5-(tert-butyl)-2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, 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,Isobutyl 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)(hexyl)amino)methyl benzoate, 2-ethylhexyl-2-((cyclohexyl(ethoxycarbonyl)amino)(phenyl)methyl)benzoate, isoamyl 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, 2-((isobutyl(ethoxycarbonyl)amino)(phenyl)methyl benzoate, 2-ethylhexyl-5-(tert-butyl)-2-(((ethoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, 2-ethylhexyl-5-(tert-butyl)-2-(((ethoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, ethyl 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoate, 2-ethylhexyl-5-(tert-butyl)-2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, 2-ethylhexyl-5-(tert-butyl)-2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)(phenyl)methyl)-3-methylbenzoate, isobutyl ester, 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)propionate, ethyl 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoate, methyl 2-(2-(hexyl(ethoxycarbonyl)amino)phenyl)-2-methylpropionate, methyl 2-(2-(cyclohexyl(methoxycarbonyl)amino)phenyl)-2-phenylacetate, methyl 2-(4-chlorophenyl)-2-(2-(ethyl(methoxycarbonyl)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, ethyl 2-(2-((ethoxycarbonyl)amino)phenyl)acetate, Benzyl (isobutyl (ethoxycarbonyl) amino) phenyl) propionate, pentyl 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, isobutyl 2-(2-((isobutoxycarbonyl) (methyl) amino) phenyl) acetate, isobutyl 2-(2-(cyclohexyl (isobutoxycarbonyl) amino) phenyl) acetate, isobutyl 2-(2-(hexyl(isobutoxycarbonyl)amino)phenyl)propionate, isobutyl 2-(2-(hexyl(isobutoxycarbonyl)amino)phenyl)-2-methylpropionate, isobutyl 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate, isobutyl 2-(2-((2-ethylhexyl)(isobutoxycarbonyl)amino)phenyl)-2-methylpropionate, 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 (5-(tert-butyl)-2-(isopropyl(isobutoxycarbonyl)amino)-3-methylphenyl)-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-ethylhexyl-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-phenyl acetate, 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-((cyclohexylmethyl)(butoxycarbonyl)amino)-3-methylphenyl)-2-(4-chlorophenyl) acetate.

[0025] Compounds of formula (I) can generally be prepared using the following synthetic routes.

[0026] Commercially available amino acids can be converted to ((alkoxy)carbonyl)amino acids using alkyl chloroformates, and the acid moiety treated under Fischer conditions in an appropriate alcohol to yield 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 a suitable primary amine and a borohydride reducing agent.

[0027] In the solid catalyst component of the present disclosure, the amount of Ti atoms is preferably higher than 2.5% wt, more preferably higher than 3.0%, relative to the total weight of the catalyst component.

[0028] As explained above, in addition to the above-mentioned electron donor, the catalyst component of the present disclosure also includes Ti, Mg and halogen. In particular, the catalyst component includes a titanium compound having at least a Ti-halogen bond and the above-mentioned electron donor compound supported on a magnesium halide. The magnesium halide is preferably MgCl2 in active form, which is widely known in the patent literature as a carrier 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. From these patents, it is known that the active form of magnesium dihalide used as a carrier or co-carrier in the components of catalysts for olefin polymerization is characterized by an X-ray spectrum in which the intensity of the strongest diffraction line appearing in the spectrum of the inactive halide is reduced and replaced by a halogen whose maximum intensity is shifted to a lower angle relative to a stronger line.

[0029] The preferred titanium compounds used in the catalyst components of the present disclosure are TiCl4 and TiCl3; in addition, compounds of the formula Ti(OR 11 ) m-y X y Ti-haloalcoholates, wherein m is the valence of titanium, y is a number between 1 and m-1, X is a halogen, and R11 is a hydrocarbon group having 1 to 10 carbon atoms.

[0030] The solid catalyst component can be prepared according to several methods. One method comprises reacting a magnesium alkoxide or chloroalkoxide (especially 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 obtained by making the formula Ti(OR 11 ) m-y X y (wherein m is the valence of titanium and y is a number between 1 and m, preferably TiCl4) and a titanium compound derived from the formula MgCl2·pR 12 OH (wherein p is a number between 0.1 and 6, preferably 2 to 3.5, and R 12 The adduct is prepared by reacting an alcohol with magnesium chloride (a hydrocarbon radical having 1 to 18 carbon atoms). The adduct can be suitably prepared in spherical form by mixing the alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100 to 130°C). The emulsion is then rapidly quenched, causing the adduct to solidify in the form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648. The adduct thus obtained can be reacted directly with the Ti compound, or it can be previously subjected to a thermally controlled dealcoholation (80 to 130°C) to obtain an adduct in which the number of moles of alcohol is less than 3, preferably between 0.1 and 2.5. The reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as is) in cold TiCl4 (about 0°C); heating the mixture to 80 to 130°C and maintaining it at this temperature for 0.5 to 2 hours. The treatment with TiCl4 can be carried out once or several times. The electron donor compound is preferably added during the treatment with TiCl4. For example, the preparation of spherical catalyst components is described in European patent applications EP-A-395083, EP-A-553805, EP-A-553806, EPA 601525 and WO 98 / 44009.

[0032] The solid catalyst component obtained according to the above method shows a surface area (by BET method) between 20 and 500 m 2 / g, and preferably between 50 and 400m 2 / g, and the total porosity (by BET method) is higher than 0.2 cm 3 / g, preferably between 0.2 and 0.6 cm 3 / g. From radius to The porosity caused by the pores (mercury method) can be from 0.3 to 1.5 cm 3 / g, preferably from 0.45 to 1 cm 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 can be added directly or, alternatively, can be obtained in situ by using appropriate precursors which can be converted to the desired electron donor compound by, for example, available chemical reactions.

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

[0036] In addition to the above-mentioned donors, the solid catalyst component may further contain an additional donor. Although there is no limitation on the type of the additional donor, it may be selected from esters, ethers, carbamates, thioesters, amides and ketones.

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

[0038]

[0039]

[0040] where R I and R II The same or different and hydrogen or a straight or branched C1-C 18 Hydrocarbon; R III The groups, identical or different from each other, are hydrogen or C1-C 18 Hydrocarbon; R IV The groups are the same or different from each other and have the same III Same meaning, except they cannot be hydrogen; R I to R IV Each of the groups may contain heteroatoms selected from halogen, N, O, S and Si.

[0041] Preferably, R IV is an alkyl group having 1 to 6 carbon atoms, more particularly a methyl group, and R III The group is preferably hydrogen. In addition, 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 R may be ethyl, butyl, sec-butyl, tert-butyl, 2-ethylhexyl, cyclohexylethyl, diphenylmethyl, p-chlorophenyl, 1-naphthyl, 1-decalinyl; I and R II They may also be the same and may be ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, phenyl, benzyl, cyclohexyl, or cyclopentyl.

[0042] Especially preferred are compounds of formula (V):

[0043]

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

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

[0046] In particular, the present disclosure is directed to a catalyst for the polymerization of olefins CH2=CHR, wherein R is hydrogen or a hydrocarbon radical having 1 to 12 carbon atoms, comprising the product obtained by contacting:

[0047] (i) a solid catalyst component as disclosed above, and

[0048] (ii) an alkylaluminum compound, 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, tri-n-octylaluminum. It is also possible (possibly in the form of a mixture with the above-mentioned trialkylaluminums) to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt2Cl and Al2Et3Cl3.

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

[0052] Another preferred class of external donor compounds is that of formula (R 13 ) a (R 14 ) b Si(OR 15 ) c A silicon compound wherein a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4; R 13 、R 14 and R 15 is a group having 1 to 18 carbon atoms which may optionally contain heteroatoms. Particularly preferred are silicon compounds wherein a is 1, b is 1, c is 2, R 13 and R 14 At least one of is selected from a branched alkyl group, a cycloalkyl group or an aryl group having 3 to 10 carbon atoms which may contain a heteroatom, and R 15 It is C1-C 10 Alkyl, in particular methyl. 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, N,N-diethylaminotriethoxysilane. In addition, preferred are those wherein a is 0, c is 3, and R 14 is a branched alkyl or cycloalkyl group optionally containing heteroatoms and R 15 Examples of preferred silicon compounds of this type are cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, and tert-hexyltrimethoxysilane.

[0053] The electron donor compound (iii) is used in such an amount that the molar ratio between the organoaluminum compound and said 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 the present disclosure, in particular when used in propylene polymerization in combination with an alkylaluminum compound and an alkylalkoxysilane, are capable of producing polypropylene under the polymerization conditions described in the experimental section with an activity higher than 50 kg / gcat, preferably higher than 55 kg / gcat, and a xylene insolubility at 25° C. higher than 96.0% wt, preferably higher than 96.5% wt, and more preferably higher than 97.0% wt.

[0055] Therefore, another object of the present disclosure is formed as follows: a process for the (co)polymerization of olefins CH2=CHR, wherein R is hydrogen or a hydrocarbon radical having 1 to 12 carbon atoms, the process being carried out in the presence of a catalyst comprising the reaction product between:

[0056] (i) a solid catalyst component of the present disclosure;

[0057] (ii) an alkylaluminum compound, and

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

[0059] The polymerization process can be carried out according to available technology, for example slurry polymerization using an inert hydrocarbon solvent as a diluent, or bulk polymerization using a liquid monomer (e.g. propylene) as a reaction medium. Additionally, the polymerization process can be carried out in the gas phase operating in one or more fluidized bed or mechanically stirred bed reactors.

[0060] The polymerization can be carried out at a temperature of from 20 to 120° C., preferably from 40 to 80° C. When the 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 examples are given to further illustrate the present disclosure but are not intended to limit the present disclosure.

[0062] Characterization

[0063] Determination 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 reflux condenser and maintained under nitrogen. The resulting mixture was heated to 135°C and maintained under stirring for approximately 60 minutes. The resulting solution was allowed to cool to 25°C under continuous stirring, and the insoluble polymer was then filtered. The filtrate was then evaporated at 140°C under a stream of nitrogen to a constant weight. The content of the xylene-soluble fraction was expressed as a percentage of the original 2.5 g and then expressed as 11% by difference.

[0065] Determination of donor.

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

[0067] Melt flow rate (MFR)

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

[0069] Example

[0070] Procedure for the preparation of spherical adducts

[0071] An initial amount of MgCl2.2.8C2H5OH adduct was prepared according to the method described in Example 2 of WO 98 / 44009, but operated 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 stream of nitrogen at 70°C for 1 hour. Then, at 30°C, under a stream of propylene, 75 mL of anhydrous hexane, 0.76 g of AlEt3, dicyclopentyldimethoxysilane as an external electron donor (to give an Al / donor molar ratio of 20), and 0.006÷0.010 g of a solid catalyst component were added in sequence. The autoclave was closed; 2.0 NL of hydrogen was subsequently added. Then, with stirring, 1.2 kg of liquid propylene was added. The temperature was raised to 70°C over 5 minutes, and polymerization was carried out at this temperature for 2 hours. At the end of the polymerization, unreacted propylene was removed; the polymer was recovered and dried under vacuum at 70°C for 3 hours. The polymer was then weighed and fractionated with o-xylene to determine the amount of the xylene-insoluble (XI) fraction.

[0074] General procedure for preparing internal donors

[0075] Inventive Example 1: Ethyl 2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoate

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

[0077] In a 250 cm 3 In a round-bottom flask, 5.0 g (33 mmol) of commercially available 2-formylbenzoic acid was dissolved in 50 cm 3Methanol, and 5.8 cm 3 (66 mmol, 2 equivalents) of methylamine in water (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 react 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(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] In a 250 cm 3 In a round-bottom flask, 5.5 g (33 mmol) of 2-((methylamino)methyl)benzoic acid was dissolved in 20 cm 3 NaOH aqueous 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 reaction 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. The yield was 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] In a 250 cm 3 In a round-bottom flask, 5.2 g (0.22 mmol) of 2-(((ethoxycarbonyl)(methyl)amino)methyl)benzoic acid and 1 cm 3 Sulfuric acid dissolved in 50cm 3 The mixture was refluxed for 5 hours, and then the solvent was removed. The crude product was dissolved in ethyl acetate and washed with aqueous sodium bicarbonate. After removal of the solvent, the final product was obtained as a colorless oil. The yield was 80%, and the purity was 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] Inventive Example 2: 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 Inventive Example 1 - Step 1, using 2M ethylamine in THF instead of aqueous 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 Inventive Example 1 - Step 2, using 2-((ethylamino)methyl)benzoic acid as the starting material. Yield: 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 prepared according to the synthesis described in Inventive Example 1-Step 3, using 2-(((ethoxycarbonyl)(ethyl)amino)methyl)benzoic acid as the starting material. Yield: 90%, purity: 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] Inventive Example 3: 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 Inventive Example 1-Step 1, using n-propylamine instead of aqueous methylamine solution. 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 Inventive Example 1 - Step 2, using 2-((propylamino)methyl)benzoic acid as the starting material. Yield: 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: Synthesis of ethyl 2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoate

[0095] This derivative was prepared according to the synthesis described in Inventive Example 1 - Step 3, using 2-(((ethoxycarbonyl)(propyl)amino)methyl)benzoic acid as the starting material. Yield: 84%, purity: 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] Inventive Example 4: 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 Inventive Example 1-Step 1, using n-butylamine instead of aqueous methylamine solution. 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 Inventive Example 1 - Step 2, using 2-((butylamino)methyl)benzoic acid as the starting material. Yield: 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 prepared according to the synthesis described in Inventive Example 1 - Step 3, using 2-((butyl(ethoxycarbonyl)amino)methyl)benzoic acid as the starting material. Yield: 89%, purity: 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] Inventive Example 5: Isobutyl 2-((Butyl(ethoxycarbonyl)amino)methyl)benzoate

[0104] Synthesis of Isobutyl 2-((Butyl(ethoxycarbonyl)amino)methyl)benzoate

[0105] This derivative was prepared according to the synthesis described in Inventive Example 4 - Step 3, using isobutanol as solvent, with a yield of 90% and a purity of 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] Inventive Example 6: 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 Inventive Example 4 - Step 3, using 2-(2-ethylhexyloxy)ethanol as 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] Inventive Example 7: 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 Inventive Example 1 - Step 1, using isobutylamine instead of aqueous methylamine solution. 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 Inventive Example 1 - Step 2, using 2-((isobutylamino)methyl)benzoic acid as the starting material. Yield: 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 prepared according to the synthesis described in Inventive Example 1 - Step 3, using 2-(((ethoxycarbonyl)(isobutyl)amino)methyl)benzoic acid as the starting material. Yield: 87%, purity: 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] Inventive Example 8: Ethyl 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate

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

[0118] This derivative was prepared according to the synthesis described in Inventive Example 1-Step 1, using n-hexylamine instead of aqueous methylamine solution. The yield was 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 Inventive Example 1 - Step 2, using 2-((hexylamino)methyl)benzoic acid as the starting material. Yield: 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: Synthesis of ethyl 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoate

[0122] This derivative was prepared according to the synthesis described in Inventive Example 1 - Step 3, using 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoic acid as the starting material. Yield: 94%, purity: 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] Inventive Example 9: Isobutyl 2-(((Ethoxycarbonyl)(hexyl)amino)methyl)benzoate

[0124] Synthesis of Isobutyl 2-(((Ethoxycarbonyl)(hexyl)amino)methyl)benzoate

[0125] This derivative was prepared according to the synthesis described in Inventive Example 8 - Step 3, using 2-(((ethoxycarbonyl)(hexyl)amino)methyl)benzoic acid as the starting material and isobutanol as the solvent. Yield: 83%, purity: 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] Inventive Example 10: Isobutyl 2-((Hexyl(isobutoxycarbonyl)amino)methyl)

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

[0128] This derivative was prepared according to the synthesis described in Inventive Example 8 - Step 2, using 2-((hexylamino)methyl)benzoic acid as the starting material and isobutyl chloroformate as the alkylating agent. Yield: 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 isobutyl 2-((hexyl(isobutoxycarbonyl)amino)methyl)benzoate

[0130] This derivative was prepared according to the synthetic method described in Inventive Example 9 using 2-((hexyl(isobutoxycarbonyl)amino)methyl)benzoic acid as the starting material. 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] Inventive Example 11: 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 Inventive Example 1 - Step 1, using (2-ethyl)hexylamine instead of aqueous methylamine solution. 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 prepared according to the synthesis described in Inventive Example 1 - Step 2, using 2-(((2-ethylhexyl)amino)methyl)benzoic acid as the starting material. Yield: 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 prepared according to the synthesis described in Inventive Example 1 - Step 3, using 2-(((ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoic acid as the starting material. Yield: 90%, purity: 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] Inventive Example 12: Isobutyl 2-(((Ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate

[0139] Synthesis of Isobutyl 2-(((Ethoxycarbonyl)(2-ethylhexyl)amino)methyl)benzoate

[0140] This derivative was prepared according to the synthesis described in Inventive Example 11 - Step 3, using isobutanol as solvent, with a yield of 92% and a purity of 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] Inventive Example 13: Isobutyl 2-(((2-ethylhexyl)(isobutoxycarbonyl)amino)methyl)benzoate

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

[0143] This derivative was prepared according to the synthesis described in Inventive Example 10 - Step 1, using 2-(((2-ethylhexyl)amino)methyl)benzoic acid as the starting material. Yield: 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 isobutyl 2-(((2-ethylhexyl)(isobutoxycarbonyl)amino)methyl)benzoate

[0145] This derivative was prepared according to the synthetic method described in Inventive Example 12 using 2-(((2-ethylhexyl)(isobutoxycarbonyl)amino)methyl)benzoic acid as the starting material. 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] Inventive Example 14: 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 Inventive Example 1 - Step 1, using N-methylcyclohexylamine instead of aqueous methylamine solution. 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 prepared according to the synthesis described in Inventive Example 1 - Step 2, using 22-(((cyclohexylmethyl)amino)methyl)benzoic acid as the starting material. Yield: 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 Inventive Example 1, Step 3, using 2-(((cyclohexylmethyl)(ethoxycarbonyl)amino)methyl)benzoic acid as the starting material. The final material was purified by gel chromatography. The yield was 40% and the purity was 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: Ethyl 2-((ethoxycarbonyl)(methyl)amino)benzoate

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

[0155] In a 250 cm 3 In a round-bottom flask, 5.0 g (30 mmol) of commercially available ethyl 2-aminobenzoate and 5.1 cm 3 (36 mmol, 1.2 equivalents) triethylamine were dissolved in 50 cm 3 Then, 3.5 cm 3 (36 mmol, 1.2 equivalents) of ethyl chloroformate were added, and the reaction was allowed to react 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 then evaporated to give the final product as a colorless oil. The yield was 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] In a 250 cm 3 In a round-bottom flask, under nitrogen atmosphere, 6.0 g (25 mmol) of ethyl 2-((ethoxycarbonyl)amino)benzoate was dissolved in 50 cm 3The mixture was heated to 30 °C and 1.9 cm 3 (30 mmol, 1.2 equivalents) of iodomethane and stirred at 40 ° C for 3 hours. Subsequently, the mixture was acidified with 1M 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. The yield was 85% and the purity was 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] Under nitrogen atmosphere, 250 cm 3 TiCl4 was introduced into a 500 cm2 flask equipped with a mechanical stirrer, a cooler, and a thermometer. 3 round-bottom flask. After cooling to 0°C, the internal donors listed in Table 1 and 10.0 g of spherical adducts were added to the flask in sequence while stirring. The amount of internal donor added was such that the molar ratio of Mg / donor was 6. The temperature was raised to 100°C and maintained for 2 hours. Thereafter, stirring was stopped, the solid product was allowed to settle and the supernatant was siphoned off at 100°C. After removing the supernatant, additional fresh TiCl4 was added to reach the initial liquid volume again. The mixture was then heated at 120°C and maintained at this temperature for 1 hour. Stirring was again stopped, the solid was allowed to settle and the supernatant was siphoned off. The solid was washed six times with anhydrous hexane in a temperature gradient down to 60°C (6 times, 100 cm3 each time). 3 ) and washed once at room temperature (100 cm 3 The solid obtained was then dried under vacuum. The solid catalyst component thus obtained was tested in propylene polymerization using the above procedure. The results are listed in Table 1.

[0160] Inventive Examples 1 to 14 and Comparative Example 1

[0161] Preparation and polymerization of solid catalyst components

[0162] The general procedure for the preparation of the solid catalyst component was carried out using as internal donor the donors reported in Table 1. The solid catalyst component thus obtained was 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, comprising Mg, Ti and an electron donor of formula (I) where R 1 Group and R 9 The groups are the same or different from each other and are selected from C1-C 15 Hydrocarbon, R 2 The group is selected from hydrogen or C1-C 10 Hydrocarbon, R 3 Group to R 8 Groups are independently selected from hydrogen or C1-C 15 Hydrocarbyl groups, these groups may be fused together to form one or more rings.

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

3. The catalyst component according to any one of the preceding claims, wherein R 1 and R 9 Independently C1-C 10 Alkyl, more preferably C1-C8 alkyl.

4. The catalyst component according to any one of the preceding claims, wherein R 2 Selected from C1-C 10 Alkyl, more preferably selected from C2-C 10 Alkyl, and in particular selected from C2-C 10 Primary alkyl group.

5. The catalyst component according to any one of the preceding claims, wherein 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 linear C1-C8 alkyl.

6. The catalyst component according to claim 5, wherein R 3 and R 4 Both are hydrogen.

7. The catalyst component according to any one of the preceding claims, wherein R 5 to R 8 independently selected from hydrogen or C1-C 20 Hydrocarbon group.

8. The catalyst component according to claim 7, wherein R 5 to R 8 independently selected from hydrogen or C1-C 15 Hydrocarbyl, and in particular selected from hydrogen or C1-C 10 Hydrocarbon group.

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

10. The catalyst component according to claim 9, wherein R 5 and R 8 Both are hydrogen.

11. The catalyst component according to any one of the preceding claims, wherein the electron donor is selected from those belonging to formula (II) where R 1 to R 4 and R 9 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.

12. The catalyst component according to claim 11, wherein R 1 and R 9 Independently C1-C 10 Primary alkyl, 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.

13. A catalyst system for olefin polymerization, comprising the reaction product of: (i) a solid catalyst component according to any one of the preceding claims, and (ii) Alkyl aluminum compounds.

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

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

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