Solid titanium catalyst component, olefin polymerizing catalyst, olefin polymerization method, and ester compound or carbamate compound

Abstract

This solid titanium catalyst component (I) is characterized by containing titanium, magnesium, a halogen, and a cyclic organic compound (a) represented by formula (1). Some forms of the cyclic organic compound (a) are novel ester compounds or carbamate compounds. [C is a carbon atom. E, E1, and E1' are carbon atoms or atoms selected from elements in group 15 of the periodic table. Ra, R1-R4, and R1'-R4' are each a hydrogen atom, a halogen atom, a hydrocarbon group, or a group selected from heteroatom-containing hydrocarbon groups. Each one of R3 and R3', of which there are multiple, is an ester group or a group selected from groups (excluding ester groups) containing a carbonyl group. l is an integer of 0-3, and m and n are integers of 1-10.]

Description

Solid titanium catalyst component, catalyst for olefin polymerization, method for olefin polymerization, and ester compound or carbamate compound

[0001] The present invention relates to a solid titanium catalyst component, a catalyst for olefin polymerization containing the solid titanium catalyst component, and a method for polymerizing olefins using the catalyst for olefin polymerization. The present invention also relates to novel ester compounds or carbamate compounds.

[0002] Conventionally, catalysts containing titanium compounds supported on activated magnesium halide have been known as catalysts used to produce olefin polymers such as ethylene-α-olefin homopolymers or ethylene-α-olefin copolymers. Hereinafter, "homopolymerization" and "copolymerization" may be collectively referred to as "polymerization."

[0003] Well-known catalysts for olefin polymerization include those containing titanium tetrachloride or titanium trichloride, known as Ziegler-Natta catalysts, and catalysts consisting of a solid titanium catalyst component comprising magnesium, titanium, halogens, and electron donors, and organometallic compounds.

[0004] The latter catalyst exhibits high activity in the polymerization of α-olefins such as ethylene, propylene, and 1-butene. Furthermore, the resulting α-olefin polymers may possess high stereoregularity.

[0005] Among the catalysts mentioned above, it has been reported that excellent polymerization activity and stereospecificity are exhibited when a catalyst consisting of a solid titanium catalyst component supported with an electron donor selected from carboxylic acid esters, such as phthalates, an aluminum-alkyl compound as a co-catalyst component, and a silicon compound having at least one Si-OR (wherein R is a hydrocarbon group) is used (for example, Patent Document 1). In addition, many electron donors other than phthalates, such as polyvalent ether compounds, have also been investigated.

[0006] Regarding the use of ester compounds as electron donors, catalysts containing carboxylic acid esters having divalent or higher ester groups have also been disclosed (for example, Patent Document 2).

[0007] As catalysts that yield polyolefins with a broad molecular weight distribution, catalysts using substituted succinic acid esters as electron donors have been reported. The present applicant has also reported catalysts containing polycarboxylic acid esters having a special cyclic structure (Patent Documents 3 and 4).

[0008] Furthermore, the applicant has disclosed an olefin polymerization catalyst that includes a solid titanium catalyst using a cyclic ester compound of a specific structure as an electron donor (Patent Documents 5 and 6).

[0009] Other reported compounds include diketones (Patent Document 7), malonic acid esters (Patent Document 8), succinic acid esters (Patent Document 9), naphthalenediol diesters (Patent Document 10), and catechol diesters (Patent Document 11), and this remains a field where active research and development is being conducted, mainly by companies. There are also reports that diamide compounds with specific structures are suitable (Patent Documents 12, 13).

[0010] Japanese Patent Publication No. 57-63310, Japanese Patent Publication No. 2005-517746, International Publication No. 2008 / 010459, International Publication No. 2006 / 077945, International Publication No. 2022 / 045232, International Publication No. 2022 / 138634, Japanese Patent Publication No. 2005-226076, Japanese Patent Publication No. 2000-516987, Japanese Patent Publication No. 2002-542347, Japanese Patent Publication No. 2011-529888, Japanese Patent Publication No. 2014-500390, Chinese Patent Publication No. 108570120, Chinese Patent Publication No. 108570119

[0011] Polypropylene (propylene polymer), a representative polymer of olefins with three or more carbon atoms, is known to possess the potential to exhibit heat resistance and rigidity comparable to general-purpose engineering plastics, despite having a hydrocarbon structure. Furthermore, polyolefins, with their hydrocarbon structure, are materials that have a relatively low environmental impact because they generate fewer toxic gases during incineration or thermal recycling (a recycling method that recovers combustion heat energy as electricity, etc.).

[0012] The heat resistance of propylene polymers largely depends on their stereoregularity, and it is known that their rigidity is influenced not only by stereoregularity but also by their molecular weight distribution. While technologies have been developed to control stereoregularity to a considerable degree, recent advancements in molding technology suggest that polymers with even higher stereoregularity may exhibit unexpected physical properties. Combining this with a broader molecular weight distribution may further improve the balance of physical properties. In addition, propylene polymers with high stereoregularity generally have high heat of fusion, and a high heat of fusion can sometimes serve as an indicator of heat resistance.

[0013] Since homopolymers of propylene polymers may have low impact resistance, so-called propylene block copolymers, which are co-produced with ethylene-containing copolymers in a series process, are also used as a preferred embodiment. If a method could be developed to produce propylene polymers with such flexible components, such as a high amount of decane-soluble components and high heat resistance, using a simpler method, it would be desirable not only from the perspective of energy efficiency but also from the perspective of environmental issues.

[0014] From the above viewpoint, the object of the present invention is to provide a solid titanium catalyst component, a catalyst for olefin polymerization, and a method for polymerizing olefins that can produce unique olefin polymers with high activity, such as those having a relatively large amount of decane-soluble components while possessing a high heat of fusion.

[0015] Another objective of the present invention is to provide a compound suitable as an internal donor component for a solid titanium catalyst component that can produce a propylene polymer with extremely high stereoregularity (expected to have a high melting point and high heat of fusion) with high productivity (high activity).

[0016] As a result of intensive studies, the present inventors have found that a solid titanium catalyst component containing a heteroatom-containing organic compound having a structure in which a plurality of special ring structures are linked has a broad molecular weight distribution and can produce an olefin polymer having a high heat of fusion or a high crystallization temperature with high activity even when the decane-soluble component is relatively large. Further, it has also been found that an ester compound or a carbamate compound having a specific structure is a suitable compound as a Lewis base of the solid titanium catalyst component, for example. Based on these findings, the present inventors have completed the present invention. Examples of aspects of the present invention are shown below.

[0017] [1] A solid titanium catalyst component (I) characterized by containing titanium, magnesium, a halogen, and a cyclic organic compound (a) represented by the following formula (1).

[0018] [In formula (1), C is a carbon atom, E, E １ and E １’ are atoms selected from a carbon atom and Group 15 elements of the periodic table, and R ａ , R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’ are each a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, and a heteroatom-containing hydrocarbon group, and each one of a plurality of R ３ and R ３’ is a group selected from an ester group and a group containing a carbonyl group (excluding an ester group), l is an integer of 0 to 3, and m and n are each an integer of 1 to 10. ]

[0019] [2] The solid titanium catalyst component (I) according to item [1], wherein the E is C (a carbon atom). [3] The solid titanium catalyst component (I) according to item [1], wherein m and n are each an integer of 2 to 4. [4] The solid titanium catalyst component (I) according to [1], wherein l is 0 or 1.

[0020] [5] A catalyst for olefin polymerization, characterized by comprising a solid titanium catalyst component (I) described in item [1] and an organometallic compound catalyst component (II) containing a metal element selected from Group 1, Group 2 and Group 13 of the periodic table. [6] The catalyst for olefin polymerization described in item [5], further comprising an electron donor (III).

[0021] [7] A method for polymerizing an olefin in the presence of an olefin polymerization catalyst as described in item [5] or [6].

[0022] [8] An ester compound or carbamate compound represented by the following formula (2). [In formula (2), C is a carbon atom, E, E １ and E １’ Each of these atoms is selected from the group consisting of carbon atoms and elements of Group 15 of the periodic table, and R ａ , R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’ Each of these is a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, and a heteroatom-containing hydrocarbon group, and R １ , R ２ , R ３ and R ４ It can directly bond and form multiple bonds, R １’ , R ２’ , R ３’ and R ４’ They can directly bond and form multiple bonds, and there are multiple R ３ and R ３’ Each of them is an ester group (-COOR ｅ ) and R ｅ [where l is a primary or secondary hydrocarbon group having two or more carbon atoms, l is an integer from 0 to 2, and m and n are integers from 1 to 10, respectively.]

[0023] [9] The aforementioned R ２ , R ３ , R ４ , R ２’ , R ３’ and R４’ An ester compound or carbamate compound as described in item [8], wherein one or more of the atoms are hydrogen atoms.

[0024]

[10] The R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’ However, the substituents are independent of each other, as described in item [8], for the ester compound or carbamate compound.

[0025] By using the solid titanium catalyst component of the present invention, olefin polymers exhibiting high heat of fusion and a broad molecular weight distribution can be produced with high activity, even with a relatively high decane-soluble component. Olefin polymers obtained by this method may have properties such as excellent impact resistance, even if they are propylene homopolymers, which are usually characterized by rigidity rather than impact resistance. Therefore, it is expected that olefin polymers with an excellent balance of transparency, rigidity, and impact resistance can be created.

[0026] Furthermore, the ester compounds or carbamate compounds of the present invention can be used, for example, as solvents, pharmaceutical intermediates, and raw materials for nylon, as well as as chelating agents and components of Ziegler-Natta catalysts.

[0027] This is the DSC chart (second heating step) of the polymers obtained in Example 2 and Comparative Example 2.

[0028] The following describes in detail the solid titanium catalyst component (I), the catalyst for olefin polymerization, the method for producing the olefin polymer, and the propylene polymer according to the present invention.

[0029] [Solid Titanium Catalyst Component (I)] The solid titanium catalyst component (I) according to the present invention is characterized by containing titanium, magnesium, a halogen, and a polyvalent ester compound having a special cyclic structure (hereinafter also referred to as "cyclic organic compound (a)").

[0030] <Cyclic Organic Compound (a)> The cyclic organic compound (a) of the present invention is represented by the following formula (1).

[0031] In formula (1), C is a carbon atom, and E, E １ and E １’ R is an atom selected from carbon atoms and elements of Group 15 of the periodic table. ａ , R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’ These are groups selected from hydrogen atoms, halogen atoms, hydrocarbon groups, and heteroatom-containing hydrocarbon groups, and there are multiple R groups. ３ and R ３’ Each of the following groups is selected from ester groups and carbonyl groups (excluding ester groups), where l is an integer from 0 to 3, and m and n are integers from 1 to 10, respectively.

[0032] The aforementioned E, E １ and E １’ When E is a Group 15 element, it is preferably nitrogen and phosphorus, and more preferably nitrogen. E is particularly preferably C (carbon atom). １ and E １’ Preferably, at least one of them is C (carbon atom).

[0033] R ａ , R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’ Two or more R atoms can bond to each other to form a monocycle or polycycle, or adjacent substituents can directly bond to each other to form a multiple bond. ２ , R ３ , R ４ , R ２’ , R ３’ and R ４’ The same applies to the following multiple Rs. ２ , R ３ , R ４ , R ２’, R ３’ and R ４’ may be the same group or different groups.

[0034] When the E, E １ and E １’ are Group 15 elements, due to the characteristics of the elements, there may be a case where the R １ , R １’ does not exist. Also, there may be a case where a part of the R ３ , R ３’ does not exist. When E, E １ and E １’ are Group 15 elements, when the R １ , R １’ , R<o000099>, R ３’ exists, the E, E １ and E １’ are cations, the R １ , R １’ , R ３ , R ３’ are anions, and the bond between the two is in the form of an ionic bond. Among the above two modes, the former mode is preferred.

[0035] Examples of the halogen atom include fluorine, chlorine, bromine, iodine, etc. Chlorine and bromine are preferred, and chlorine is more preferred.

[0036] R ａ , R １ , R ２ , R ３ , R ４ , R<o000112>, R ２’ , R ３’ and R ４’ are hydrocarbon groups, specifically substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms.

[0037] It should be noted that there is a misspelling in the original text where "o000099" and "o000112" should probably be " ３ " and " １’ ". This has been maintained in the translation as it is in the original.The hydrocarbon groups described above are monovalent hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10, more preferably 2 to 8, even more preferably 3 to 8, even more preferably 4 to 8, and particularly preferably 4 to 6 carbon atoms. Examples of such hydrocarbon groups include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, such as substituted or unsubstituted aryl groups, substituted or unsubstituted cycloalkenyl groups, and methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, hexyl groups, heptyl groups, octyl groups, 2-ethylhexyl groups, decyl groups, dodecyl groups, tetradecyl groups, hexadecyl groups, octadecyl groups, eicosyl groups, cyclohexyl groups, and phenyl groups. The alicyclic hydrocarbon groups and aromatic hydrocarbon groups may contain substituents. Among these, n-butyl groups, isobutyl groups, hexyl groups, octyl groups, and phenyl groups are preferred, and n-butyl groups, isobutyl groups, and phenyl groups are even more preferred. These substituents are groups that are substantially free of heteroatoms and represent one of the preferred embodiments in the present invention. In other words, the specific examples described above are groups that consist substantially only of carbon and hydrogen.

[0038] The hydrocarbon group may be a hydrocarbon group containing nitrogen, oxygen, phosphorus, halogen, and silicon. Such substituents can be selected from known structures. More specifically, suitable examples include carboxylic acid ester groups, aldehyde groups, acetyl groups, carbonyl structure-containing groups such as oxycarbonylalkyl groups, alkoxy groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted alkenyloxy groups, substituted or unsubstituted cycloalkyloxy groups, substituted or unsubstituted cycloalkenyloxy groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted heteroaryloxy groups, and siloxy groups. The heteroatoms are preferably nitrogen and oxygen, and more preferably oxygen.

[0039] Among the heteroatom-containing substituents mentioned above, aryl groups containing oxygen-containing substituents are preferred. Specifically, preferred examples include structures in which an oxygen-containing substituent such as an alkoxy group, an allyloxy group, an alkoxyalkyl group, an allyloxyalkyl group, or a substituent in which the oxygen of the substituent is replaced with a carboxyl group is bonded to an aromatic skeleton. Among the above, substituents in which an alkoxy group or an allyloxy group is bonded to an aromatic skeleton are preferred, and substituents in which an alkoxy group is bonded to an aromatic skeleton are more preferred. The number of carbon atoms in the oxygen-containing substituent is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6. More specifically, in addition to the methoxyphenyl group mentioned above, ethoxyphenyl group, propyloxyphenyl group, isopropyloxyphenyl group, butoxyphenyl group, phenoxyphenyl group, etc. are preferred examples. Such aryl groups containing oxygen-containing substituents are R ３ , R ３’ It may be particularly preferred for this purpose.

[0040] Among the hydrocarbon groups mentioned above, hydrocarbon groups such as substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted cycloalkenyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted alkenyloxy groups, and substituted or unsubstituted aryl groups are preferred; and heteroatom-containing hydrocarbon groups such as substituted or unsubstituted cycloalkyloxy groups, substituted or unsubstituted cycloalkenyloxy groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted heteroaryloxy groups, and substituted or unsubstituted heteroaryloxy groups are preferred. Of these, hydrocarbon groups that do not contain heteroatoms are more preferred, and substituted or unsubstituted alkyl groups are particularly preferred.

[0041] R ａ , R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’The case where is a heteroatom-containing hydrocarbon group will be explained. The aforementioned heteroatom-containing hydrocarbon group is a functional group containing a heteroatom, for example, C, E, E that form the cyclic skeleton of formula (1) via the heteroatom. １ and E １’ C, E, E are structures that bond to the base or form the cyclic skeleton of formula (1) via functional groups containing heteroatoms. １ and E １’ These are structural groups that bond to an atom. For example, typical oxygen-mediated groups include alkoxy groups and ester groups (-OCO type), typical nitrogen-mediated groups include amino groups, and functional groups containing heteroatoms include ester groups (-COO type) and groups containing carbonyl groups (excluding ester groups).

[0042] Examples of heteroatom-containing hydrocarbon groups as described above include alkoxy groups, alkylthio groups, aryloxy groups, arylthio groups, acyl groups, ester groups (-COO type, -OCO type), thioester groups, amide groups, imide groups, amino groups, imino groups, sulfone ester groups, sulfonamide groups, cyano groups, nitro groups, carboxyl groups, sulfo groups, mercapto groups, aluminum-containing groups, or hydroxyl groups, silyl groups, and siloxy groups. Examples of hydrocarbon groups that form the aforementioned groups include the aforementioned hydrocarbon groups.

[0043] The above R １ , R ２ , R ４ , R １’ , R ２’ and R ４’ It is sometimes preferable that the substituent has a relatively small number of carbon atoms. Specifically, substituents with 6 or fewer carbon atoms, more preferably 4 or fewer, even more preferably 2 or fewer, and particularly preferably 1 or fewer.

[0044] In the present invention, the plurality of R ３ and R ３’Each of these groups is selected from groups containing an ester group and a carbonyl group (excluding ester groups). The ester group may be either a "-COO type ester group" or a "-OCO type ester group". Preferably, it is a "-COO type ester group". A characteristic feature is that the above group is bonded to E in formula (1), and these substituents themselves, or the surrounding area containing these groups, are considered important as the structure that exhibits the main electron-donating properties of the present invention. Such groups containing ester groups or carbonyl groups (excluding ester groups) usually have a structure that includes a hydrocarbon group. Specific examples of such hydrocarbon groups are the same as the hydrocarbon groups mentioned above, such as the methyl group, ethyl group, butyl group, phenyl group, and alkoxyphenyl group. Among these, hydrocarbon groups with two or more carbon atoms are preferred. More preferably, hydrocarbon groups with three or more carbon atoms, and even more preferably, four or more carbon atoms.

[0045] In the present invention, R ａ , R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’ These may be the same group or different groups.

[0046] In the present invention, R ２ , R ４ , R ２’ and R ４’ It is preferable that the hydrocarbon group does not contain a carbonyl group, and more preferably that it is a hydrocarbon group containing only carbon and hydrogen.

[0047] In this invention, the description of substituents such as halogen atoms and hydrogen atoms, as well as other forms of atoms, may refer to the configurations that have bonds, such as "H-" and "Cl-" as represented in the structural formula.

[0048] In formula (1) of the present invention, l (lowercase L) is an integer from 0 to 3, preferably 0 and 1, and more preferably 0.

[0049] In formula (1) of the present invention, m and n are each integers from 1 to 10, preferably integers from 2 to 8, more preferably integers from 2 to 6, and particularly preferably integers from 2 to 4.

[0050] Solid titanium catalyst components containing compounds with the structure described above tend to yield olefin polymers with high heat of fusion, i.e., high crystallinity.

[0051] Examples of such cyclic organic compounds (a) include the following structures. Note that the structural formulas of the example compounds below include stereoisomers, and while some are shown with their isomer structures, others may also include isomer structures not shown.

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059] Note that the above structural formula uses a conventional notation method. Therefore, each line represents a covalent bond, and the vertices are represented as "-(CH)". ２ This refers to the corresponding hydrocarbon structure, such as "-" or "=CH-". In addition, in the above structural formulas, the methyl group may be represented as "Me", the ethyl group as "Et", the butyl group as "Bu", and the phenyl group as "Ph". Furthermore, "n" indicates "normal", "i" indicates "iso", and "t" indicates "tertiary".

[0060] Compounds having the structure described above contain R of formula (1). ３ , R ３’ Although isomers such as cis and trans may exist, any isomer structure will have the effect that is consistent with the objectives of the present invention.

[0061] These compounds may be used individually or in combination of two or more. Furthermore, as long as the objective of the present invention is not impaired, these cyclic organic compounds (a) may be used in combination with catalyst components (b) and (c) described later.

[0062] The cyclic compound (a) can be synthesized by a combination of known methods, such as the same method as the method for synthesizing the cyclic compound (a') described later.

[0063] Furthermore, the cyclic organic compound (a) may be formed during the process of preparing the solid titanium catalyst component (I). For example, when preparing the solid titanium catalyst component (I), the cyclic organic compound (a) can be incorporated into the solid titanium catalyst component by including a step in which a carboxylic anhydride or carboxylic acid halide corresponding to catalyst component (a) is substantially brought into contact with the corresponding polyol.

[0064] The present invention's method for producing olefin polymers tends to yield polymers with a broad molecular weight distribution and high heat of fusion, while maintaining high activity. On the other hand, these polymers exhibit a peculiar tendency to contain a relatively large amount of decane-soluble components, which is considered unfavorable from the standpoint of heat of fusion.

[0065] The reason why the solid titanium catalyst component containing the cyclic organic compound (a) used in the present invention exhibits such unique performance as described in the present invention is currently unknown. On the other hand, the inventors speculate on the following regarding the manifestation of the above-mentioned effects.

[0066] The cyclic organic compound (a) of the present invention has two cyclic skeletons, [-CR ａ ２ - The structure is linked by a single bond or a single bond, and both ring skeletons are basically structures that can rotate independently, ３ and R ３’ The presence of this element is thought to impose some degree of constraint on rotation. Due to this double-ring structure with some rotational constraints, R ３ and R ３’When forming structures that interact with the titanium atoms of the solid titanium catalyst component described later, it readily adopts a suitable conformation, thus tending to yield polymers with high stereoregularity. On the other hand, because it is a structure that can rotate relatively freely, it can adopt various conformations, or its structure may change slightly (fluctuate) over time. In other words, it is thought that active species with multiple structures within a specific range are formed. Such numerous structures and structural fluctuations mainly affect chain transfer reactions by hydrogen, etc., resulting in the production of polymers with diverse molecular weights. As a result, polymers with a wide molecular weight distribution are produced, and a certain amount of low molecular weight or low stereoregularity polymers that become decane-soluble components are also produced. A solid titanium catalyst component that yields such a unique olefin polymer with a high heat of fusion while having a large amount of decane-soluble components is considered to be a novel component.

[0067] The performance characteristics of the resulting propylene polymer may differ slightly depending on whether E in the cyclic organic compound (a) contained in the solid titanium catalyst component (I) of the present invention is a Group 15 element of the periodic table (e.g., nitrogen) or C (carbon atom). Specifically, in the former case (E is a Group 15 element), the heat of fusion and Mz / Mw measured by DSC tend to be relatively higher than in the latter case (E is C (carbon atom)), while in the latter case, the distribution of melting points and molecular weight measured by DSC is slightly narrower than in the former, and the crystallization temperature tends to be slightly higher than in the former. This is because the former has more restricted degrees of rotational freedom than the latter, making it easier to generate high molecular weight components, while the latter is considered to have a structure with less conformational change in the cyclic structure compared to the former, so the molecular weight distribution and melting point distribution are slightly narrower than in the former, i.e., it is easier to form crystals with relatively high uniformity, and therefore the crystallization temperature is higher.

[0068] As described above, by using the solid titanium catalyst component (I) of the present invention, it is possible to produce olefin polymers with various desired properties in the olefin polymerization method described later, depending on the selection of the cyclic organic compound (a). However, the scope of the present invention is not limited by the above-mentioned assumptions.

[0069] In addition to the cyclic organic compound (a) described above, magnesium compounds and titanium compounds are used to prepare the solid titanium catalyst component (I) of the present invention.

[0070] [Ester compounds, carbamate compounds (cyclic organic compounds (a'))] Some of the compounds of cyclic organic compounds (a) according to the present invention are novel compounds. Specifically, the basic skeleton is the same as general formula (1) of cyclic organic compound (a), but it is represented by the following general formula (2) with a different substituent structure.

[0071] In formula (2), C is a carbon atom, and E, E １ and E １’ Each of these atoms is selected from the group consisting of carbon atoms and elements of Group 15 of the periodic table, and R ａ , R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’ Each of these is a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, and a heteroatom-containing hydrocarbon group, and R １ , R ２ , R ３ and R ４ It can directly bond and form multiple bonds, R １’ , R ２’ , R ３’ and R ４’ They can directly bond and form multiple bonds, and there are multiple R ３ and R ３’ Each of them is an ester group (-COOR ｅ ) and R ｅ is a primary or secondary hydrocarbon group having two or more carbon atoms, l is an integer from 0 to 2, and m and n are integers from 1 to 10, respectively.

[0072] The aforementioned E, E １ and E １’ When is a Group 15 element, it is preferably nitrogen and phosphorus, and more preferably nitrogen. E is particularly preferably C (carbon atom) or N (nitrogen atom).１ and E １’ Preferably at least one of them is C (carbon atom). Furthermore, E, E １ and E １’ Preferably, at least one of these elements is a Group 15 element, and more preferably, it is N (nitrogen atom). Compounds specified by such formula (2) may hereafter be referred to as cyclic compounds (a').

[0073] R ａ , R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’ Two or more of these can bond to each other to form a monocycle or polycycle. In the cyclic organic compound (a') of the present invention, R １ , R ２ , R ３ and R ４ It can directly bond and form multiple bonds, R １’ , R ２’ , R ３’ and R ４’ While multiple bonds can be formed by direct bonding, such multiple bonds can be considered a special case of the aforementioned forms of monocyclic or polycyclic bonding. Typically, such multiple bonds can be formed by multiple substituents directly bonded to adjacent carbon atoms, or by multiple substituents bonded to the same carbon atom (for example, multiple R atoms). ２ This also includes embodiments in which ) directly bond to form a multiple bond.

[0074] Also, there are multiple R ２ , R ３ , R ４ , R ２’ , R ３’ and R ４’ These may be the same group or different groups.

[0075] Among the above, R ａ , R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R３’ and R ４’ It is preferable that the relationships are independent. In the present invention, the independent relationships are synonymous with the configuration in which the plurality of substituents do not bond to each other to form a ring structure of three or more members.

[0076] In the above general formula (2), E, ​​E １ , E １’ , R ａ , R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’ The specific structural example is basically the same as the general formula (1) above, R ３ , R ３’ , R ｅ The difference lies in the fact that the numerical range of l is limited to the aforementioned range.

[0077] In the general formula (2) of the present invention, the plurality of R ３ and R ３’ Each of these is an ester group. The aforementioned ester group is "-COOR ｅ It is a so-called C-ester group having the structure of " and the R ｅ R is a primary or secondary hydrocarbon group having two or more carbon atoms. ｅ For example, R ａ , R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’ Among the substituents exemplified above, those that satisfy the requirement of being a primary or secondary hydrocarbon group with two or more carbon atoms can be cited as preferred examples. In this invention, so-called aryl groups such as phenyl groups are secondary hydrocarbon groups. Also, the ester group ("-COOR") ｅ One or more E that are joined by '' are R ２ , R ４ , R ２’ and R ４’It is preferable that the structure is directly bonded to any of the carbon atoms forming the cyclic skeleton to which it is bonded. Hereafter, the positional relationship between E and carbon as shown above may be described as "adjacent positions".

[0078] In the above general formula (2), R ｅ A preferred embodiment is a primary or secondary hydrocarbon group having 2 to 15 carbon atoms, more preferably 2 to 12 carbon atoms, even more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 8 carbon atoms. More specifically, examples include alkyl groups such as ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, hexyl group, octyl group, and decyl group; alkenyl groups such as vinyl group, isopropenyl group, butenyl group, and hexenyl group; phenyl group, naphthyl group, and their derivatives such as aryl group.

[0079] A key feature of the present invention is that the substituents bond to E in formula (2). These substituents themselves, or the surrounding region containing these groups, are considered important structures that exhibit the main electron-donating properties of the present invention.

[0080] In the above general formula (2), among the substituents, there are multiple R ３ and R ３’ A preferred embodiment is one in which an ester group is present. In this case, substituent R other than the ester group is also present. ３ (Hereinafter, R ３ (Sometimes denoted as (W).) is preferably hydrogen or a hydrocarbon group, and more preferably the hydrocarbon group contains only carbon and hydrogen. In particular the R ３ A configuration in which (W) is hydrogen is preferred.

[0081] In the above general formula (2) of the present invention, R １ , R ２ , R ４ , R １’ , R ２’ and R ４’ It is preferably a hydrocarbon group that does not contain a carbonyl group, and more preferably a hydrocarbon group that contains only carbon and hydrogen. Even more preferably, R １ , R ２ , R ４ , R１’ , R ２’ and R ４’ A configuration in which one or more of are hydrogen is preferred. Particularly preferred is R ２ , R ４ , R ２’ and R ４’ This is a mode in which one or more of the elements are hydrogen. On the other hand, R １ , R １’ Hydrogen or an absence of hydrogen is preferred (see the examples below).

[0082] Other preferred embodiments include R ２ , R ３ , R ４ , R ２’ , R ３’ and R ４’ One example is a configuration in which one or more of the atoms are hydrogen atoms. More preferably, １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’ This is a configuration in which one or more atoms are hydrogen atoms.

[0083] In formula (2) of the present invention, l is an integer between 0 and 2, preferably 0 and 1, and more preferably 0.

[0084] Similar to the cyclic organic compound (a) described above, a suitable application for the above-mentioned cyclic organic compound (a) is as an internal donor for a solid titanium catalyst component.

[0085] Examples of such cyclic organic compounds (a') include the following structures. Note that the structural formulas of the example compounds below include those with stereoisomers; some are shown with their isomer structures, but others may include isomer structures not shown. Furthermore, some of the compounds below are identical to the example compounds of cyclic organic compound (a) mentioned above.

[0086]

[0087]

[0088]

[0089]

[0090] Similar to the cyclic organic compound (a) described above, in the above structural formula, the methyl group is represented as "Me," the ethyl group as "Et," the propyl group as "Pr," the butyl group as "Bu," and the phenyl group as "Ph." Also, "n" indicates "normal," "i" indicates "iso," and "t" indicates "tertiary." Furthermore, carbon atoms are present at the vertices and ends of the above structural formula, and "-" indicates a covalent bond. This form of compound structural formula is well known to those skilled in the art. Note that in some cases, the symbols indicating isomers are not attached to "Pr" and "Bu." These can basically be recognized as "normal," but other isomeric forms may also be included.

[0091] <Method for producing cyclic organic compound (a) and cyclic organic compound (a')> The method for producing the cyclic organic compound (a) and the cyclic organic compound (a') (hereinafter, these may be collectively referred to as "cyclic organic compound (aA)") is not particularly limited, and for example, the "synthesis examples" in the examples described later can be used. Alternatively, the cyclic organic compound (aA) may be synthesized using known reactions. The cyclic organic compound (aA) may also be synthesized by a so-called coupling reaction, in which each part is synthesized using known synthesis methods and then joined together using known methods. More specifically, it can be produced using reactions as described later. Below, we will mainly introduce synthesis examples of the cyclic organic compound (a') (carbamate compound, ester compound).

[0092] The dicarbamate compounds according to the present invention can be synthesized, for example, by the reaction of a diamine compound with a chloroformate ester in the presence of a base, as shown in reaction formula 1 below. The diamine compound used may be the corresponding hydrochloride salt. The base used is not particularly limited, but examples include triethylamine, N,N-diisopropylethylamine, pyridine, sodium hydroxide, potassium hydroxide, and sodium hydride.

[0093]

[0094] Furthermore, another method for producing the dicarbamate compound generated in reaction formula 1 above is to react a diamine compound with a dicarbonate diester, as shown in reaction formula 2 below.

[0095]

[0096] Furthermore, the dicarbamate compound can also be produced by reacting a diamine compound with a diester carbonate, as shown in reaction formula 3 below.

[0097]

[0098] The diester compounds according to the present invention can be synthesized, for example, by a coupling reaction using a transition metal catalyst, as shown in reaction formula 4 below. Examples of the transition metal catalyst include palladium, nickel, and copper.

[0099]

[0100] The method for producing the cyclic organic compound (aA) of the present invention is not limited to the method described above, and it is also possible to produce it by combining known synthesis reactions.

[0101] As described above, the cyclic organic compound (aA) of the present invention is suitable as an internal donor component for solid titanium catalysts, but it can also be used in other known applications as appropriate. For example, because it has a relatively large hydrocarbon structure relative to multiple ester groups and carbamate groups, it is possible that it can be applied as a surfactant or antistatic agent. Taking advantage of its unique structure, it has the potential to be developed for various applications, and the industrial value of the present invention is considered to be high.

[0102] <Magnesium Compounds> Examples of such magnesium compounds include: magnesium halides such as magnesium chloride and magnesium bromide; alkoxymagnesium halides such as magnesium methoxychloride, magnesium ethoxychloride, and magnesium phenoxychloride; alkoxymagnesiums such as magnesium ethoxymagnesium, magnesium isopropoxy, magnesium butoxy, and magnesium 2-ethylhexoxymagnesium; allyloxymagnesium such as magnesium phenoxymagnesium; and magnesium carboxylates such as magnesium stearate.

[0103] These magnesium compounds may be used individually or in combination of two or more. Furthermore, these magnesium compounds may be complex compounds, polycompounds, or mixtures with other metal compounds.

[0104] Among these, magnesium compounds containing halogens are preferred. Magnesium halides, particularly magnesium chloride, are preferred. In addition, alkoxymagnesium compounds such as ethoxymagnesium are also preferred. Furthermore, the magnesium compound may be derived from other substances, for example, obtained by contacting an organomagnesium compound such as a Grignard reagent with titanium halide, silicon halide, or halogenated alcohol.

[0105] <Titanium Compounds> Examples of titanium compounds include those with the general formula: Ti(OR') g X 4-gExamples of tetravalent titanium compounds can be given as shown by (where R' is a hydrocarbon group, X is a halogen atom, and g is 0 ≤ g ≤ 4). More specifically, examples include titanium tetrahalides such as TiCl4 and TiBr4; trihalogenated alkoxytitaniums such as Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(O-n-C4H9)Cl3, Ti(OC2H5)Br3, and Ti(O-iso-C4H9)Br3; dihalogenated alkoxytitaniums such as Ti(OCH3)2Cl2 and Ti(OC2H5)2Cl2; monohalogenated alkoxytitaniums such as Ti(OCH3)3Cl, Ti(O-n-C4H9)3Cl, and Ti(OC2H5)3Br; and tetraalkoxytitaniums such as Ti(OCH3)4, Ti(OC2H5)4, Ti(OC4H9)4, and Ti(O-2-ethylhexyl)4.

[0106] Among these, titanium tetrahalides are preferred, and titanium tetrachloride is particularly preferred. These titanium compounds may be used individually or in combination of two or more. Examples of the magnesium and titanium compounds described above include those described in detail in Patent Documents 1 and 2, for example.

[0107] In preparing the solid titanium catalyst component (I) used in the present invention, known methods can be used without limitation, except for the use of a cyclic organic compound (a). Specific preferred methods include, for example, the methods (P-1) to (P-4) described below.

[0108] (P-1) A method of contacting a solid adduct consisting of a magnesium compound and a catalyst component (b), a cyclic organic compound (a), and a liquid titanium compound in a suspended state in the presence of an inert hydrocarbon solvent.

[0109] (P-2) A method of contacting a solid adduct consisting of a magnesium compound and a catalyst component (b) with a cyclic organic compound (a) and a liquid titanium compound in multiple separate steps.

[0110] (P-3) A method of contacting a solid adduct consisting of a magnesium compound and catalyst component (b), a cyclic organic compound (a), and a liquid titanium compound in a suspended state in the presence of an inert hydrocarbon solvent, and in multiple stages.

[0111] (P-4) A method of contacting a liquid magnesium compound, comprising a magnesium compound and catalyst component (b), a liquid titanium compound, and a cyclic organic compound (a).

[0112] The reaction temperature is preferably in the range of -30°C to 150°C, more preferably -25°C to 130°C, and even more preferably -25°C to 120°C.

[0113] Furthermore, the production of the above-mentioned solid titanium catalyst component can be carried out in the presence of a known medium as needed. Examples of such mediums include aromatic hydrocarbons such as toluene, which have some polarity, and known aliphatic hydrocarbons and alicyclic hydrocarbon compounds such as heptane, octane, decane, and cyclohexane. Among these, aliphatic hydrocarbons are preferred examples.

[0114] By carrying out the reaction within the above range, it is possible to obtain polymers with a broad molecular weight distribution while simultaneously achieving a higher level of activity and stereoregularity in the resulting polymers.

[0115] (Catalyst component (b)) The catalyst component (b) used for forming the above-mentioned solid adduct or liquid magnesium compound is preferably a known compound that can solubilize the above-mentioned magnesium compound in a temperature range of room temperature to about 300°C, such as alcohols, aldehydes, amines, carboxylic acids, and mixtures thereof. Examples of such compounds include those described in detail in Patent Document 1 and Patent Document 2.

[0116] More specifically, examples of alcohols having the ability to solubilize magnesium compounds include: aliphatic alcohols such as methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, and dodecanol; alicyclic alcohols such as cyclohexanol and methylcyclohexanol; aromatic alcohols such as benzyl alcohol and methylbenzyl alcohol; and aliphatic alcohols having an alkoxy group such as n-butyl cellulose.

[0117] Examples of carboxylic acids include organic carboxylic acids with 7 or more carbon atoms, such as caprylic acid and 2-ethylhexanoic acid. Examples of aldehydes include aldehydes with 7 or more carbon atoms, such as capric aldehyde and 2-ethylhexyl aldehyde.

[0118] Examples of amines include amines with six or more carbon atoms, such as heptylamine, octylamine, nonylamine, laurylamine, and 2-ethylhexylamine.

[0119] The catalyst component (b) above is preferably one of the alcohols listed above, and particularly preferably ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, decanol, etc.

[0120] The amount of magnesium compound and catalyst component (b) used when preparing the above-mentioned solid adduct or liquid magnesium compound varies depending on the type and contact conditions, but the magnesium compound is used in an amount of 0.1 to 20 moles / liter, preferably 0.5 to 5 moles / liter, per unit volume of catalyst component (b). In addition, an inert medium for the above-mentioned solid adduct can be used in combination as needed. As the above-mentioned medium, known hydrocarbon compounds such as heptane, octane, and decane are given as preferred examples.

[0121] The composition ratio of magnesium to catalyst component (b) in the resulting solid adduct or liquid magnesium compound cannot be specified in general terms as it varies depending on the type of compound used. However, for every mole of magnesium in the magnesium compound, the amount of catalyst component (b) is preferably 2.0 moles or more, more preferably 2.2 moles or more, even more preferably 2.6 moles or more, particularly preferably 2.7 moles or more, and preferably 5 moles or less.

[0122] <Aromatic carboxylic acid esters and / or compounds having two or more ether bonds via multiple carbon atoms> The solid titanium catalyst component (I) of the present invention may further contain aromatic carboxylic acid esters and / or compounds having two or more ether bonds via multiple carbon atoms (hereinafter also referred to as "catalyst component (c)"). When the solid titanium catalyst component (I) of the present invention contains catalyst component (c), its activity and stereoregularity may be enhanced, or its molecular weight distribution may be broadened.

[0123] As this catalyst component (c), any known aromatic carboxylic acid esters or polyether compounds that have been conventionally used as catalysts for olefin polymerization, such as those described in Patent Document 2 or Japanese Patent Application Publication No. 2001-354714, can be used without limitation.

[0124] Examples of aromatic carboxylic acid esters include aromatic carboxylic acid monoesters such as benzoic acid esters and toluic acid esters, as well as aromatic polycarboxylic acid esters such as phthalate esters. Among these, aromatic polycarboxylic acid esters are preferred, and phthalate esters are more preferred. Among these phthalate esters, alkyl phthalate esters such as ethyl phthalate, n-butyl phthalate, isobutyl phthalate, hexyl phthalate, and heptyl phthalate are preferred, and diisobutyl phthalate is particularly preferred.

[0125] More specifically, examples of the polyether compound include compounds represented by the following formula (3).

[0126]

[0127] In the above formula (3), m is an integer between 1 and 10, more preferably an integer between 3 and 10, and R 11 , R 12 , R 31 ~R 36 Each substituent has a hydrogen atom or at least one element selected from carbon, hydrogen, oxygen, fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron, and silicon.

[0128] If m is 2 or greater, there are multiple R 11 and R 12 These may be the same or different. Any R 11 , R 12 , R 31 ~R 36 Preferably R 11 and R 12 These may jointly form rings other than a benzene ring.

[0129] A specific example of such a compound is 2-isopropyl-1 , 3-Dimethoxypropane, 2-S-Butyl-1 , 3-Dimethoxypropane, 2-Cumyl-1 , 3-Dimethoxypropane and other monosubstituted dialkoxypropanes; 2-Isopropyl-2-Isobutyl-1 , 3-dimethoxypropane, 2 , 2-Dicyclohexyl-1 , 3-Dimethoxypropane, 2-Methyl-2-Isopropyl-1 , 3-Dimethoxypropane, 2-methyl-2-cyclohexyl-1 , 3-Dimethoxypropane, 2-Methyl-2-Isobutyl-1 , 3-dimethoxypropane, 2 , 2-Diisobutyl-1 , 3-dimethoxypropane, 2 , 2-Bis(cyclohexylmethyl)-1 , 3-dimethoxypropane, 2 , 2-Diisobutyl-1 , 3-Diethoxypropane, 2 , 2-Diisobutyl-1 ,3-Dibutoxypropane, 2 , 2-di-s-butyl-1 , 3-dimethoxypropane, 2 , 2-Dineopentyl-1 , 3-Dimethoxypropane, 2-Isopropyl-2-Isopentyl-1 , 3-Dimethoxypropane, 2-Cyclohexyl-2-Cyclohexylmethyl-1 , 3-Dimethoxypropane and other disubstituted dialkoxypropanes; 2 , 3-Dicyclohexyl-1 , 4-Diethoxybutane, 2 , 3-Dicyclohexyl-1 , 4-Diethoxybutane, 2 , 3-Diisopropyl-1 , 4-Diethoxybutane, 2 , 4-diphenyl-1 , 5-Dimethoxypentane, 2 , 5-diphenyl-1 , 5-dimethoxyhexane, 2 , 4-Diisopropyl-1 , 5-Dimethoxypentane, 2 , 4-Diisobutyl-1 , 5-Dimethoxypentane, 2 , 4-Diisoamyl-1 , Dialkoxyalkanes such as 5-dimethoxypentane; 2-methyl-2-methoxymethyl-1 , 3-Dimethoxypropane, 2-Cyclohexyl-2-Ethoxymethyl-1 , 3-Diethoxypropane, 2-Cyclohexyl-2-Methoxymethyl-1 , Trialkoxyalkanes such as 3-dimethoxypropane; 2 , 2-Diisobutyl-1 , 3-Dimethoxy-4-cyclohexenyl, 2-Isopropyl-2-isoamyl-1 , 3-Dimethoxy-4-cyclohexenyl, 2-cyclohexyl-2-methoxymethyl-1 , 3-Dimethoxy-4-cyclohexenyl, 2-Isopropyl-2-methoxymethyl-1 ,3-Dimethoxy-4-cyclohexenyl, 2-Isobutyl-2-methoxymethyl-1 , 3-Dimethoxy-4-cyclohexenyl, 2-cyclohexyl-2-ethoxymethyl-1 , 3-Dimethoxy-4-cyclohexenyl, 2-Isopropyl-2-ethoxymethyl-1 , 3-Dimethoxy-4-cyclohexenyl, 2-Isobutyl-2-ethoxymethyl-1 , Examples include dialoxycycloalkanes such as 3-dimethoxy-4-cyclohexenyl.

[0130] Of these, 1 , 3-diethers are preferred, and in particular 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 is preferred. These compounds may be used individually or in combination of two or more.

[0131] The cyclic organic compound (a), catalyst component (b), and catalyst component (c) described above can be considered to belong to a group of components called electron donors by the company in question. These electron donor components are known to exhibit effects such as enhancing the stereoregularity of the resulting polymer while maintaining high catalytic activity, controlling the compositional distribution of the resulting copolymer, and acting as a flocculant to control the particle shape and size of the catalyst particles. In the present invention, based on the results of the examples described later, the influence of the cyclic organic compound (a) is considered to be particularly strong.

[0132] The cyclic organic compound (a) of the present invention is also thought to demonstrate the effect of further controlling the molecular weight distribution by an electron donor.

[0133] In the solid titanium catalyst component (I) used in the present invention, the halogen / titanium (atomic ratio) (i.e., the number of moles of halogen atoms / the number of moles of titanium atoms) is preferably 2 to 100, more preferably 4 to 90, the cyclic organic compound (a) / titanium (molar ratio) (i.e., the number of moles of cyclic organic compound (a) / the number of moles of titanium atoms) is preferably 0.01 to 100, more preferably 0.2 to 10, the catalyst component (b) / titanium atom (molar ratio) of catalyst component (b) and catalyst component (c) is preferably 0 to 100, more preferably 0 to 10, and the catalyst component (c) / titanium atom (molar ratio) is preferably 0 to 100, more preferably 0 to 10. The magnesium / titanium (atomic ratio) (i.e., the number of moles of magnesium atoms / the number of moles of titanium atoms) is preferably 2 to 100, more preferably 4 to 50.

[0134] Furthermore, the content of components other than the aforementioned cyclic organic compound (a), such as catalyst component (b) and catalyst component (c), is preferably 20% by mass or less, and more preferably 10% by mass or less, relative to 100% by mass of the cyclic organic compound (a).

[0135] As for more detailed preparation conditions for the solid titanium catalyst component (1), other than using a cyclic organic compound (a), conditions described in, for example, EP585869A1 (European Patent Application Publication No. 0585869) and Patent Document 2 can be preferably used.

[0136] [Catalyst for Olefin Polymerization] The catalyst for olefin polymerization according to the present invention is characterized by comprising the above-mentioned solid titanium catalyst component (I) and an organometallic compound catalyst component (II) containing a metal element selected from Group 1, Group 2, and Group 13 of the periodic table.

[0137] <Organometallic Compound Catalyst Component (II)> As the organometallic compound catalyst component (II), compounds containing a group 13 metal, such as organoaluminum compounds, complex alkylates of group 1 metals and aluminum, and organometallic compounds of group 2 metals can be used. Among these, organoaluminum compounds are preferred. Specifically, as organometallic compound catalyst components (II), the organometallic compound catalyst components described in known literature such as EP585869A1 can be cited as preferred examples.

[0138] <Electron Donor (III)> The olefin polymerization catalyst of the present invention may also contain an electron donor (III) as needed, together with the organometallic compound catalyst component (II) described above. Preferably, the electron donor (III) is an organosilicon compound. Examples of this organosilicon compound include compounds represented by the following general formula (4). R S n Si (OR) 4-n ...(4) In formula (4), R S And R'' is a hydrocarbon group, and n is an integer between 0 and 4.

[0139] Specific examples of organosilicon compounds represented by the general formula (4) above include diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, and cyclopentyldimethylethoxysilane.

[0140] Of these, vinyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, and dicyclopentyldimethoxysilane are preferably used.

[0141] Furthermore, the silane compound represented by the following formula (5), as described in International Publication No. 2004 / 016662, is also a preferred example of the organosilicon compound. Si(OR a )3(NR b R c ) ... (5)

[0142] In formula (5), R a R is a hydrocarbon group having 1 to 6 carbon atoms. a Examples include unsaturated or saturated aliphatic hydrocarbon groups having 1 to 6 carbon atoms, with hydrocarbon groups having 2 to 6 carbon atoms being particularly preferred. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n-hexyl group, and cyclohexyl group, among which the ethyl group is particularly preferred.

[0143] In formula (5), R b R is a hydrocarbon group having 1 to 12 carbon atoms or hydrogen, b Examples include unsaturated or saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms, or hydrogen. Specific examples include hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, iso-propyl groups, n-butyl groups, iso-butyl groups, sec-butyl groups, n-pentyl groups, iso-pentyl groups, cyclopentyl groups, n-hexyl groups, cyclohexyl groups, octyl groups, etc., with the ethyl group being particularly preferred among these.

[0144] In formula (5), R c R is a hydrocarbon group having 1 to 12 carbon atoms. cExamples include unsaturated or saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms, or hydrogen. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, octyl group, etc., with the ethyl group being particularly preferred among these.

[0145] Specific examples of compounds represented by the above formula (5) include dimethylaminotriethoxysilane, diethylaminotriethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, diethylaminotri-n-propoxysilane, di-n-propylaminotriethoxysilane, methyl-n-propylaminotriethoxysilane, t-butylaminotriethoxysilane, ethyl-n-propylaminotriethoxysilane, ethyliso-propylaminotriethoxysilane, and methylethylaminotriethoxysilane.

[0146] Furthermore, another example of the organosilicon compound is the compound represented by the following formula (6). N NSi(OR a ) 3 ... (6)

[0147] In formula (6), R N N is a cyclic amino group, and examples of such cyclic amino groups include perhydroquinolino group, perhydroisoquinolino group, 1,2,3,4-tetrahydroquinolino group, 1,2,3,4-tetrahydroisoquinolino group, and octamethyleneimino group.

[0148] Specific examples of compounds represented by formula (6) above include (perhydroquinolino)triethoxysilane, (perhydroisoquinolino)triethoxysilane, (1,2,3,4-tetrahydroquinolino)triethoxysilane, (1,2,3,4-tetrahydroisoquinolino)triethoxysilane, and octamethyleneiminotriethoxysilane. Two or more of these organosilicon compounds can also be used in combination.

[0149] Furthermore, other useful compounds as electron donors (III) include the polyether compounds described as examples of aromatic carboxylic acid esters and / or compounds having two or more ether bonds via multiple carbon atoms (catalyst component (c)).

[0150] Among these polyether compounds, 1 , 3-diethers are preferred, and in particular 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 is preferred. These compounds can be used individually or in combination of two or more.

[0151] When electron donors (III) as described above are used in combination, it is often possible to adjust stereoregularity and molecular weight. Specifically, increasing the proportion of electron donors (III) to the organometallic compound catalyst component tends to result in polymers with high stereoregularity and higher molecular weight. On the other hand, decreasing the proportion of electron donors (III) tends to result in polymers with lower stereoregularity (for example, polymers with a higher decane-soluble component content, as described later) and lower molecular weight.

[0152] Furthermore, the olefin polymerization catalyst of the present invention may contain other components useful for olefin polymerization as needed, in addition to the components described above. Examples of these other components include carriers such as silica, antistatic agents, particle flocculants, and preservative stabilizers.

[0153] [Method for Polymerizing Olefins] The olefin polymerization method according to the present invention is characterized by carrying out olefin polymerization using the olefin polymerization catalyst of the present invention. In the present invention, "polymerization" may include not only homopolymerization but also copolymerization such as random copolymerization and block copolymerization.

[0154] In the olefin polymerization method of the present invention, it is also possible to carry out the main polymerization in the presence of a prepolymerization catalyst obtained by prepolymerizing α-olefin in the presence of the olefin polymerization catalyst of the present invention. This prepolymerization is carried out by prepolymerizing α-olefin in an amount of 0.1 to 1000 g, preferably 0.3 to 500 g, and particularly preferably 1 to 200 g per gram of olefin polymerization catalyst.

[0155] In prepolymerization, the catalyst can be used at a higher concentration than the catalyst concentration in the system during main polymerization. The concentration of the solid titanium catalyst component (I) in prepolymerization is preferably in the range of about 0.001 to 200 millimoles, more preferably about 0.01 to 50 millimoles, and more preferably 0.1 to 20 millimoles, in terms of titanium atoms, per liter of liquid medium.

[0156] The amount of the organometallic compound catalyst component (II) in the prepolymerization should be such that 0.1 to 1000 g, preferably 0.3 to 500 g, of polymer is produced per gram of solid titanium catalyst component (I). It is desirable that the amount is typically about 0.1 to 300 moles, preferably about 0.5 to 100 moles, and particularly preferably 1 to 50 moles, per mole of titanium atoms in the solid titanium catalyst component (I).

[0157] In the prepolymerization, the electron donor (III) and other components may be used as needed. In this case, these components are used in an amount of 0.1 to 50 moles, preferably 0.5 to 30 moles, and more preferably 1 to 10 moles, per mole of titanium atoms in the solid titanium catalyst component (I). By adjusting the amount of the electron donor (III), the stereoregularity of the resulting olefin polymer can sometimes be adjusted.

[0158] Prepolymerization can be carried out under mild conditions by adding the olefin and the above-mentioned catalyst components to an inert hydrocarbon medium.

[0159] In this case, the inert hydrocarbon media used may specifically include: aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cycloheptane, methylcycloheptane, 4-cycloheptane, and methyl-4-cycloheptane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof.

[0160] Among these inert hydrocarbon media, aliphatic hydrocarbons are particularly preferred. When using inert hydrocarbon media, prepolymerization is preferably carried out in a batch manner.

[0161] On the other hand, prepolymerization can be carried out using the olefin itself as the solvent, or it can be carried out in a substantially solvent-free state. In this case, it is preferable to carry out prepolymerization continuously.

[0162] The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described later, and specifically, propylene is preferred.

[0163] The temperature during prepolymerization is typically in the range of approximately -20 to +100°C, preferably approximately -20 to +80°C, and more preferably 0 to +40°C.

[0164] Next, we will describe the main polymerization, which is carried out either after or without the aforementioned prepolymerization.

[0165] Examples of olefins that can be used (i.e., polymerized) in this polymerization include α-olefins having 3 to 20 carbon atoms, such as linear olefins like propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, and branched olefins like 4-methyl-1-pentene, 3-methyl-1-pentene, and 3-methyl-1-butene. Propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and 3-methyl-1-butene are preferred. Furthermore, from the viewpoint that the advantages of polymers with a broad molecular weight distribution are easily expressed in highly rigid resins, propylene, 1-butene, 4-methyl-1-pentene, and 3-methyl-1-butene are particularly preferred.

[0166] Along with these α-olefins, aromatic vinyl compounds such as ethylene, styrene, and allylbenzene; and alicyclic vinyl compounds such as vinylcyclohexane and vinylcycloheptane can also be used. Furthermore, compounds having polyunsaturated bonds, such as conjugated and unconjugated dienes, including cyclopentene, cycloheptene, norbornene, tetracyclododecene, isoprene, and butadiene, can also be used as polymerization raw materials along with ethylene and α-olefins. These compounds may be used individually or in combination of two or more (hereinafter, olefins used together with the above-mentioned ethylene or "α-olefins with 3 to 20 carbon atoms" will also be referred to as "other olefins").

[0167] Among the other olefins mentioned above, ethylene and aromatic vinyl compounds are preferred. In addition, other olefins such as ethylene may be used in combination in small amounts, for example, 10% by mass or less, preferably 5% by mass or less, of the total amount of olefins (100% by mass).

[0168] In the present invention, prepolymerization and main polymerization can be carried out using any of the following methods: liquid-phase polymerization methods such as bulk polymerization, dissolution polymerization, or suspension polymerization, or gas-phase polymerization.

[0169] When this polymerization adopts the reaction mode of slurry polymerization, the reaction solvent can be either an inert hydrocarbon used in the prepolymerization described above, or an olefin that is liquid at the reaction temperature.

[0170] In the polymerization method of the present invention, the solid titanium catalyst component (I) is usually used in an amount of about 0.0001 to 0.5 millimoles, preferably about 0.005 to 0.1 millimoles, when converted to titanium atoms per liter of polymerization volume. The organometallic compound catalyst component (II) is usually used in an amount of about 1 to 2000 moles, preferably about 5 to 500 moles, more preferably 10 to 350 moles, even more preferably 30 to 350 moles, and particularly preferably 50 to 350 moles, per mole of titanium atoms in the prepolymerization catalyst component in the polymerization system. If the electron donor (III) is used, it is used in an amount of 0.001 to 50 moles, preferably 0.01 to 30 moles, and particularly preferably 0.05 to 20 moles, per mole of metal atoms in the organometallic compound catalyst component (II). As described above, the stereoregularity and molecular weight can be adjusted by the amount of electron donor (III) used.

[0171] If this polymerization is carried out in the presence of hydrogen, the molecular weight of the resulting polymer can be adjusted, and a polymer with a high melt flow rate can be obtained.

[0172] In the polymerization of the olefin according to the present invention, the polymerization temperature is usually about 20 to 200°C, preferably about 30 to 100°C, and more preferably 50 to 90°C. The pressure is usually set to atmospheric pressure to 10 MPa, preferably 0.20 to 5 MPa. In the polymerization method of the present invention, polymerization can be carried out by batch, semi-continuous, or continuous methods. Furthermore, polymerization can be carried out in two or more stages by changing the reaction conditions. By performing such multi-stage polymerization, it is possible to further broaden the molecular weight distribution of the olefin polymer.

[0173] The olefin polymer obtained in this way may be a homopolymer, a random copolymer, or a block copolymer. When olefin polymerization, particularly propylene polymerization, is carried out using the above-described catalyst for olefin polymerization, a highly stereoregular propylene polymer is obtained in which the decane-insoluble component content is 70% or more, preferably 85% or more, and particularly preferably 90% or more.

[0174] Furthermore, according to the olefin polymerization method of the present invention, even without multi-stage polymerization, a polyolefin with a broad molecular weight distribution, particularly polypropylene, can be obtained with a small number of polymerization stages, such as single-stage polymerization. In particular, the olefin polymerization method of the present invention is characterized in that it often yields an olefin polymer with a higher proportion of high molecular weight components and a lower proportion of low molecular weight components (especially those called beta components) compared to conventional olefin polymers with equivalent melt flow rates (MFRs). This characteristic can be confirmed by gel permeation chromatography (GPC) measurement described later, and polymers with high Mw / Mn and Mz / Mw values ​​can be obtained.

[0175] Conventional polypropylenes obtained using solid titanium catalyst components containing magnesium, titanium, halogens, and electron donors typically have Mw / Mn values ​​of 5 or less and Mz / Mw values ​​of less than 4, which are indicators of molecular weight distribution determined by GPC measurement, in the region of MFR of 1 to 10 g / 10 min. However, using the olefin polymerization method of the present invention, olefin polymers with Mw / Mn values ​​of 6 to 30, preferably 7 to 20, can be obtained under the same polymerization conditions as described above. Furthermore, olefin polymers with Mz / Mw values ​​of 4 to 15, more preferably 4.5 to 10, can be obtained. In particular, polymers with high Mz / Mw values ​​can often be obtained using the olefin polymerization method of the present invention.

[0176] It is common knowledge among this industry that polypropylene with a high Mw / Mn value exhibits superior moldability and rigidity. On the other hand, a high Mz / Mw value indicates a high proportion of high molecular weight components, and it is expected that the resulting polypropylene will have a high melt tension and excellent moldability.

[0177] The olefin polymerization method of the present invention makes it possible to obtain polymers with a broad molecular weight distribution without performing multi-stage polymerization, potentially simplifying polymer manufacturing equipment. Furthermore, when applied to conventional multi-stage polymerization methods, it is expected that polymers with superior melt tension and moldability can be obtained.

[0178] Other methods for obtaining polymers with a broad molecular weight distribution include dissolving and mixing polymers with different molecular weights, or melt-kneading. However, polymers obtained by these methods may not sufficiently improve melt tension or moldability despite the relatively complicated work involved. This is presumed to be because polymers with different molecular weights are fundamentally difficult to mix. On the other hand, polymers obtained by the olefin polymerization method of the present invention are expected to have high melt tension and excellent moldability because they are a mixture of polymers with an extremely wide range of different molecular weights at the catalyst level, i.e., the nano level.

[0179] Furthermore, as explained with respect to the solid titanium catalyst component (I), by using the olefin polymerization catalyst of the present invention to polymerize olefins, it is possible to selectively produce olefin polymers with various desired properties by selecting the cyclic organic compound (a) contained in the solid titanium catalyst component (I).

[0180] As described above, the polymers obtained by the olefin polymerization method of the present invention have high stereoregularity. Therefore, the olefin polymers obtained by the method of the present invention tend to have a high melting point. The melting point is usually determined by differential scanning calorimetry (DSC).

[0181] As described above, olefin polymers, particularly propylene polymers, obtained by the method of the present invention tend to have a broad molecular weight distribution. More specifically, they tend to exhibit a broad molecular weight distribution that extends to both the high and low molecular weight sides, so (a) the sum of the "Mw / Mn" value and the "Mz / Mw" value tends to be high. Also, (b) the quotient between the "Mz / Mw" value, or the "Mz / Mw" value, and "Mw / Mn" tends to be relatively large, so they may also tend to have a distribution that extends widely towards the high molecular weight side. Olefin polymers obtained by the method of the present invention tend to show high values ​​for (a) and / or (b) above. Particularly preferable is an olefin polymer with high values ​​for both (a) and (b). Since olefin polymers generally have different molecular mobility depending on their molecular weight, in the case of polymers with a broad molecular weight distribution, the chart obtained by DSC measurement may be multi-peaked or broad rather than unimodal.

[0182] On the other hand, the DSC chart of the propylene polymer obtained using the method of the present invention tends to show a broadening towards relatively low temperatures. This suggests that the polymer obtained using the method of the present invention may have a tendency for high stereoregularity, particularly in the low molecular weight components rather than in the ultra-high molecular weight region. In other words, according to the examples of the present invention described later, polymer components with relatively low melting points (e.g., 158°C or below) show an unexpected tendency to have relatively high heat of fusion (ΔH). The reason why polymers with high heat of fusion despite low melting points can be obtained is currently unknown, but the inventors believe that factors such as the following may be involved.

[0183] As described above, the cyclic organic compound (aA) of the present invention has a structure that is somewhat restricted in terms of rotation. Therefore, it is thought that the cyclic organic compound (aA) is prone to undergoing conformational changes due to rotation over time in the vicinity of titanium, which is the active species of the solid titanium catalyst component. Consequently, the time during which it can adopt a conformation that easily yields a highly stereoregular polymer is relatively short, and the molecular weight of the highly stereoregular polymer does not increase sufficiently. As a result, it can be considered that the proportion of polymers that are highly stereoregular but have relatively low molecular weights tends to increase. On the other hand, it is said that if the molecular weight of the polymer is too low, the melting point may not increase. Due to these factors, it can be considered that when using the olefin polymerization catalyst containing the solid titanium catalyst component of the present invention, the heat of fusion (ΔH) in the low melting point region tends to be high.

[0184] The olefin polymers obtained with the olefin polymerization catalyst of the present invention, such as propylene polymers, are often polymers with a relatively high decane-soluble component content. Specifically, this content is 3 to 15% by mass, more preferably 3 to 12% by mass, and even more preferably 4 to 10% by mass.

[0185] Typically, polymers with a high decane-soluble component content tend to have low stereoregularity and low melting points and heats of fusion. However, in the present invention, even with a relatively high amount of decane-soluble component content, there are cases where the heat of fusion is high, which is a unique characteristic. This trend is consistent with the idea that the low molecular weight components may have high stereoregularity, as indicated by the DSC measurement results mentioned above.

[0186] The propylene polymers obtained using the olefin polymerization catalyst of the present invention can be used without limitation for known applications. For example, they are suitably used in extruded sheets, T-die films, inflation films, blow-molded articles, vacuum-formed articles, injection-molded articles, stamping-molded articles, calendered articles, rotational-molded articles, and the like. More specific examples include applications as separators in lithium-ion batteries and capacitors.

[0187] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the following examples, the bulk density, melt flow rate, decane-soluble (insoluble) component content, molecular weight distribution, final melting point, melting point, crystallization temperature, and heat of fusion of the propylene polymer were measured by the following methods.

[0188] (1) Bulk density: Measured according to JIS K-6721. (2) Melt flow rate (MFR): Measured according to ASTM D1238E, with a measurement temperature of 230°C for propylene polymers.

[0189] (3) Amount of decane-soluble (insoluble) components: Approximately 3 grams of propylene polymer (10) in a glass measuring container. -4 The weight was measured to the gram. This weight was represented as b (grams) in the following formula. 500 ml of decane and a small amount of heat-resistant stabilizer soluble in decane were added, and under a nitrogen atmosphere, the mixture was heated to 150°C over 2 hours while stirring with a stirrer to dissolve the propylene polymer. After holding at 150°C for 2 hours, it was slowly cooled to 23°C over 8 hours. The resulting liquid containing the precipitated propylene polymer was filtered under reduced pressure using a glass filter of Tokyo Glass Machinery Co., Ltd., 25G-4 standard. 100 ml of the filtrate was taken and dried under reduced pressure to obtain a portion of the decane-soluble components, and the weight of this was divided into 10 -4 The weight was measured to the nearest gram (this weight is represented as 'a' (grams) in the following formula). After this operation, the amount of decane-soluble component was determined by the following formulas: Decane-soluble component content = 100 × (500 × a) / (100 × b) Decane-insoluble component content = 100 - 100 × (500 × a) / (100 × b)

[0190] (4) Molecular weight distribution: Gel permeation chromatograph: HLC-8321 GPC / HT type manufactured by Tosoh Corporation Detector: Differential refractometer Column: Two TSKgel GMH6-HT and two TSKgel GMH6-HTL columns manufactured by Tosoh Corporation were connected in series. Mobile phase medium: o-dichlorobenzene Flow rate: 1.0 ml / min Measurement temperature: 140°C Calibration curve preparation method: Standard polystyrene samples were used. Sample concentration: 0.1% (w / w) Sample solution volume: 0.4 ml Measurements were taken under these conditions, and the weight-average molecular weight (Mw), number-average molecular weight (Mn), Z-average molecular weight (Mz), and Mw / Mn and Mz / Mw values, which are indicators of molecular weight distribution (MWD), were calculated by analyzing the obtained chromatograms using known methods. The measurement time per sample was 60 minutes.

[0191] (5) Melting point of polymer (Tm): The melting point (Tm), crystallization temperature (Tc), and heat of fusion (ΔH) of the polymer in this invention were measured using a differential scanning calorimeter (DSC) with a Perkin Elmer DSC8500 instrument. 3 to 10 mg of the sample was sealed in an aluminum pan and heated from room temperature to 200°C at 100°C / min. The sample was held at 200°C for 5 minutes and then cooled to 30°C at 10°C / min. The peak temperature observed in this cooling test was defined as the crystallization temperature (Tc), and the heat of fusion, determined by the area of ​​the peak, was defined as ΔH (1st-cool). Subsequently, after being left at 30°C for 5 minutes, the sample was heated a second time to 200°C at 10°C / min. The peak temperature observed in this second heating test was defined as the melting point (Tm) (if multiple peaks were observed, the two higher-temperature points were listed in the table).

[0192] Furthermore, the amount of endothermic heat identified by the area of ​​the peak observed in the second heating test process was defined as ΔH(ΔH(2nd-heat)). In addition, the peak area results of ΔH(2nd-heat) were calculated by dividing them into three temperature ranges: "less than 160°C", "160°C to 165°C", and "greater than 165°C", and the ratio of these areas was defined as ΔH(low), ΔH(mid), and ΔH(high) (the sum of ΔH(low), ΔH(mid), and ΔH(high) was set to 100%). For convenience, in this application, all ΔH-related measurements are given as absolute values ​​(positive values).

[0193] The final melting point (Tmf) of the polymer in this invention was measured using a differential scanning calorimeter (DSC) with a Perkin Elmer DSC8500 instrument. 3–10 mg of the sample was sealed in an aluminum pan and heated from room temperature to 240°C at 80°C / min. The sample was held at 240°C for 1 minute, then cooled to 0°C at 80°C / min. After holding at 0°C for 1 minute, the sample was heated to 150°C at 80°C / min and held at 150°C for 5 minutes. Finally, the sample was heated to 180°C at 1.35°C / min, and the intersection of the tangent to the inflection point on the high-temperature side of the peak obtained in this final heating test and the baseline was adopted as the final melting point (Tmf).

[0194] Tmf can be considered a parameter for evaluating the crystal structure of components exhibiting very high stereoregularity, as well as the ease of crystallization and crystal structure of polymers in the ultra-high molecular weight region, which are generally considered difficult to crystallize. More specifically, the higher the value of Tmf, the more likely the ultra-high molecular weight polymer component is to form crystals with high heat resistance.

[0195] Note that some of the structural formulas of the compounds used in the following examples and comparative examples have stereoisomers. The structural formulas showing the stereoisomers of the exemplified compounds indicate the isomer that is the main component of the compound used in the examples and comparative examples. Furthermore, in this invention, the main component refers to a component that is greater than 50 mol%, preferably 70 mol or more.

[0196] [Example 1] <Preparation of Solid Titanium Catalyst Component [α1]> After thoroughly purging a 1 L glass container with nitrogen, 85.8 g of anhydrous magnesium chloride, 321 g of decane, and 352 g of 2-ethylhexyl alcohol were added and heated at 130°C for 3 hours to obtain a homogeneous solution. 241 g of this solution and 6.43 g of ethyl benzoate were added to the glass container and stirred and mixed at 50°C for 1 hour.

[0197] After the homogeneous solution obtained in this manner was cooled to room temperature, 38.3 ml of this homogeneous solution was added dropwise to 100 ml of titanium tetrachloride, which was kept at -20°C, over 45 minutes while stirring at 300 rpm. After the addition was complete, the temperature of this mixture was raised to 80°C over 3.8 hours, and at 80°C, 1.37 g of compound 1 was added to the mixture. The temperature was then raised again to 120°C over 40 minutes and held at the same temperature with stirring for 35 minutes. After the reaction was complete, the solid portion was collected by thermal filtration, and this solid portion was resuspended in 100 ml of titanium tetrachloride, and the reaction was carried out again at 120°C for 35 minutes. After the reaction was complete, the solid portion was collected again by thermal filtration and thoroughly washed with 100°C decane and room temperature decane until no free titanium compounds were detected in the washings. The solid titanium catalyst component [α1] prepared by the above procedure was stored as a decant slurry, and a portion of it was dried for the purpose of investigating the catalyst composition. The composition of the solid titanium catalyst component [α1] obtained in this way was 0.27% by mass of titanium, 1.6% by mass of magnesium, and 0.1% by mass of 2-ethylhexyl alcohol residue.

[0198]

[0199] <Main Polymerization> In a polymer chamber with an internal volume of 2 liters, 500 g of propylene and 1 NL of hydrogen were added at room temperature. Then, a mixture of 7 ml of heptane, 0.5 mmol of triethylaluminum, 0.1 mmol of cyclohexylmethyldimethoxysilane, and 0.004 mmol (in terms of titanium atoms) of solid titanium catalyst component [α1] was added and mixed at 25°C for 10 minutes. The temperature inside the polymer chamber was then rapidly raised to 70°C. Polymerization was carried out at 70°C for 1.5 hours, after which the reaction was stopped with a small amount of methanol and the propylene was purged. The resulting polymer particles were then dried under reduced pressure at 80°C overnight. The activity, bulk density, MFR, decane-insoluble component amount, Tm, Tmf, MWD, etc. are shown in Table 1.

[0200] [Example 2] <Preparation of Solid Titanium Catalyst Component [α2]> Solid titanium catalyst component [α2] was obtained in the same manner as in Example 1, except that 1.51 g of compound 2 below was used instead of 1.37 g of compound 1.

[0201]

[0202] <Main Polymerization> Polymerization of propylene was carried out in the same manner as in Example 1, except that solid titanium catalyst component [α2] was used instead of solid titanium catalyst component [α1]. The results are shown in Table 2.

[0203] [Example 3] <Preparation of Solid Titanium Catalyst Component [α3]> Solid titanium catalyst component [α3] was obtained in the same manner as in Example 1, except that 1.51 g of the following compound 3 was used instead of 1.37 g of compound 1.

[0204]

[0205] <Main Polymerization> Polymerization of propylene was carried out in the same manner as in Example 1, except that solid titanium catalyst component [α3] was used instead of solid titanium catalyst component [α1]. The results are shown in Table 1.

[0206] [Example 4] <Preparation of Solid Titanium Catalyst Component [α4]> Solid titanium catalyst component [α4] was obtained in the same manner as in Example 1, except that 1.38 g of the following compound 4 was used instead of 1.37 g of compound 1.

[0207]

[0208] <Main Polymerization> Polymerization of propylene was carried out in the same manner as in Example 1, except that solid titanium catalyst component [α4] was used instead of solid titanium catalyst component [α1]. The results are shown in Table 1.

[0209] [Example 5] <Preparation of Solid Titanium Catalyst Component [α5]> A solid titanium catalyst component [α5] was obtained in the same manner as in Example 1, except that 0.83 g of the following compound 5 was used instead of 1.37 g of compound 1.

[0210]

[0211] <Main Polymerization> Polymerization of propylene was carried out in the same manner as in Example 1, except that solid titanium catalyst component [α5] was used instead of solid titanium catalyst component [α1]. The results are shown in Table 2.

[0212] [Example 6] <Preparation of Solid Titanium Catalyst Component [α6]> Solid titanium catalyst component [α6] was obtained in the same manner as in Example 1, except that 1.65 g of the following compound 6 was used instead of 1.37 g of compound 1.

[0213]

[0214] <Main Polymerization> Polymerization of propylene was carried out in the same manner as in Example 1, except that solid titanium catalyst component [α6] was used instead of solid titanium catalyst component [α1]. The results are shown in Table 2.

[0215] [Example 7] <Preparation of Solid Titanium Catalyst Component [α7]> A solid titanium catalyst component [α7] was obtained in the same manner as in Example 1, except that 1.28 g of the following compound 7 was used instead of 1.37 g of compound 1.

[0216]

[0217] <Main Polymerization> Polymerization of propylene was carried out in the same manner as in Example 1, except that solid titanium catalyst component [α7] was used instead of solid titanium catalyst component [α1]. The results are shown in Table 1.

[0218] [Example 8] <Preparation of Solid Titanium Catalyst Component [α8]> A solid titanium catalyst component [α8] was obtained in the same manner as in Example 1, except that 1.58 g of the following compound 8 was used instead of 1.37 g of compound 1.

[0219]

[0220] <This Polymerization> Propylene polymerization was carried out in the same manner as in Example 1, except that 0.0032 mmol (in terms of titanium atoms) of solid titanium catalyst component [α8] was used instead of solid titanium catalyst component [α1], the amount of triethylaluminum used was changed from 0.5 mmol to 0.4 mmol, and the amount of cyclohexylmethyldimethoxysilane used was changed from 0.10 mmol to 0.08 mmol. The results are shown in Table 1.

[0221] [Example 9] <Preparation of Solid Titanium Catalyst Component [α9]> A solid titanium catalyst component [α9] was obtained in the same manner as in Example 1, except that 2.07 g of the following compound 9 was used instead of 1.37 g of compound 1.

[0222]

[0223] <This polymerization> Propylene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalyst component [α9] was used instead of the solid titanium catalyst component [α1]. The results are shown in Table 1.

[0224] [Comparative Example 1] <Preparation of solid titanium catalyst component [β1]> A solid titanium catalyst component [β1] was obtained in the same manner as in Example 1, except that 1.37 g of the following compound - c1 was used instead of 1.37 g of Compound 1.

[0225]

[0226] <This polymerization> Propylene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalyst component [β1] was used instead of the solid titanium catalyst component [α1]. The results are shown in Table 1.

[0227] [Comparative Example 2] <Preparation of solid titanium catalyst component [β2]> A solid titanium catalyst component [β2] was obtained in the same manner as in Example 1, except that 1.51 g of the following compound - c2 was used instead of 1.26 g of Compound 1.

[0228]

[0229] <This polymerization> Propylene polymerization was carried out in the same manner as in Example 1, except that the solid titanium catalyst component [β2] was used instead of the solid titanium catalyst component [α1]. The results are shown in Table 2.

[0230]

[0231]

[0232] Hereinafter, some synthesis examples of the cyclic organic compounds used in the above examples are disclosed. [Compound analysis method] 1 1H - NMR spectrum (400 MHz, manufactured by JEOL Ltd., JNM - ECZ400S / L1 type measuring device) measurement was carried out, and the peaks were assigned by a conventional method to determine the structure.

[0233] [Synthesis Example 1] The above Compound 8 was synthesized by the following method.

[0234] In a 200 mL three-necked flask containing a well-heated and dried stir bar, 3,3'-bipiperidine (2.58 g, 1 equivalent), dehydrated chloroform (77 mL), and dehydrated pyridine (2.67 g, 2.2 equivalents) were added under a nitrogen atmosphere. After cooling the reaction solution in an ice bath, ethyl chloroformate (3.51 g, 2.1 equivalents) was slowly added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature and stirred for 17.5 hours. Then, the reaction solution was ice-cooled, and dehydrated methanol (3 mL) was added. Water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed three times with water and once with saturated brine, dried over magnesium sulfate, and concentrated using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (developing solvent: hexane:ethyl acetate = 90:10 → 70:30). Then, it was dissolved in 50 mL of ethyl acetate and washed three times with a 1.5% aqueous ammonium chloride solution and once with saturated brine. After drying over magnesium sulfate, it was concentrated using a rotary evaporator to obtain 4.66 g (yield 97%) of Compound 8. The obtained Compound 8's 1 1H-NMR data are shown below.

[0235] 1 1H NMR (400 MHz, CDCl3): δ 4.22 - 3.89 (m, 8H), 2.84 - 2.43 (m, 4H), 1.95 - 1.79 (m, 2H), 1.73 - 1.61 (m, 2H), 1.57 - 1.07 (m, 12H).

[0236] [Synthesis Example 2] Compound 9 was synthesized by the following method.

[0237] In a 200 mL three-necked flask containing a thoroughly heated and dried stirring bar, 6.75 g (2.1 equivalents) of diphenyl carbonate and 80 mL of water were added under a nitrogen atmosphere. Then, 2.52 g (1 equivalent) of 3,3'-bipiperidine dissolved in 14 mL of THF was slowly added dropwise at room temperature, and the mixture was stirred at room temperature for 5 hours. Subsequently, 100 mL of ethyl acetate was added, and the mixture was extracted with ethyl acetate. The organic layer was washed three times with 1% aqueous sodium hydroxide solution, once with saturated brine, and then washed with sodium sulfate. The mixture was then concentrated using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: hexane:ethyl acetate = 91:9 → 80:20 → 50:50) to obtain 5.86 g of compound 9 (yield 96%). 1 The H-NMR data is shown below.

[0238] 1 H NMR (400MHz, CDCl3): δ7.40-7.27 (m, 4H), 7.22-7.14 (m, 2H), 7.13-7.01 (m, 4H), 4.34-3.99 (m, 4H), 3.09-2.56 (m, 4H), 2.05-1.88 (m, 2H), 1.84-1.72 (m, 2H), 1.63-1.42 (m, 4H), 1.39-1.20 (m, 2H).

[0239] [Synthesis Example 3] Compound 4 was synthesized by the following method.

[0240] In a 100 mL three-necked flask containing a thoroughly heated and dried stirring bar, Pd(OAc) was added under a nitrogen atmosphere. 2 ​(0.47 g, 0.1 equivalent), BINAP (1.13 g, 0.15 equivalent), Cs2CO3 (32.78 g, 5 equivalents), and toluene (20 mL) were added and stirred to form a suspension. Then, a toluene (5 mL) solution of ethyl 3-piperidinecarboxylate (4.12 g, 1 equivalent) and ethyl 3-bromobenzoate (4.59 g, 1.3 equivalents) was added, and the mixture was heated under reflux overnight. After cooling to room temperature, the mixture was filtered, and the solid was washed with ethyl acetate. The filtrate was concentrated to obtain the crude product. The crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 100:0 → 70:30) to obtain the target product (4.34 g, yield 71%). 1 The H-NMR data is shown below.

[0241] 1 H NMR (400MHz, CDCl3): δ7.61 (dd, J = 1.4, 2.6 Hz, 1H), 7.51 (dt, J = 1.2, 7.6 Hz, 1H), 7.30 (t, J = 7.8 Hz, 1H), 7.13 (ddd, J = 0.9, 2.7, 8.3 Hz, 1H), 4.37 (q, J = 7.2 Hz, 2H), 4.17 (q, J = 7.2 Hz, 2H), 3.77-3.70 (m, 1H), 3.56-3.48 (m, 1H), 3.09 (dd, J = 9.8, 12.6 Hz, 1H), 2.93-2.82 (m, 1H), 2.73-2.62 (m, 1H), 2.09-1.98 (m, 1H), 1.89-1.77 (m, 1H), 1.76-1.63 (m, 1H), 1.39 (t, J = 7.2 Hz, 3H), 1.28 (t, J = 7.2 Hz, 3H).

Claims

1. A solid titanium catalyst component (I) characterized by containing titanium, magnesium, a halogen, and a cyclic organic compound (a) represented by the following formula (1). [In formula (1), C is a carbon atom, E, E １ and E １’ are atoms selected from a carbon atom and a Group 15 element of the periodic table, and R ａ , R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’ are each a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, and a heteroatom-containing hydrocarbon group, and each one of a plurality of R ３ and R ３’ is a group selected from an ester group and a group containing a carbonyl group (excluding the ester group), l is an integer of 0 to 3, and m and n are each an integer of 1 to 10. ] 2. The solid titanium catalyst component (I) according to claim 1, wherein E is C (carbon atom).

3. The solid titanium catalyst component (I) according to claim 1, wherein m and n are each integers from 2 to 4.

4. The solid titanium catalyst component (I) according to claim 1, wherein l is 0 or 1.

5. A catalyst for olefin polymerization, characterized by comprising a solid titanium catalyst component (I) as described in claim 1, and an organometallic compound catalyst component (II) containing a metal element selected from Group 1, Group 2, and Group 13 of the periodic table.

6. The catalyst for olefin polymerization according to claim 5, further comprising an electron donor (III).

7. A method for polymerizing an olefin, characterized by carrying out polymerization of an olefin in the presence of the catalyst for olefin polymerization described in claim 5 or 6.

8. An ester compound or carbamate compound represented by the following formula (2). [In formula (2), C is a carbon atom, E, E １ and E １’ Each of these atoms is selected from the group consisting of carbon atoms and elements of Group 15 of the periodic table, and R ａ , R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’ Each of these is a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, and a heteroatom-containing hydrocarbon group, and R １ , R ２ , R ３ and R ４ It can directly bond and form multiple bonds, R １’ , R ２’ , R ３’ and R ４’ They can directly bond and form multiple bonds, and there are multiple R ３ and R ３’ Each of them is an ester group (-COOR ｅ ) and R ｅ [where l is a primary or secondary hydrocarbon group having two or more carbon atoms, l is an integer from 0 to 2, and m and n are integers from 1 to 10, respectively.] 9. The aforementioned R ２ , R ３ , R ４ , R ２’ , R ３’ and R ４’ The ester compound or carbamate compound according to claim 8, wherein one or more of the atoms are hydrogen atoms.

10. The aforementioned R １ , R ２ , R ３ , R ４ , R １’ , R ２’ , R ３’ and R ４’ The ester compound or carbamate compound according to claim 8, wherein the substituents are independent of each other.

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