catalyst component

Abstract

The present invention relates to components useful in propylene polymerization catalysts, and more particularly to a solid, hydrocarbon-insoluble catalyst component containing magnesium, titanium, and a halogen, and further comprising a modifier compound having the following structure (1): 1 is selected from H, an aryl group or an alkyl group having 1 to 10 carbon atoms, and R 2 is selected from alkyl groups having 1 to 10 carbon atoms, and R 3 ~R 6 are each independently selected from H, an alkylaryl group, an aryl group, or an alkyl group having 1 to 10 carbon atoms, and a halogen, with the proviso that R 4 and R 5 at least one of is H, and any alkylaryl, aryl, or alkyl group may contain one or more heteroatoms, and / or R 3 and R 4 or R 5 and R 6 may be bonded to form a cyclic group) JPEG2025538763000009.jpg51150

Description

[Technical Field]

[0001] This invention relates to components useful in catalysts, and in particular to modifier components used in combination with magnesium-containing supported titanium-containing catalyst components. [Background technology]

[0002] The use of solid transition metal-based olefin polymerization catalyst components is well known in the art, including such solid components supported on metal oxides, halides, or other salts, such as the broadly described magnesium-containing titanium halide-based catalyst components. While many polymerization and copolymerization processes and catalyst systems for polymerizing or copolymerizing alpha-olefins have been described, it is advantageous to tailor the process and catalyst system to obtain a specific set of properties for the resulting polymer or copolymer product. For example, certain applications require a combination of high activity, good morphology, a desired particle size distribution, acceptable bulk density, etc., along with polymer properties such as stereospecificity and molecular weight distribution. Typically, supported catalyst components useful for polymerizing propylene and higher alpha-olefins, and for polymerizing propylene and higher olefins with small amounts of ethylene and other alpha-olefins, contain an electron donor component as an internal modifier. Such internal modifiers are an integral part of the solid supported component and are distinct from any external electron donor component, which may comprise a catalyst system together with an alkylaluminum component. Typically, a cocatalyst such as an alkylaluminum and any external electron donor are combined with the solid catalyst component, either immediately before contacting the combination with an olefin monomer or in the presence of the olefin monomer.

[0003] The selection of internal modifiers and other electron donor components can affect catalyst performance and the resulting polymer. Numerous organic electron donors have been described as useful in the preparation of stereospecific supported catalyst components, including organic compounds containing oxygen, nitrogen, sulfur, and / or phosphorus. Such compounds include organic acids, organic acid anhydrides, organic acid esters, alcohols, ethers, aldehydes, ketones, amines, amine oxides, amides, thiols, various phosphate esters and amides, and the like. Mixtures of organic electron donors have been described as useful for incorporation into supported catalyst components. Specific examples of organic electron donors commonly used as internal modifiers include alkyl phthalates, dicarboxylic acid esters such as succinates, and other bidentate donors such as diethers. It is also known that the external donor component of the catalyst can contain several components in addition to the cocatalyst. For example, WO2005 / 30815 and WO2009 / 85649 describe propylene polymerization catalysts that contain one or more aluminum-containing cocatalysts in addition to a combination of external donors, in particular a combination of at least one alkoxysilane referred to as a "selectivity control agent" (SCA) and at least one aliphatic or alicyclic mono- or polycarboxylic acid or its ester derivative referred to as an "activity limiting agent" (ALA).

[0004] Furthermore, numerous individual process steps or methods for producing improved magnesium- and titanium-containing electron donor-containing supported olefin polymerization or copolymerization catalysts have been disclosed. For example, U.S. Pat. No. 4,866,022 discloses a method for forming an advantageous α-olefin polymerization or copolymerization catalyst or catalyst component involving a specific series of individual process steps. U.S. Pat. No. 4,540,679 discloses a method for preparing magnesium hydrocarbyl carbonate by reacting a suspension of magnesium alcoholate in alcohol with carbon dioxide and reacting the magnesium hydrocarbyl carbonate with a transition metal component. U.S. Pat. No. 4,612,299 discloses a method for preparing magnesium carboxylate by reacting a solution of a hydrocarbyl magnesium compound with carbon dioxide to precipitate a magnesium carboxylate, which is then reacted with a transition metal component. The specific uses of the polymers that can be produced depend on the molecular weight, viscosity, stiffness, flexural modulus, and polydispersity index (Molecular weight distribution (M w / M n In addition, the polymer or copolymer morphology usually depends on the catalyst morphology. Summary of the Invention

[0005] The present invention relates to catalyst components and catalysts, particularly catalyst components and catalysts containing novel modifier components. Thus, in a first aspect, the present invention provides a solid, hydrocarbon-insoluble catalyst component containing magnesium, titanium, and a halogen, further comprising a modifier compound having the following structure (1):

[0006] [ka] (In the formula, R 1 is selected from H, an aryl group or an alkyl group having 1 to 10 carbon atoms; R 2 is selected from alkyl groups having 1 to 10 carbon atoms; R 3 ~R6 are each independently selected from H, an alkylaryl group, an aryl group, or an alkyl group having 1 to 10 carbon atoms, and a halogen, with the proviso that R 4 and R 5 at least one of is H, Any alkylaryl, aryl, or alkyl group may contain one or more heteroatoms, and / or R 3 and R 4 or R 5 and R 6 may be bonded to form a cyclic group)

[0007] The catalyst component is particularly useful as a catalyst for the polymerization of olefins in combination with a cocatalyst. Thus, in a second aspect, the present invention also provides a catalyst useful in the polymerization of olefins, comprising: (i) a solid, hydrocarbon-insoluble catalyst component containing magnesium, titanium, and a halogen, and further comprising a modifier compound having the following structure (1):

[0008] [ka] (In the formula, R 1 is selected from H, an aryl group or an alkyl group having 1 to 10 carbon atoms; R 2 is selected from alkyl groups having 1 to 10 carbon atoms; R 3 ~R 6 are each independently selected from H, an alkylaryl group, an aryl group, or an alkyl group having 1 to 10 carbon atoms, and a halogen, with the proviso that R 4 and R 5 at least one of is H, Any alkylaryl, aryl, or alkyl group may contain one or more heteroatoms, and / or R 3 and R 4 or R 5 and R 6 may be bonded to form a cyclic group), and (ii) at least one cocatalyst component; Also provided is a catalyst comprising:

[0009] For the avoidance of doubt, the modifier is, and may also be considered to be, an electron donor compound. Although the claimed modifier may be used as an external electron donor in the first and second aspects of the invention, in preferred embodiments it is used as an internal electron donor, or specifically an "internal modifier". DETAILED DESCRIPTION OF THE INVENTION

[0010] (As used herein, the term "modifier" is used as a shorthand to refer to a modifier compound of structure (1), and the terms "modifier" and "modifier compound" can be used interchangeably. The term "modifier" is used herein to clearly distinguish the modifier of structure (1) from other electron donors that may appear in any aspect or embodiment.) The terms "internal" and "external" as used in this context are well understood in the art. Generally, and as used herein, the term "internal," when used with respect to a modifier (or other electron donor), refers to a compound that is an integral part of the solid supported catalyst component. Typically, this is accomplished by adding the internal modifier (or other electron donor) during catalyst preparation. In contrast, the term "external," when used with respect to a modifier (or other electron donor), refers to a compound that is combined with other portions of the solid catalyst component just prior to contacting the combination with an olefin monomer, or a compound that is combined with other portions of the solid catalyst component in the presence of an olefin monomer, for example, in a reactor.

[0011] In the present invention, R 1 is selected from H (hydrogen), an aryl group or an alkyl group having 1 to 10 carbon atoms, R 2 is selected from alkyl groups having 1 to 10 carbon atoms; R 3 ~R6 are each independently selected from H (hydrogen), an alkylaryl group, an aryl group, or an alkyl group having 1 to 10 carbon atoms, and a halogen, with the proviso that R 4 and R 5 At least one of is H. Any alkylaryl, aryl, or alkyl group present may contain one or more heteroatoms. 3 and R 4 may be bonded to form a cyclic group. 5 and R 6 may be linked to form a cyclic group.

[0012] R 1 is selected from hydrogen, an aryl group or an alkyl group having 1 to 10 carbon atoms. 1 Preferably, R does not contain a heteroatom. 1 is R 2 ~R 6 It is also preferred that none of R is bonded to form a cyclic group (i.e., not bonded to any other group other than that shown in structure (1)). 1 is preferably selected from hydrogen, aryl groups or alkyl groups having 1 to 6 carbon atoms. 1 When R is an aryl group, it is preferably a phenyl group. 1 More preferably, R is selected from hydrogen and alkyl groups having 1 to 6 carbon atoms. 1 is selected from hydrogen, methyl, ethyl, and propyl, for example, hydrogen and methyl. 1 Most preferably, is hydrogen. R 2 is selected from alkyl groups having 1 to 10 carbon atoms. 2 Preferably, R does not contain heteroatoms. 2 is R 1 and R 3 ~R 6 It is also preferred that none of R is bonded to form a cyclic group (i.e., not bonded to any other group other than that shown in structure (1)). 2is preferably selected from alkyl groups having 1 to 6 carbon atoms. 2 is selected from methyl, ethyl, propyl, and butyl, with methyl, ethyl, and butyl being most preferred.

[0013] R 3 ~R 6 are each independently selected from hydrogen, an alkylaryl group, an aryl group, or an alkyl group having 1 to 10 carbon atoms, and halogen, with the proviso that R 4 and R 5 At least one of R is H. R is an alkylaryl group, an aryl group, or an alkyl group having 1 to 10 carbon atoms. 3 ~R 6 Preferably, none of R 3 ~R 6 does not contain heteroatoms if it is not itself a halogen). 3 and R 4 may be bonded to form a cyclic group. 5 and R 6 may be bonded to form a cyclic group. (R 4 and R 5 is H, so in the same structure, R 3 and R 4 If and combine to form a cyclic group, R 5 should be H, and R 5 and R 6 It should be noted that cannot be linked to form a cyclic group, and vice versa. In the first embodiment, R 3 ~R 6 are each hydrogen. In three particularly preferred structures according to this embodiment, R 1 is also hydrogen, and R 2 Each is an alkyl selected from methyl, ethyl, or butyl. In further preferred structures according to this embodiment, R 1 and R 2 are both methyl. In a further preferred structure according to this embodiment, R 1 is phenyl and R 2is methyl.

[0014] In the second embodiment, R 3 ~R 6 At least one of R is halogen. 5 is a halogen, most preferably bromine (in which case R 4 (It will be clear that R must be H.) In the preferred structure, R 5 is a halogen, most preferably bromine, while R 3 , R 4 , and R 6 Each of R is hydrogen. Most preferably, R 1 is hydrogen and R 2 is methyl and R 3 , R 4 , and R 6 are each hydrogen, and R 5 is a halogen, most preferably bromine in particularly preferred structures according to this embodiment. In the third embodiment, R 3 ~R 6 At least one of R is alkyl, preferably alkyl having 1 to 6 carbon atoms. 3 ~R 6 It is possible that at least one of R can be halogen. However, this is not preferred. Preferably, R 3 ~R 6 At least two of R are hydrogen, i.e., R 3 ~R 6 At most two of R are alkyl. 3 and R 5 In particularly preferred structures according to this option, at least one of R 1 is hydrogen and R 2 is methyl and R 3 and R 5 is tert-butyl, and R 4 and R 6 are each hydrogen. In another preferred option, at least R 6 is alkyl. In particularly preferred structures according to this option, R1 is hydrogen and R 2 is butyl and R 3 ~R 5 are each hydrogen, and R 6 is methyl.

[0015] As already mentioned, R 3 and R 4 or R 5 and R 6 may be linked to form a cyclic group. In some preferred embodiments disclosed above, R 3 and R 4 do not bond to form a cyclic group, and R 5 and R 6 do not join to form a cyclic group. In these embodiments, R 1 ~R 6 Among them is R 1 ~R 6 It is more generally preferred that none of the aromatic rings in structure (1) are attached to any other ring to form a cyclic group (i.e., no cyclic groups are present other than the aromatic rings in structure (1)). When cyclic groups (other than the aromatic rings of structure (1)) are present, they are most preferably R 3 and R 4 and bond to form the cyclic group. In this case, R 5 is H. In this case, R 1 , R 2 , and R 6 Among them is R 1 , R 2 , and R 6 does not bind to any other of R 3 and R 4 It is also preferred that there is no bond to the group formed by (i.e., there are no further cyclic groups).

[0016] In this embodiment, the following structure (2) is particularly preferred. [ka] (In the formula, R 1 , R 2 , and R 6is as already defined, R 5 is H, R 7 ~R 10 are each independently selected from H, alkylaryl, aryl, or alkyl groups having 1 to 6 carbon atoms, and halogen, and the alkylaryl, aryl, and alkyl groups may contain one or more heteroatoms. R 1 , R 2 , and R 6 is preferably as defined above for structure (1).

[0017] R 7 ~R 10 are each independently selected from hydrogen, alkylaryl, aryl, or alkyl groups having 1 to 6 carbon atoms, and halogen, and the alkylaryl, aryl, and alkyl groups may contain one or more heteroatoms. 7 ~R 10 does not contain heteroatoms (most preferably R 1 , R 2 , and R 6 ~R 10 (None of these contain any heteroatoms). In this structure (2), R 1 , R 2 , and R 6 ~R 10 Among them is R 1 , R 2 , and R 6 ~R 10 It is also preferred that there is no further attachment to any of the other cyclic groups (ie, there are no further cyclic groups). Preferably, R 7 ~R 10 are each independently selected from hydrogen and alkyl groups having 1 to 6 carbon atoms, and more preferably selected from hydrogen, methyl, ethyl, and propyl. 7 ~R 10 Most preferably, each is hydrogen.

[0018] In the preferred structure according to structure (2), R 2 is ethyl, and R 1 and R 5 ~R 10 are all hydrogen. More generally, in the present invention, although not preferred, any of alkylaryl group, aryl group or alkyl group can be substituted with heteroatom.Examples include oxygen, sulfur, nitrogen, phosphorus, silicon or halogen.For example, the alkyl group used in the present invention can be substituted with nitrogen in the form of amine group, or with nitrogen and oxygen in the form of amide group, or with chloro group, bromo group or silyl group.Cyclic alkyl or aryl structure can contain heteroatom such as oxygen, sulfur, nitrogen, silicon and phosphorus.

[0019] As already mentioned, R 3 ~R 6 Preferably, R in structure (1) is 0 or 1, except when one or more of is halogen. 1 ~R 6 or R in structure (2) 1 , R 2 , or R 6 ~R 10 None of the groups contain heteroatoms, i.e., they contain only H atoms or only C and H atoms. In a preferred embodiment, the modifier, in particular one of the preferred modifiers described above, is present in the catalyst component as an internal modifier. It should also be noted that mixtures of such compounds may be used, as well as mixtures of modifier compounds described by Structure (1) with other donor compounds known in the art. Examples of this are described further below. (For the avoidance of doubt, references herein to compounds of Structure (1) also include a "subset" of such compounds that are also described by Structure (2), even if no direct reference is made to said structure, since compounds of Structure (2) are also compounds according to Structure (1).)

[0020] The solid hydrocarbon-insoluble catalyst component generally comprises a titanium compound supported on a magnesium-containing compound in combination with a modifier compound. In a preferred embodiment, when the modifier is an internal modifier, the supported titanium-containing olefin polymerization catalyst component is typically formed by reacting a titanium compound, a modifier compound, and a magnesium-containing compound. Such supported titanium-containing reaction product may be further processed or modified by additional chemical treatment. Suitable magnesium-containing compounds include reaction products of magnesium halides, such as magnesium chloride or magnesium bromide, with organic compounds, such as alcohols or organic acid esters, or organometallic compounds of Group I-III metals, magnesium alcoholates, or magnesium alkyls.

[0021] A particularly preferred titanium compound for use in such a step is TiCl4, although a number of other species are known to be suitable, such as other titanium(IV) halides or titanium alcoholates. The present invention is not limited to catalyst components prepared by any particular preparation method. For example, a catalyst component containing an internal modifier may be prepared by reacting a magnesium compound, a titanium compound, and a modifier compound in any suitable order. For example, the catalyst component may be prepared by first reacting a magnesium compound with a titanium compound and then incorporating the modifier compound. Alternatively, the modifier may be incorporated before the titanium compound, during the addition of the titanium compound, or a combination thereof (multiple steps). Generally, the aforementioned modifier compound and titanium compound can be contacted with solid particles of the magnesium compound in the presence of an inert hydrocarbon or halogenated diluent, although other suitable techniques may be employed. Suitable diluents are substantially inert to the components employed and are liquid at the temperatures and pressures employed.

[0022] Most typically, a solution of titanium tetrachloride and modifier compounds is contacted with the magnesium-containing material, for example, by adding it to a slurry of magnesium-containing particles in a suitable hydrocarbon. Such magnesium-containing material is usually in the form of discrete particles and may contain other materials, such as transition metals and organic compounds. Alternatively, the mixture of magnesium chloride, titanium tetrachloride, and modifiers can be formed into an active catalyst component by ball milling. However, in a preferred method, a slurry of magnesium-containing material is first contacted, usually with stirring, with a solution of the modifier. The resulting solution is then treated with a suitable titanium-containing species. Several steps may be applied for the addition of the internal donor or titanium, or both. In one particularly advantageous procedure, magnesium chloride-based support particles suspended in a liquid hydrocarbon diluent such as toluene are first contacted with titanium tetrachloride and then with a modifier compound; these two contacting steps are repeated one or more times, followed by a final contacting step using titanium tetrachloride (i.e., no subsequent further modifier addition step). The diluent used may be decanted between each step, and fresh diluent is added before the next step. After the final step, the diluent is removed, and the product is washed one or more times with a liquid hydrocarbon such as heptane, and then dried.

[0023] The conditions for such steps are known in the art. Each step is usually carried out at elevated temperatures, typically 75-135°C, at atmospheric pressure or at slightly elevated pressures of 1-3 bar. Typical individual treatment times for each step may vary from a few minutes to several hours, usually 0.25-3 hours. The preparation step results in a solid reaction product suitable for use as a catalyst or catalyst component. Prior to such use, it is desirable to remove incompletely reacted starting materials from the solid reaction product. This is conveniently accomplished by washing the solid with a suitable solvent, such as a liquid hydrocarbon or chlorocarbon, after separation from any preparation diluent, and preferably within a short time after completion of the preparation reaction, since prolonged contact of the catalyst component with unreacted starting materials can adversely affect catalyst component performance. Although not required, the final solid reaction product may be washed with an inert liquid hydrocarbon or halogenated hydrocarbon prior to contact with the Lewis acid. If such washing is performed, it is preferred to substantially remove the inert liquid before contacting the washed solid with the Lewis acid.

[0024] In typical catalyst components of the present invention, the magnesium to titanium molar ratio is at least 1:1, preferably up to 20:1. Larger amounts of magnesium may be employed without adversely affecting catalyst component performance, but typically it is not necessary to exceed a magnesium to titanium ratio of 20:1. More preferably, the magnesium to titanium ratio is in the range of 2:1 to 20:1, such as 5:1 to 20:1. The catalyst component of the present invention generally contains 1 to 6 mass % titanium, 10 to 25 mass % magnesium, and 45 to 65 mass % halogen. Preferably, the catalyst component contains 2 to 4 mass % titanium, 15 to 21 mass % magnesium, and 55 to 65 mass % chlorine. When used as an internal modifier, the modifier component is typically incorporated into the solid catalyst component at a molar ratio of modifier to titanium of at least 0.1:1 and / or at most 10:1. The molar ratio is preferably at least 0.2:1, more preferably at least 0.4:1. The molar ratio is preferably at most 5:1, such as at most 2:1. A molar ratio of modifier to titanium in the range of 0.4:1 to 1.2:1 is most preferred.

[0025] As previously mentioned, mixtures of electron donors may be used in embodiments of the present invention, including mixtures of two or more modifier compounds described by structure (1) with other electron donor compounds known in the art, as well as mixtures of such compounds. For example, when a modifier of structure (1) is used as an internal modifier (internal electron donor), the modifier may be used as a component of an internal donor mixture. Preferably, in these embodiments, the internal donor mixture is a mixture of at least one compound of structure (1) and at least one other electron donor compound known in the art (hereinafter referred to as an "additional internal donor"). In one embodiment, the additional internal donor may be a dialkyl phthalate. For example, the additional internal donor may be a dialkyl phthalate, each alkyl group of which may be the same or different and containing 3 to 5 carbon atoms, preferably dibutyl phthalate, and more preferably di-n-butyl phthalate or di-i-butyl phthalate. Alternatively, the additional internal donor may be a dialkyl phthalate, each alkyl group of which may be the same or different and containing at least 6 carbon atoms, preferably up to 10 carbon atoms. Specific suitable dialkyl phthalates include dihexyl phthalate and dioctyl phthalate.

[0026] In one alternative, the additional internal donor may be a dicycloaliphatic ester of an aromatic dicarboxylic acid, where each alicyclic moiety may be the same or different and each contains 5 to 7 carbon atoms, preferably 6 carbon atoms. Preferably, the ester is a dicycloaliphatic diester of an ortho-aromatic dicarboxylic acid. Suitable specific dicycloaliphatic esters include dicyclopentyl phthalate, dicyclohexyl phthalate, and di-(methylcyclopentyl) phthalate. Alternatively, the additional internal donor may be an alkyl-arylalkyl phthalate, where the alkyl portion contains 2 to 10, preferably 3 to 6, carbon atoms and the arylalkyl portion contains from 7 carbon atoms up to 10, preferably up to 8 carbon atoms. In particular, suitable alkyl-arylalkyl phthalates include benzyl n-butyl phthalate and benzyl i-butyl phthalate.

[0027] The additional internal donor may also be an alkyl ester of an aliphatic monocarboxylic acid, the carboxylic acid moiety of which contains 2 to 20, preferably 3 to 6, carbon atoms, and the alkyl moiety of which contains 1 to 3 carbon atoms. Preferably, the additional internal donor is an alkyl ester of an aliphatic monocarboxylic acid. Suitable specific alkyl esters include methyl valerate, ethyl pivalate, methyl pivalate, methyl butyrate, and ethyl propionate. In another alternative, such additional internal donors may also be alkyl esters of aromatic monocarboxylic acids, where the monocarboxylic acid moiety contains 6 to 8 carbon atoms and the alkyl moiety contains 1 to 3 carbon atoms, with suitable specific alkyl esters in this case including methyl toluate, ethyl toluate, methyl benzoate, ethyl benzoate, and propyl benzoate.

[0028] In another alternative embodiment, the additional internal donor may also be a 1,3-diether, particularly a 2,2-di-substituted-1,3-diether. Preferred examples include 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, and 9,9-bis(methoxymethyl)fluorene. Of these, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 9,9-bis(methoxymethyl)fluorene are preferred. The molar ratio of additional internal donor to (internal) modifier in all the above options may be in the range of, for example, 5:95 to 95:5.

[0029] The catalyst or catalyst component of the present invention can be used in the polymerization or copolymerization of alpha-olefins. Prepolymerization or encapsulation of the catalyst or catalyst component may be carried out before use in polymerization. A particularly useful prepolymerization procedure is described in U.S. Pat. No. 4,579,836. Typically, the catalyst component of the present invention is used in polymerization in combination with a cocatalyst component. The cocatalyst component may be a Group II or Group III metal alkyl. Useful Group II and IIIA metal alkyls have the formula MR, where M is a Group II or Group III metal, each R is independently an alkyl group of 1 to 20 carbon atoms, and m corresponds to the valence of M. m Examples of useful metals M include magnesium, calcium, zinc, cadmium, aluminum, and gallium. Examples of suitable alkyl groups R include methyl, ethyl, butyl, hexyl, decyl, tetradecyl, and eicosyl. From the standpoint of catalyst or catalyst component performance, preferred Group II and Group IIIA metal alkyls are those of magnesium, zinc, and aluminum in which the alkyl group contains 1 to 12 carbon atoms. Specific examples of such compounds include Mg(CH3)2, Mg(C2H5)2, Mg(C2H5)(C4H9), Mg(C4H9)2, Mg(CH 13 )2, Mg(C 12 H 25 )2, Zn(CH3)2, Zn(C2H5)2, Zn(C4H9)2, Zn(C4H9)(C8H 17 ), Zn(CH 13 )2, Zn(CH 13 )3, and AI(C 12 H 25 ) 3. Magnesium alkyls, zinc alkyls, or aluminum alkyls containing 1 to 6 carbon atoms per alkyl group can be preferably used.

[0030] Alkyl aluminums are most preferred as cocatalysts, with trialkyl aluminums containing 1 to 6 carbon atoms per alkyl group being even more preferred. In particular, triethyl aluminum and triisobutyl aluminum or combinations thereof can be used. However, if desired, metal alkyls having one or more halogen or hydride groups such as ethylaluminum dichloride, diethylaluminum chloride, etc. may be employed. A catalyst for the polymerization or copolymerization of alpha olefins can be formed by combining the supported titanium-containing catalyst component of the first aspect of the present invention with a cocatalyst component, preferably an alkylaluminum compound. Typically, useful aluminum to titanium molar ratios in such catalyst systems are from 10:1 to 2000:1, preferably from 50:1 to 1500:1. Typically, the catalyst components of the present invention are used for polymerization in combination with a cocatalyst and also in combination with one or more additional electron donor compounds. In particular, in one embodiment of the present invention, the modifier of structure (1) can be used as both an internal and an external electron donor for the catalyst, either alone or in combination with other suitable electron donors.

[0031] However, in a preferred embodiment, the modifier is used as an internal modifier (or internal electron donor), which may be used as part of an internal donor mixture as described, and which is further used in conjunction with one or more other external electron donors. Typical aluminum to external electron donor molar ratios in such catalyst systems are 2-60. A preferred external electron donor is a silane. Typical aluminum to silane compound molar ratios in such catalyst systems are 3 to 50. Preferred silanes include alkyl-, aryl-, and / or alkoxy-substituted silanes containing hydrocarbon moieties having 1 to 20 carbon atoms. Particularly preferred are silanes having the formula SiY4, where each Y group is the same or different and is an alkyl or alkoxy group containing 1 to 20 carbon atoms. Preferred silanes include isobutyltrimethoxysilane, diisobutyldimethoxysilane, diisopropyldimethoxysilane, n-propyltriethoxysilane, isobutylmethyldimethoxysilane, isobutylisopropyldimethoxysilane, dicyclopentyldimethoxysilane, tetraethylorthosilicate, dicyclohexyldimethoxysilane, diphenyldimethoxysilane, di-t-butyldimethoxysilane, and t-butyltrimethoxysilane.

[0032] Other compounds useful as external electron donors, either as an alternative to or in addition to one or more silanes, are organic compounds containing oxygen, nitrogen, sulfur, and / or phosphorus. Such compounds include organic acids, organic acid anhydrides, organic acid esters, alcohols, ethers, aldehydes, ketones, amines, amine oxides, amides, thiols, various phosphate esters and amides, and the like. Mixtures of external electron donors may also be used. Particular organic acids and esters are benzoic acid, halobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and their alkyl esters in which the alkyl group contains 1 to 6 carbon atoms, such as methyl chlorobenzoate, butyl benzoate, isobutyl benzoate, methyl anisate, ethyl anisate, methyl p-toluate, hexyl benzoate, cyclohexyl benzoate, and diisobutyl phthalate, because they show good results in terms of activity and stereospecificity and are convenient to use. The catalysts or catalyst components of the present invention are useful for the stereospecific polymerization or copolymerization of alpha-olefins containing three or more carbon atoms, such as propylene, butene-1, pentene-1, 4-methylpentene-1, and hexene-1, as well as mixtures thereof and mixtures thereof with ethylene.

[0033] Thus, in a third aspect, the present invention provides a process for polymerizing propylene or a mixture of propylene with ethylene or a C4-C5 alpha olefin comprising using a catalyst according to the second aspect. The catalyst or catalyst component of the present invention is particularly effective for the stereospecific polymerization or copolymerization of propylene or mixtures thereof with up to 30 mole percent ethylene or higher alpha-olefins. Highly crystalline polyalphaolefin homopolymers or copolymers can be prepared by contacting at least one alpha-olefin with the catalyst or catalyst component under polymerization or copolymerization conditions. Such conditions include polymerization or copolymerization temperature and time, monomer pressure, avoidance of catalyst poisoning, selection of polymerization or copolymerization medium in slurry processes, use of additives to control homopolymer or copolymer molecular weight, and other conditions well known to those skilled in the art. Slurry, bulk, and gas-phase polymerization or copolymerization processes are contemplated in the present invention.

[0034] The amount of catalyst or catalyst component used will vary depending on the polymerization or copolymerization method selected, reactor size, the monomers to be polymerized or copolymerized, and other factors known to those skilled in the art, and can be determined based on the examples provided below. Typically, the catalyst or catalyst component of the present invention is used in an amount ranging from 0.2 to 0.02 mg of catalyst per gram of polymer or copolymer produced. Regardless of the polymerization or copolymerization process employed, the polymerization or copolymerization should be carried out at a temperature high enough to ensure a reasonable polymerization or copolymerization rate and avoid excessively long reactor residence times, but not so high that an overly rapid polymerization or copolymerization rate would result in the production of unreasonably high levels of stereoirregular products. Generally, the temperature is in the range of 0°C to 120°C, with a range of 20°C to 95°C being preferred from the standpoint of achieving good catalyst performance and high production rates. More preferably, the polymerization is carried out at a temperature in the range of 50°C to 80°C. Olefin polymerization or copolymerization can be carried out at a monomer pressure at or above atmospheric pressure. Typically, the monomer pressure is in the range of 140 to 4100 kPa, but in gas-phase polymerization or copolymerization, the monomer pressure should not be less than the vapor pressure of the α-olefin being polymerized or copolymerized at the polymerization or copolymerization temperature.

[0035] Polymerization or copolymerization times generally range from 1 / 2 to several hours in a batch process and would correspond to the average residence time in a continuous process. Polymerization or copolymerization times in the range of 1 to 4 hours are typical for autoclave reactions. In a slurry process, polymerization or copolymerization times can be adjusted as desired. Polymerization or copolymerization times in the range of 1 / 2 to several hours are generally sufficient for a continuous slurry process. Suitable diluents for use in slurry polymerization or copolymerization processes include alkanes and cycloalkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane, and methylcyclohexane; alkylaromatics such as toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethylbenzene, and mono- and dialkylnaphthalenes; halogenated and hydrogenated aromatics such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene, tetrahydronaphthalene, decahydronaphthalene; high molecular weight liquid paraffins or mixtures thereof, and other well-known diluents. It is often desirable to purify the polymerization or copolymerization medium prior to use by distillation, filtration through molecular sieves, contact with compounds such as alkylaluminum compounds capable of removing trace impurities, or by other suitable means.

[0036] Examples of gas-phase polymerization or copolymerization processes in which the catalyst or catalyst components of the present invention can be used include both stirred-bed and fluidized-bed reactor systems and are described in U.S. Pat. Nos. 3,957,448, 3,965,083, 3,971,786, 3,970,611, 4,129,701, 4,101,289, 3,652,527, and 4,003,712. A typical gas-phase olefin polymerization or copolymerization reactor system includes at least one reactor vessel to which olefin monomer and catalyst components can be added and which contains a stirred bed of forming polymer particles. Typically, the catalyst components are added together or separately through one or more valve-controlled ports in a single or first reactor vessel. Olefin monomer is typically fed to the reactor through a recycle gas system in which unreacted monomer removed as off-gas and fresh feed monomer are mixed and injected into the reactor vessel. For the production of impact copolymers, a homopolymer formed from a first monomer in a first reactor is reacted with a second monomer in a second reactor. A quench liquid, which may be a liquid monomer, may be added to the polymerizing or copolymerizing olefins through a recycle gas system to control the temperature.

[0037] Regardless of the polymerization or copolymerization method, the polymerization or copolymerization is generally carried out under conditions that exclude water and other materials that act as catalyst poisons. The polymerization or copolymerization can also be carried out in the presence of additives to control polymer or copolymer molecular weight. For this purpose, hydrogen is typically employed in a manner known to those skilled in the art. Although not usually required, upon completion of the polymerization or copolymerization, or when it is desired to terminate the polymerization or copolymerization or at least temporarily deactivate the catalyst or catalyst components of the present invention, the catalyst may be contacted with water, alcohol, acetone, or other suitable catalyst deactivators in a manner known to those skilled in the art. The resulting product is typically a solid, predominantly isotactic polyalphaolefin. The homopolymer or copolymer yield is sufficiently high relative to the amount of catalyst employed that useful products can be obtained without separating the catalyst residues. Furthermore, the level of stereoirregular by-products is sufficiently low that useful products can be obtained without separating the by-products. The polymer or copolymer products produced in the presence of the catalyst or catalyst components can be processed into useful articles by extrusion, injection molding, and other common techniques.

[0038] The polymer product contains primarily highly crystalline polymers of propylene. Polymers of propylene having a substantial polypropylene crystalline content are now well known in the art. It has long been recognized that crystalline propylene polymers, described as "isotactic" polypropylene, contain crystalline domains interspersed with some amorphous domains. The amorphous domains may result from defects in the regular isotactic polymer chains that inhibit complete polymer crystal formation. The degree of polypropylene tacticity in a polymer can be determined by well-known techniques such as isotactic index, crystalline melting point, flexural modulus, and more recently, carbon-13 nuclear magnetic resonance (CNMR). 13 The relative percentage of mesopentads (%m) can be measured by C NMR (C NMR). The invention described herein is illustrative, but not limited, by the following examples. [Example]

[0039] ( Example 1 ) Supported catalyst components according to the present invention were prepared and tested for propylene polymerization as described below. In each example, a magnesium alkoxide support prepared according to the examples in WO2005044873A1 was used. To a slurry of 0.15 g of the Mg alkoxide support, 2 mL of toluene and 0.1 mmol of the corresponding modifier were added. The resulting slurry was stirred at 100° C. for 10 minutes. The mixture was then left to settle for 30 minutes, and the liquid phase was decanted with a pipette. The remaining solid was then mixed with 1 mL of toluene and 1 mL of TiCl4 and then heated to 100°C. The modifier (0.1 mmol) (see Table 1) was then added at 100°C, and the reaction mixture was stirred at the above temperature for 1 hour. The slurry was allowed to settle for 30 minutes and cooled to room temperature. The liquid was decanted with a pipette. The solid residue was mixed with 1 mL of toluene and 1 mL of TiCl4, and the reaction mixture was stirred at 120 °C for 30 min. The resulting suspension was allowed to cool to room temperature for 30 min and settle. The liquid was decanted, and the resulting catalyst was washed with heptane (4 × 2.5 mL, 10 min). The catalyst was then dried under reduced pressure.

[0040] ( Examples 2 to 9 ) The procedure of Example 1 was repeated except that the modifiers shown in Table 1 were used. Propylene polymerization Batch slurry phase propylene polymerization reactions were carried out in a 2 L autoclave reactor at 71° C. and 1.0 MPa total reactor pressure with stirring at 500 rpm for a reaction time of 2 hours. Triethylaluminum (TEA) is used as a cocatalyst with diisobutyldimethoxysilane as an external donor. The reactor is charged with the TEA / donor, catalyst components, hydrogen, and propylene in that order.

[0041] In a typical procedure, a dry, nitrogen-purged 2 L stainless steel autoclave reactor was charged at 40 °C with catalyst (-20 mg), triethylaluminum (3.6 mL of a 0.75 M solution in heptane), and diisobutyldimethoxysilane (1.0 mL of a 0.15 M solution in heptane), and 850 mL of heptane. 7 mmol of hydrogen was introduced at approximately 85 kPa. Stirring and heating were started, and a 100 kPa pressure drop from a 75 mL vessel containing hydrogen was introduced into the reactor, followed by an approximately 30 g portion of propylene. When the temperature reached 71 °C, the propylene reservoir vessel was opened to the reactor, and a constant propylene pressure of 1.0 MPa psig was maintained for 1 hour. The reactor was then vented, and the resulting polymer slurry was discharged from the reactor, filtered, and dried.

[0042] The results are shown in Table 1. [Table 1] JPEG2025538763000006.jpg33170

[0043] The results show that the catalyst according to the present invention produces polypropylene in good yield.

Claims

1. A solid, hydrocarbon-insoluble catalyst component containing magnesium, titanium, and a halogen, and further comprising a modifier compound having the following structure (1): 【Chemistry 1】 (In the formula, R 1 is selected from H, an aryl or alkyl group having 1 to 10 carbon atoms; R 2 is selected from alkyl groups having 1 to 10 carbon atoms; R 3 ~R 6 are each independently selected from H, an alkylaryl group, an aryl group, or an alkyl group having 1 to 10 carbon atoms, and a halogen, with the proviso that R 4 and R 5 at least one of is H; Any alkylaryl, aryl, or alkyl group may contain one or more heteroatoms, and / or R 3 and R 4 Or R 5 and R 6 may be bonded to form a cyclic group)

2. R 1 2. The catalyst component of claim 1, wherein is hydrogen or methyl.

3. R 2 3. The catalyst component of claim 1, wherein is an alkyl group selected from methyl, ethyl, propyl, and butyl.

4. R 3 ~R 6 The catalyst component according to any one of claims 1 to 3, wherein each is hydrogen.

5. R 1 is hydrogen, and R 2 5. The catalyst component of claim 4, wherein is an alkyl group selected from methyl, ethyl, and butyl.

6. R 3 ~R 6 4. The catalyst component according to claim 1, wherein at least one of the following is a halogen.

7. R 1 is hydrogen, and R 2 is methyl, and R 3 , R 4 and R 6 is hydrogen, and R 5 7. The catalyst component of claim 6, wherein is bromine.

8. R 3 ~R 6 7. The catalyst component according to any one of claims 1 to 3 and 6, wherein at least one of is an alkyl having 1 to 6 carbon atoms.

9. R 1 is hydrogen, and R 2 is methyl, and R 3 and R 5 is t-butyl, and R 4 and R 6 9. The catalyst component of claim 8, wherein is hydrogen.

10. R 1 is hydrogen, and R 2 is butyl, and R 3 ~R 5 is hydrogen, and R 6 9. The catalyst component of claim 8, wherein is methyl.

11. 2. The catalyst component of claim 1, wherein the modifier has the following structure: 【Chemistry 2】 (In the formula, R 5 is H, R 7 ~R 10 are each independently selected from H, alkylaryl, aryl, or alkyl groups having 1 to 6 carbon atoms, and halogen, wherein the alkylaryl, aryl, and alkyl groups may contain one or more heteroatoms.

12. R 2 is ethyl, and R 1 and R 5 ~R 10 12. The catalyst component of claim 11, wherein all of

13. Catalyst component according to any one of claims 1 to 12, wherein said modifier compound having structure (1) is an internal modifier.

14. 1. A catalyst useful in the polymerization of olefins, comprising: i) a solid, hydrocarbon-insoluble catalyst component according to any one of claims 1 to 13; ii) at least one cocatalyst component; A catalyst comprising:

15. 15. A method for polymerizing propylene or propylene with ethylene or C, comprising using the catalyst of claim 14. 4 -C 5 A method for polymerizing a mixture with alpha olefins.

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