Solid titanium catalyst component, catalyst for olefin polymerization, and olefin polymerization method

Abstract

A solid titanium catalyst component (I) containing titanium, magnesium, a halogen, and a compound (a) represented by formula (1). A catalyst for olefin polymerization, which contains the solid titanium catalyst component (I) and an organometallic compound catalyst component (II) that contains a metal element selected from the group consisting of Group 1, Group 2 and Group 13 of the periodic table. An olefin polymerization method in which olefin polymerization is performed in the presence of the olefin polymerization catalyst.

Description

TECHNICAL FIELD

[0001] The present application relates to a solid titanium catalyst component, a catalyst for olefin polymerization comprising the solid titanium catalyst component, and a method for polymerization of olefin using the catalyst for olefin polymerization. BACKGROUND

[0002] Hitherto, as a catalyst for producing an olefin polymer such as a homopolymer of ethylene or an α-olefin or an ethylene-α-olefin copolymer, a catalyst comprising a titanium compound supported on an active magnesium halide has been known. Hereinafter, "homopolymerization" and "copolymerization" are sometimes collectively referred to as "polymerization".

[0003] As such a catalyst for olefin polymerization, widely known are a catalyst comprising titanium tetrachloride, titanium trichloride, which is called a Ziegler-Natta catalyst; a catalyst comprising a solid titanium catalyst component composed of magnesium, titanium, halogen and an electron donor, and an organometallic compound; and the like.

[0004] The latter catalyst exhibits high activity not only for ethylene but also for polymerization of α-olefins such as propylene and 1-butene. In addition, the resulting α-olefin polymer sometimes has high stereoregularity.

[0005] In the above catalyst, it has been reported that particularly in the case of using a catalyst composed of a solid titanium catalyst component in which an electron donor selected from a carboxylic acid ester typified by phthalate is supported, an aluminum-alkyl compound as a cocatalyst component, and a silicon compound having at least one Si-OR (in the formula, R is a hydrocarbon group), excellent polymerization activity and stereospecificity are exhibited (for example, Patent Literature 1). In addition, various electron donors such as polyether compounds other than phthalate have been studied.

[0006] As a discussion of an ester compound as an electron donor, a catalyst comprising a carboxylic acid ester having an ester group of 2 or more has also been disclosed (for example, Patent Literature 2). The present applicant has also reported an ester compound having a special cyclic structure to provide a polyolefin having a wide molecular weight distribution at high activity (Patent Literatures 3 to 5).

[0007] As a catalyst for providing a polyolefin having a wide molecular weight distribution, a catalyst using a substituted succinate as an electron donor has been reported. The present applicant has also reported a catalyst comprising a polycarboxylic acid ester having a special cyclic structure (Patent Literature 6).

[0008] PRIOR ART DOCUMENTS

[0009] PATENT LITERATURE

[0010] Patent Literature 1: Japanese Patent Application Laid-Open No. 57-63310

[0011] Patent Literature 2: Japanese Patent Application Laid-Open No. 2005-517746

[0012] Patent Literature 3: International Publication No. 2008 / 010459

[0013] Patent Literature 4: International Publication No. 2022 / 045232

[0014] Patent Literature 5: International Publication No. 2022 / 138634

[0015] Patent Literature 6: International Publication No. 2006 / 077945 SUMMARY

[0016] PROBLEMS TO BE SOLVED BY THE INVENTION

[0017] Polypropylene (propylene polymer), which is a typical polymer of an olefin having 3 or more carbon atoms, is known to have a hydrocarbon structure while having a potential to show heat resistance and rigidity rivaling general-purpose engineering plastics. In addition, polyolefins having a hydrocarbon structure are also materials that have a relatively low load on the environment because of less generation of toxic gas at the time of disposal based on combustion and heat recovery (recycling method of recovering combustion heat energy in the form of electric power or the like).

[0018] It is also known that the heat resistance of a propylene polymer greatly depends on its stereoregularity, and the rigidity is affected by the molecular weight distribution in addition to the stereoregularity. For the above stereoregularity, a technology capable of controlling it to a considerably high degree has been developed, but with the recent high-levelization of molding technology, it is considered that a polymer having higher stereoregularity is likely to exhibit unexpected physical properties. By having a wider molecular weight distribution, it is also possible to further improve the balance of physical properties. On the other hand, from the viewpoints of environmental protection and economy, it is required to develop a catalyst showing higher activity. As such a catalyst, for example, the catalysts disclosed in Patent Literatures 4 to 6 described above are examples, and the structure of the electron donor component, which is a feature thereof, is a compound having an alicyclic structure as its main skeleton, and it is seen that a compound having a complex alicyclic structure shows a tendency to exhibit high performance.

[0019] From the above viewpoints, the object of the present application is to provide a solid titanium catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for polymerization of an olefin, which are capable of producing an olefin polymer having higher stereoregularity and excellent molecular weight distribution than ever before with high activity.

[0020] METHOD FOR SOLVING THE PROBLEMS

[0021] The present inventors have conducted intensive studies, and as a result, have found that a solid titanium catalyst component containing a compound having a plurality of functional groups containing specific nitrogen and oxygen has a wide molecular weight distribution, and can produce a polymer having extremely high stereoregularity with high activity, thereby completing the present invention. Note that the main skeleton of the above compound is not limited to an alicyclic structure. Examples of the present invention are shown below.

[0022] [1] A solid titanium catalyst component (I) characterized by containing titanium, magnesium, halogen, and a compound (a) represented by the following formula (1).

[0023] [Chemical Formula 1]

[0024]

[0025] [In formula (1),

[0026] A is a substituent having a "-CR2-R 100 -CR2- " structure,

[0027] R 1 and R 2 are each a substituent having a "R 10 -CR2- " structure,

[0028] R 3 is a hydrogen atom or a substituent having a "R 10 -CR2- " structure,

[0029] R 4 is a substituent selected from a substituent having a "R 10 -CR2- " structure, a substituent having a "R 10 -At 16 - " structure, and a substituent having a "R 10 2-At 15 - " structure,

[0030] At 15 is a Group 15 atom of the periodic table, and At 16 is a Group 16 atom of the periodic table,

[0031] R and R 10 are each a group containing an atom selected from carbon, hydrogen, and Group 15, 16, and 17 elements of the periodic table,

[0032] R 100 is a group containing an atom selected from carbon, hydrogen, and Group 15, 16, and 17 elements of the periodic table, or is a bond selected from a single bond, a double bond, and a triple bond,

[0033] R 1 ~ R 4and A can be bonded to each other to form a single ring or a multiple ring,

[0034] the plurality of R in A and R 100 may be bonded to each other to form a single ring or a multiple ring, and can form a multiple bond.

[0035] [2] The solid titanium catalyst component (I) according to item [1], wherein the R 100 is a group containing an atom selected from carbon, hydrogen, and elements of Group 15, Group 16, and Group 17 of the periodic table.

[0036] [3] The solid titanium catalyst component (I) according to item [1] or [2], wherein A is a cyclic structure.

[0037] [4] The solid titanium catalyst component (I) according to any one of items [1] to [3], wherein A is an aromatic structure.

[0038] [5] The solid titanium catalyst component (I) according to any one of items [1] to [4], wherein the R 3 is a substituent having a "R 10 -CR2-" structure.

[0039] [6] The solid titanium catalyst component (I) according to any one of items [1] to [5], wherein the R 4 is a substituent having a "R 10 -CR2-" structure.

[0040] [7] The solid titanium catalyst component (I) according to any one of items [1] to [6], wherein At 15 is a nitrogen atom.

[0041] [8] The solid titanium catalyst component (I) according to any one of items [1] to [7], wherein At 16 is an oxygen atom.

[0042] [9] An olefin polymerization catalyst characterized by comprising the solid titanium catalyst component (I) according to any one of items [1] to [8], and an organometallic compound catalyst component (II) containing a metal element selected from Group 1, Group 2, and Group 13 of the periodic table.

[0043]

[10] The olefin polymerization catalyst according to item [9], further comprising an electron donor (III).

[0044]

[11] An olefin polymerization method characterized by performing polymerization of an olefin in the presence of the olefin polymerization catalyst according to item [9] or

[10] .

[0045] Effects of the Invention

[0046] According to the present application, it is possible to produce an olefin polymer having a very high stereoregularity, a high melting point, a high heat of fusion, and a wide molecular weight distribution, with a high activity. In addition, in applications such as films, it is possible to produce a polymer that is expected to have an excellent transparency.

[0047] In addition, if the solid titanium catalyst component of the present application, the catalyst for olefin polymerization, and the polymerization method of olefin are used, it is expected that an olefin polymer having not only moldability and rigidity but also a higher heat resistance can be produced. DETAILED DESCRIPTION

[0048] Hereinafter, the solid titanium catalyst component (I), the catalyst for olefin polymerization, the method for producing an olefin polymer, and the propylene polymer of the present application will be described in detail.

[0049] [Solid titanium catalyst component (I)]

[0050] The solid titanium catalyst component (I) of the present application is characterized by containing titanium, magnesium, a halogen, and a compound (a) having a special structure containing a plurality of heteroatoms.

[0051] [Compound (a)]

[0052] The above compound (a) is represented by the following formula (1).

[0053] [Formula (1)]

[0054]

[0055] [In formula (1),

[0056] A is a substituent having a "-CR2-R 100 -CR2- " structure,

[0057] R 1 and R 2 each is a substituent having a "R 10 -CR2- " structure,

[0058] R 3 is a hydrogen atom or a substituent having a "R 10 -CR2- " structure,

[0059] R 4 is a substituent selected from a substituent having a "R 10 -CR2- " structure, a substituent having a "R 10 -At 16 - " structure, and a substituent having a "R 10 2-At 15 - " structure,

[0060] At 15 is a Group 15 atom of the periodic table, At 16 is a Group 16 atom of the periodic table,

[0061] R and R 10 each is a group containing an atom selected from the group consisting of carbon, hydrogen, and Group 15, 16, 17 elements of the periodic table,

[0062] R 100 is a group containing an atom selected from the group consisting of carbon, hydrogen, and Group 15, 16, 17 elements of the periodic table, or is a bond selected from a single bond, a double bond, and a triple bond,

[0063] R 1 ~ R 4 and A can be bonded to each other to form a monocyclic or polycyclic ring,

[0064] a plurality of R and R 100 in A can be bonded to each other to form a monocyclic or polycyclic ring, and can form a multiple bond.

[0065] the above-mentioned Group 15 atom of the periodic table, At 15 is preferably an atom selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, and the like, more preferably an atom selected from the group consisting of nitrogen and phosphorus, and particularly preferably a nitrogen atom.

[0066] the above-mentioned Group 16 atom of the periodic table, At 16 is preferably an atom selected from the group consisting of oxygen, sulfur, selenium, and the like, more preferably an atom selected from the group consisting of oxygen and sulfur, and particularly preferably an oxygen atom.

[0067] Note that the symbol "-" above indicates a covalent bond, and the term "atom" sometimes indicates an atom itself, but this description includes a structure having a covalent bond in a compound, a substituent. For example, in the case of an oxygen atom, the case where it is represented as "-O-" is sometimes referred to as an oxygen atom.

[0068] the above-mentioned R and R 100 each is a group containing an atom selected from the group consisting of carbon, hydrogen, Group 15, 16, 17 elements of the periodic table. As the above-mentioned Group 15, 16 elements, the same elements as the above-mentioned At 15 , At 16 can be exemplified. As the above-mentioned Group 17 elements, fluorine, chlorine, bromine, iodine can be given as preferable examples, more preferably an atom selected from the group consisting of fluorine, chlorine, and bromine, further preferably an atom selected from the group consisting of fluorine and chlorine, and particularly chlorine.

[0069] the above-mentioned R 100 in addition to the same groups as the above-mentioned R and R 10 , includes a case where it represents a bond selected from a single bond, a double bond, and a triple bond. As such a structure, for example, a group having "-CR2-R 100The substituent of the "—CR2—" structure can also be represented by the structural formula defined by the following formula (1-1).

[0070] [Chemical Formula 3]

[0071]

[0072] In the above formula (1-1), n is 0 or 1, R 101 is a group containing an atom selected from carbon, hydrogen, Group 15, Group 16, and Group 17 elements of the periodic table.

[0073] The above R 101 is a group containing the same atom selected from carbon, hydrogen, Group 15, Group 16, and Group 17 elements of the periodic table as the above R 10

[0074] In the above formula (1-1), in the case where n = 0, it corresponds to a structure in which two CR2's are connected by a single bond.

[0075] These substituents can be bonded to each other to form a cyclic structure, a heterocyclic structure, an aromatic structure, or the like. Note that in the present application, unless otherwise specified, a double bond or a triple bond is regarded as one of the cyclic structures as a two-membered ring.

[0076] The above R, R 10 There can be a plurality of these substituents, but each can be the same structure or a different structure. As specific examples of such substituents, there are substituted or unsubstituted hydrocarbon groups having 1 to 30 carbon atoms. As such substituents, there are aliphatic substituents, alicyclic substituents, hydrocarbon groups having 6 to 20 carbon atoms having an aromatic group, and the like. These can be structures containing atoms of Groups 15 to 17 of the periodic table (sometimes referred to as heteroatoms in the present application) as described above. It is preferable that the hydrocarbon groups be composed only of carbon and hydrogen.

[0077] As the above hydrocarbon group, a monovalent hydrocarbon group having 1 to 20, preferably 1 to 10, more preferably 2 to 8, further preferably 4 to 8, particularly preferably 4 to 6 carbon atoms can be preferably exemplified. As such a hydrocarbon group, specifically, there are substituted or unsubstituted aryl groups, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, cyclohexyl group, phenyl group, and the like. Among these, n-butyl group, isobutyl group, hexyl group, octyl group, phenyl group, and the like are preferable, and n-butyl group, isobutyl group, and phenyl group are further preferable.

[0078] ​As mentioned above, the above-mentioned hydrocarbon group can be a hydrocarbon group containing heteroatoms such as nitrogen, oxygen, phosphorus and halogen. As such heteroatoms, particularly oxygen and nitrogen. Such substituents can be selected from known structures. More specifically, groups containing carbonyl structures such as carboxylate groups, aldehyde groups, acetyl groups, oxycarbonyl alkyl groups, alkoxy groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted alkenyloxy groups, substituted or unsubstituted cycloalkoxy groups, substituted or unsubstituted cycloalkenyloxy groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted heteroaryloxy groups, siloxy groups, etc. can be enumerated as suitable examples.

[0079] As the above R 100 , the above R, R 10 The divalent and trivalent structures of the substituent structures exemplified in the above are preferred examples. Specifically, methylene, ethylene, 1,3-propylene, 1-methylethylene (isopropylene), n-butylene, 1-methyl-1,3-propylene (isobutylene), 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 2-ethyl-1,6-hexamethylene, etc., substituted or unsubstituted arylene groups such as phenylene and naphthylene, substituted or unsubstituted cycloalkylene groups such as aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups can be mentioned. Among them, ethylene, propylene, butylene, phenylene, naphthyl, dibenzyl, naphthyl methylene, etc. are preferred.

[0080] In addition, examples include oxymethylene, oxyethylene, 1-oxy, 1,3-propylene, 1-oxy-1-methylethylene, 1-oxy-n-butyl, 1-oxy-1-methylpropylene, 1-oxyhexamethylene; substituted or unsubstituted oxyarylene groups, substituted or unsubstituted oxycycloalkylene groups, such as oxyphenylene and oxynaphthylene; and polyvalent substituents such as dioxymethylene, 1,2-dioxyethylene, 1,3-dioxy, 1,3-propylene, 1,2-dioxy-1-methylethylene, 1,4-dioxy-n-butyl, 1,3-dioxy-1-methylpropylene, 1-oxyhexamethylene; substituted or unsubstituted dioxyarylene groups, substituted or unsubstituted dioxycycloalkylene groups, such as dioxyphenylene and dioxynaphthylene; and polyvalent substituents such as aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and heteroatom-containing groups corresponding to the above. Among them, ethylene, propylene, butylene, phenylene, naphthyl, dibenzyl, naphthalenedimethylene and the like are preferred.

[0081] Furthermore, R 100 Sometimes, it refers to only a bond. That is, A may have a "-CR2-CR2-" structure, a "-RC=CR-" structure, or a carbon-carbon triple bond structure.

[0082] In addition, R 100 It can be bonded with the above R to form a ring structure. 100It directly bonds to the above-mentioned R to form a double bond (which can be regarded as a two-membered ring). In the present invention, it is sometimes preferable to form such a ring structure.

[0083] The above A is a compound having "-CR2-R 100 -CR2-" structure substituent.

[0084] Specific examples of such substituents include the following: 100 The same structure as the example of R 100 The difference is that the element at the terminal portion (the portion bonded to the nitrogen and oxygen of the functional groups such as the carbamate group and amide group described later) is limited to carbon. Therefore, the preferred embodiment is preferably ethylene, propylene, butylene, phenylene, naphthylene, dibenzyl, naphthalenedimethylene, etc. More preferably, it is a bulky branched aliphatic structure, alicyclic structure, or aromatic hydrocarbon group, and more preferably an aromatic structure, and in particular, phenylene, naphthyl, and its substituents can be cited. In particular, naphthyl and substituted naphthyl, more specifically, a structure having a 1,9-naphthalene skeleton.

[0085] As described later, the preferred structure of A is sometimes preferably a relatively rigid structure with minimal displacement as described above. Furthermore, since it is a structure bonded to a carbamate group or an amide group via a heteroatom, a structure containing multiple bonds is preferred. A structure containing multiple bonds is expected to more effectively exhibit electronically active properties.

[0086] The above R 1 and R 2 Each has "R 10 -CR2-" structure substituents. As examples of such substituents, substantially the same as the above R, R 10 The substituents exemplified in the following are generally the same, except that the site of bonding to the nitrogen of the carbamate group described below is limited to carbon. For example, structures such as alkoxy and amino groups bonded to other groups via oxygen or nitrogen are not included. Specific examples of such substituents include ethyl, propyl, isopropyl, n-butyl, isobutyl, hexyl, octyl, and phenyl. Ethyl, propyl, isopropyl, n-butyl, isobutyl, and phenyl are more preferred, and ethyl, propyl, isopropyl, and phenyl are particularly preferred.

[0087] The above R 3 In the above R 1 、R 2 The content obtained by adding hydrogen atoms to the definition of . 10 -CR2-" structure substituent. Therefore, the specific examples of preferred substituents are also the same as R 1 、R 2 same.

[0088] The above R 4For the selected 10 -CR2-" structure, a substituent having "R 10 -At 16 -" structure and the substituents having "R 10 2-At 15 -" structure. 4 Specific example, and the above R, R 10 、R 1 、R 2 The substituents exemplified in are substantially the same. 16 , preferably oxygen, as At 15 , preferably nitrogen. As a specific "R 10 -At 16 -" structure, alkoxy and aryloxy groups can be mentioned, and more specific preferred substituents include ethoxy, propoxy, butoxy, acetoxy, ethylcarbonyloxy, methacryloyloxy, phenoxy, and substituted phenoxy groups.

[0089] As a specific “R 10 -At 15 -" structure, for example, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, methylethylamino, methylpropylamino, diphenylamino, and ditolylamino.

[0090] As shown in formula (1), the compound (a) of the present invention is characterized by having a structure having a carbamate substituent and an amide substituent. In particular, the carbamate substituent is bonded to A via oxygen (O-), and the amide substituent is bonded to A via nitrogen (N-). (In the present invention, the carbamate group and amide group may be simply referred to as functional groups.)

[0091] Since the compound (a) of the present invention has such a specific structure, the solid titanium catalyst component containing this compound tends to have an excellent balance among activity, stereospecificity, molecular weight controllability, reaction control, etc. The reason for such an effect is currently unknown, but the present inventors speculate as follows.

[0092] As described above, in the above-mentioned functional groups bonded to A, the atom directly bonded to A is different elements such as nitrogen and oxygen, and it can be considered that the compound (a) is a structure in which the electron is unbalanced and the electron movement is active due to the electron cloud concentration. Further, each of these functional groups is a group including a structure including two or more heteroatoms, and these heteroatoms are bonded via one carbon atom. From this viewpoint, it is also considered to be a structure that can cause electron cloud concentration. That is, it can be considered to be a structure in which the electron movement is active in a double, triple sense. In addition, since it can also be an asymmetric structure in the molecular structure, it can be expected to be able to form a more diverse active species.

[0093] Since such a diverse active species can be formed, it is expected that a polymer having a wide molecular weight distribution is produced. In addition, it is expected that the concentration of electrons makes the appropriate electron supply to the titanium compound component described later active. This can be one of the main reasons why the polymerization activity is high. In addition, since such a high activity also enables the formation of an active species that can be high molecular weight, it can be considered that, if the solid titanium catalyst component of the present application is used as described later, an olefin polymer in which the molecular weight distribution is extended to the high molecular weight side is easily obtained.

[0094] On the other hand, in the case where too diverse active species are formed, it is possible to easily obtain an active species having low activity and stereospecificity. Therefore, the A substituent of formula (1) is preferably a structure that is somewhat rigid.

[0095] As such a compound (a), the following structures can be exemplified. Note that the structural formula of the following exemplified compounds has stereoisomers, and part of the isomer structures are explicitly described, but sometimes also includes isomer structures not exemplified.

[0096] [Chemical Formula 4]

[0097]

[0098] [Chemical Formula 5]

[0099]

[0100] [Chemical Formula 6]

[0101]

[0102] [Chemical Formula 7]

[0103]

[0104] [Chemical Formula 8]

[0105]

[0106] [Chemical Formula 9]

[0107]

[0108] [Chemical Formula 10]

[0109]

[0110] [Chemical Formula 11]

[0111]

[0112] [Chemical Formula 12]

[0113]

[0114] [Chemical Formula 13]

[0115]

[0116] [Chemical Formula 14]

[0117]

[0118] [Chemical Formula 15]

[0119]

[0120] [Chemical Formula 16]

[0121]

[0122] [Chemical Formula 17]

[0123]

[0124] [Chemical Formula 18]

[0125]

[0126] [Chemical Formula 19]

[0127]

[0128] [Chemical Formula 20]

[0129]

[0130] [Chemical Formula 21]

[0131]

[0132] [Chemical Formula 22]

[0133]

[0134] [Chemical Formula 23]

[0135]

[0136] [Chem. 24]

[0137]

[0138] [Chem. 25]

[0139]

[0140] [Chem. 26]

[0141]

[0142] [Chem. 27]

[0143]

[0144] [Chem. 28]

[0145]

[0146] [Chem. 29]

[0147]

[0148] [Chem. 30]

[0149]

[0150] [Chem. 31]

[0151]

[0152] [Chem. 32]

[0153]

[0154] [Chem. 33]

[0155]

[0156] [Chem. 34]

[0157]

[0158] [Chem. 35]

[0159]

[0160] [Chem. 36]

[0161]

[0162] [Chem. 37]

[0163]

[0164] [Chem. 38]

[0165]

[0166] [Chem. 39]

[0167]

[0168] [Chem. 40]

[0169]

[0170] [Chem. 41]

[0171]

[0172] [Chem. 42]

[0173]

[0174] [Chem. 43]

[0175]

[0176] [Chem. 44]

[0177]

[0178] [Chem. 45]

[0179]

[0180] [Chem. 46]

[0181]

[0182] [Chem. 47]

[0183]

[0184] [Chem. 48]

[0185]

[0186] It should be noted that in the above structural formulas, methyl is represented as "Me", ethyl as "Et", butyl as "Bu", phenyl as "Ph", benzyl as "Bn", cyclohexyl as "Cy", and trifluoromethyl as "CF3". In addition, "i" means "iso", and "t" means "tert".

[0187] These compounds can be used alone or in combination of two or more. In addition, these compounds (a) can be used in combination with the catalyst component (b) and the catalyst component (c) described later, as long as the object of the present application is not impaired.

[0188] In addition, the compound (a) can be formed in the process of producing the solid titanium catalyst component (I).

[0189] In the method for producing the olefin polymer of the present application, there is a tendency that a polymer having a wide molecular weight distribution and a high stereoregularity is easily obtained with high activity.

[0190] In the production of the solid titanium catalyst component (I) of the present application, a magnesium compound and a titanium compound are used in addition to the above-mentioned compound (a).

[0191] <Magnesium compound>

[0192] As such a magnesium compound, specifically, the following can be mentioned:

[0193] Magnesium halides such as magnesium chloride, magnesium bromide;

[0194] Alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, phenoxy magnesium chloride;

[0195] Alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, 2-ethylhexyloxymagnesium;

[0196] Aryloxymagnesium such as phenoxy magnesium;

[0197] Known magnesium compounds such as carboxylates of magnesium such as magnesium stearate.

[0198] These magnesium compounds can be used alone or in combination of two or more. In addition, these magnesium compounds can be a coordination compound with other metals, a complex, or a mixture with other metal compounds.

[0199] Among them, magnesium compounds containing halogen are preferred. It is preferred to use magnesium halides, particularly magnesium chloride. In addition, it is also preferred to use alkoxymagnesium such as ethoxymagnesium. In addition, the magnesium compound can be a substance derived from other substances, for example, a substance obtained by contacting an organomagnesium compound such as Grignard reagent with a titanium halide, a silicon halide, a halogenated alcohol, or the like.

[0200] <Titanium compound>

[0201] As the titanium compound, for example, a tetravalent titanium compound represented by the following general formula can be mentioned.

[0202] Ti(OR') g X 4-g (R' is a hydrocarbon group, X is a halogen atom, and g is 0 ≤ g ≤ 4.)

[0203] More specifically, there can be mentioned:

[0204] Titanium tetrachloride, titanium tetrabromide, and the like;

[0205] Titanium trialkoxychloride such as Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(O-n-C4H9)Cl3, Ti(OC2H5)Br3, Ti(O-iso-C4H9)Br3, and the like;

[0206] Titanium dialkoxychloride such as Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2, and the like;

[0207] Titanium monoalkoxychloride such as Ti(OCH3)3Cl, Ti(O-n-C4H9)3Cl, Ti(OC2H5)3Br, and the like;

[0208] Titanium tetraalkoxide such as Ti(OCH3)4, Ti(OC2H5)4, Ti(OC4H9)4, Ti(O-2-ethylhexyl)4, and the like.

[0209] Among them, titanium tetrachloride is preferred, and titanium tetrachloride is particularly preferred. These titanium compounds can be used alone or in combination of two or more.

[0210] As the magnesium compound and the titanium compound as described above, there can be mentioned, for example, the compounds described in detail in Patent Document 1, Patent Document 2, and the like.

[0211] <Method for producing solid titanium catalyst component>

[0212] In the production of the solid titanium catalyst component (I) used in the present application, in addition to the use of the compound (a), publicly known methods can be used without any limitation. As a specific preferred method, there can be mentioned, for example, the methods of (P-1) to (P-4) described below.

[0213] (P-1) A method in which a solid adduct composed of a magnesium compound and a catalyst component (b), the compound (a), and a titanium compound in a liquid state are contacted in a suspended state in the presence of a non-activated hydrocarbon solvent.

[0214] (P-2) A method in which a solid adduct composed of a magnesium compound and a catalyst component (b), the compound (a), and a titanium compound in a liquid state are contacted in multiple stages.

[0215] (P-3) A method in which a solid adduct composed of a magnesium compound and a catalyst component (b), the compound (a), and a titanium compound in a liquid state are contacted in a suspended state in the presence of a non-activated hydrocarbon solvent, and they are contacted in multiple stages.

[0216] (P-4) A method of bringing into contact a liquid-state magnesium compound composed of a magnesium compound and a catalyst component (b), a liquid-state titanium compound, and a compound (a).

[0217] The reaction temperature is preferably in the range of -30°C to 150°C, more preferably in the range of -25°C to 130°C, and further preferably in the range of -25 to 120°C.

[0218] In addition, in the production of the above-mentioned solid titanium catalyst component, it can be performed in the presence of a known medium as needed. As the above-mentioned medium, there can be mentioned a known aromatic hydrocarbon such as toluene having a weak polarity, a known aliphatic hydrocarbon such as heptane, octane, decane, cyclohexane, and an alicyclic hydrocarbon compound, and among them, an aliphatic hydrocarbon can be mentioned as a preferable example.

[0219] If the reaction is performed within the above-mentioned range, it is possible to achieve both a polymer having a wide molecular weight distribution and high activity, and the stereoregularity of the obtained polymer at a higher level.

[0220] < Catalyst component (b) >

[0221] As the catalyst component (b) for forming the above-mentioned solid addition product and liquid-state magnesium compound, a known compound capable of dissolving the above-mentioned magnesium compound in the temperature range of room temperature to about 300°C is preferable, and for example, an alcohol, an aldehyde, an amine, a carboxylic acid, and a mixture thereof, and the like are preferable. As these compounds, for example, the compounds described in detail in Patent Literature 1 and Patent Literature 2 can be mentioned.

[0222] As the alcohol having the ability to dissolve the above-mentioned magnesium compound, more specifically, there can be mentioned:

[0223] methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2- ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, dodecanol, and the like aliphatic alcohol;

[0224] cyclohexanol, methylcyclohexanol, and the like alicyclic alcohol;

[0225] benzyl alcohol, methylbenzyl alcohol, and the like aromatic alcohol;

[0226] n-butyl cellosolve, and the like aliphatic alcohol having an alkoxy group, and the like.

[0227] As the carboxylic acid, there can be mentioned an organic carboxylic acid having 7 or more carbon atoms such as octanoic acid, 2-ethylhexanoic acid, and the like. As the aldehyde, there can be mentioned an aldehyde having 7 or more carbon atoms such as decanal, 2-ethylhexanal, and the like.

[0228] As the amine, there can be mentioned an amine having 6 or more carbon atoms such as heptylamine, octylamine, nonylamine, laurylamine, 2-ethylhexylamine, and the like.

[0229] As the above-mentioned catalyst component (b), the above-mentioned alcohol is preferred, and ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, decanol, and the like are particularly preferred.

[0230] As for the use amount of the magnesium compound and the catalyst component (b) at the time of preparing the above-mentioned solid addition product and the liquid-state magnesium compound, it differs depending on the kind thereof, the contact conditions, and the like, but the use amount of the magnesium compound is 0.1 to 20 moles per liter, and preferably 0.5 to 5 moles per liter, with respect to each unit volume of the catalyst component (b). In addition, a medium which is not active for the above-mentioned solid addition product can also be used as necessary. As the above-mentioned medium, well-known hydrocarbon compounds such as heptane, octane, decane, and the like are preferred.

[0231] The composition ratio of magnesium of the obtained solid addition product, liquid-state magnesium compound, and the catalyst component (b) differs depending on the kind of the compound used, and thus cannot be generalized, but with respect to 1 mole of magnesium in the magnesium compound, the catalyst component (b) is preferably 2.0 moles or more, more preferably 2.2 moles or more, further preferably 2.6 moles or more, particularly preferably 2.7 moles or more, and preferably 5 moles or less.

[0232] <aromatic carboxylic acid ester and / or compound having 2 or more ether bonds separated by a plurality of carbon atoms>

[0233] The solid titanium catalyst component (I) of the present application can further contain an aromatic carboxylic acid ester and / or a compound having 2 or more ether bonds separated by a plurality of carbon atoms (hereinafter also referred to as "catalyst component (c)"). If the solid titanium catalyst component (I) of the present application contains the catalyst component (c), it is sometimes possible to improve the activity, stereoregularity, or make the molecular weight distribution wider.

[0234] As the catalyst component (c), well-known aromatic carboxylic acid esters and polyether compounds which are preferably used in the conventional catalysts for olefin polymerization, such as the compounds described in Patent Document 2, Japanese Patent Application Publication No. 2001-354714, and the like, can be used without any limitation.

[0235] As the aromatic carboxylic acid ester, specifically, aromatic carboxylic acid monoesters such as benzoate, toluic acid ester, and aromatic polycarboxylic acid esters such as phthalic acid esters can be mentioned. Among these, aromatic polycarboxylic acid esters are preferred, and phthalic acid esters are more preferred. As the phthalic acid esters, alkyl phthalic acid esters such as ethyl phthalate, n-butyl phthalate, isobutyl phthalate, hexyl phthalate, heptyl phthalate, and the like are preferred, and diisobutyl phthalate is particularly preferred.

[0236] In addition, as the above-mentioned polyether compound, more specifically, the compound represented by the following formula (3) can be mentioned.

[0237] [Chemical Formula 49]

[0238]

[0239] Note that, in the above formula (3), m is an integer of 1≤m≤10, more preferably an integer of 3≤m≤10, R 11 , R 12 , R 31 to R 36 each are a hydrogen atom or a substituent having at least one element selected from the group consisting of carbon, hydrogen, oxygen, fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron, and silicon.

[0240] In the case where m is 2 or more, a plurality of R 11 and R 12 each can be the same or different. Any of R 11 , R 12 , R 31 to R 36 , preferably R 11 and R 12 may collectively form a ring other than a benzene ring.

[0241] As specific examples of such compounds, the following can be exemplified:

[0242] 1-substituted dialkoxypropanes such as 2-isopropyl-l,3-dimethoxypropane, 2-sec-butyl-l,3-dimethoxypropane, 2-cumyl-l,3-dimethoxypropane, and the like;

[0243] 2,2-dicyclohexyl-l,3-dimethoxypropane, 2-methyl-2-isopropyl-l,3-dimethoxypropane, 2-methyl-2-cyclohexyl-l,3-dimethoxypropane, 2-methyl-2-isobutyl-l,3-dimethoxypropane, 2,2-diisobutyl-l,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-l,3-dimethoxypropane, 2,2-diisobutyl-l,3-diethoxypropane, 2,2-diisobutyl-l,3-dibutoxypropane, 2,2-di-sec-butyl-l,3-dimethoxypropane, 2,2-dineopentyl-l,3-dimethoxypropane, 2-isopropyl-2-isopentyl-l,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-l,3-dimethoxypropane, and the like;

[0244] 2,3-dicyclohexyl-l,4-diethoxybutane, 2,3-diisopropyl-l,4-diethoxybutane, 2,4-diphenyl-l,5-dimethoxypentane, 2 、5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl-1,5-dimethoxy-pentane, 2,4-diisobutyl-1,5-dimethoxy-pentane, 2,4-diisoamyl-1,5-dimethoxy-pentane, and the like dialkoxyalkanes;

[0245] 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane, and the like trialkoxyalkanes;

[0246] 2,2-diisobutyl-1,3-dimethoxy-4-cyclohexenyl, 2-isopropyl-2-isopentyl-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-1,3-dimethoxy-4-cyclohexenyl, and the like dialkoxy cycloalkanes.

[0247] Among these, 1,3-diethers are preferred, and 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 are particularly preferred.

[0248] In addition, of course, the polyhydric ether compounds disclosed in Patent Documents 3 to 5 described above can also be used in combination.

[0249] These compounds can be used singly or in combination of two or more.

[0250] The compound (a), the catalyst component (b), and the catalyst component (c) described above can also be considered to belong to components known as electron donors by those skilled in the art. The electron donor components described above are known to exhibit effects of improving the stereoregularity of the obtained polymer in a state in which the high activity of the catalyst is maintained; effects of controlling the composition distribution of the obtained copolymer; effects of controlling the particle shape and particle size of the catalyst particles; and the like.

[0251] The compound (a) of the present application can also be expected to be able to perform more diverse reaction control by being used in combination with other electron donors.

[0252] In the solid titanium catalyst component (I) used in the present application, 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,

[0253] The compound (a) / titanium (molar ratio) (i.e., the number of moles of compound (a) / the number of moles of titanium atoms) is preferably 0.01 to 100, more preferably 0.2 to 10,

[0254] The catalyst component (b) / titanium atom (molar ratio) 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.

[0255] 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.

[0256] In addition, the content of the component other than the above-mentioned compound (a), such as the catalyst component (b) and the catalyst component (c), is preferably 20% by weight or less, more preferably 10% by weight or less, with respect to 100% by weight of the compound (a).

[0257] As the more detailed preparation conditions of the solid titanium catalyst component (I), in addition to the use of the compound (a), the conditions described in, for example, EP 585869 A1 (European Patent Application Publication No. 0585869), Patent Literature 2, and the like can be preferably used.

[0258] [Catalyst for olefin polymerization]

[0259] The olefin polymerization catalyst of the present application is characterized by comprising the above-mentioned solid titanium catalyst component (I) of the present application, and an organometallic compound catalyst component (II) containing a metal element selected from Group 1, Group 2, and Group 13 of the periodic table.

[0260] [Organometallic compound catalyst component (II)]

[0261] As the above-mentioned organometallic compound catalyst component (II), a compound containing a Group 13 metal, such as an organoaluminum compound, a coordination alkylate of a Group 1 metal and aluminum, an organometallic compound of a Group 2 metal, and the like can be used. Among them, an organoaluminum compound is preferred.

[0262] As the organometallic compound catalyst component (II), specifically, the organometallic compound catalyst components described in the above-mentioned EP 585869 A1 and the like known documents can be cited as preferred examples.

[0263] <electron donor (III)>

[0264] Further, the olefin polymerization catalyst of the present application can contain an electron donor (III) as needed together with the above-mentioned organometallic compound catalyst component (II). As the electron donor (III), an organosilicon compound is preferable. As the organosilicon compound, for example, a compound represented by the following general formula (4) can be exemplified.

[0265] R S n Si(OR" 4-n ···(4)

[0266] In formula (4), R S and R" are hydrocarbon groups, and n is an integer of 0 < n < 4.

[0267] As the organosilicon compound represented by the above-mentioned general formula (4), specifically, 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, cyclopentyldimethylethoxysilane, and the like can be used.

[0268] Among them, vinyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane are preferable.

[0269] Further, a silane compound represented by the following formula (5) described in International Publication No. 2004 / 016662 is also a preferable example of the above-mentioned organosilicon compound.

[0270] Si(OR a )3(NR b R c )···(5)

[0271] In formula (5), R a is a hydrocarbon group having 1 to 6 carbon atoms, and R aAs the unsaturated or saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, specifically, a hydrocarbon group having 2 to 6 carbon atoms is preferable. As specific examples, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, and the like are given, of which an ethyl group is particularly preferable.

[0272] In formula (5), R b is a hydrocarbon group having 1 to 12 carbon atoms or hydrogen, and as R b , an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or hydrogen is given. As specific examples, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an octyl group, and the like are given, of which an ethyl group is particularly preferable.

[0273] In formula (5), R c is a hydrocarbon group having 1 to 12 carbon atoms, and as R c , an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or hydrogen is given. As specific examples, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an octyl group, and the like are given, of which an ethyl group is particularly preferable.

[0274] As specific examples of the compound represented by the above formula (5), dimethylaminotriethoxysilane, diethylaminotriethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, diethylaminotri-n-propoxysilane, di-n-propylaminotriethoxysilane, methyl-n-propylaminotriethoxysilane, t-butylaminotriethoxysilane, ethyl-n-propylaminotriethoxysilane, ethylisopropylaminotriethoxysilane, methylethylaminotriethoxysilane are given.

[0275] Further, as other examples of the above silicone compound, a compound represented by the following formula (6) is given.

[0276] R N NSi(OR a )3···(6)

[0277] In formula (6), R N N is a cyclic amino group, and as the cyclic amino group, for example, a perhydroquinolinyl group, a perhydroisoquinolinyl group, a 1,2,3,4-tetrahydroquinolinyl group, a 1,2,3,4-tetrahydroisoquinolinyl group, an octamethylene imino group, and the like are given.

[0278] As the compound represented by the above formula (6), specifically, (perhydroquinolinyl)triethoxysilane, (perhydroisoquinolinyl)triethoxysilane, (1,2,3,4-tetrahydroquinolinyl)triethoxysilane, (1,2,3,4-tetrahydroisoquinolinyl)triethoxysilane, octamethylene imino triethoxysilane can be given.

[0279] These organosilicon compounds can also be used in combination of two or more.

[0280] Further, as other compounds which can be used as the electron donor (III), polyether compounds described as examples of the above-mentioned aromatic carboxylic acid ester and / or compound having two or more ether bonds separated by a plurality of carbon atoms (the above-mentioned catalyst component (c)) can be given as preferred examples.

[0281] Among these polyether compounds, 1,3-diether compounds are preferred, and 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 are particularly preferred.

[0282] These compounds can be used alone or in combination of two or more.

[0283] In the case where the above-mentioned electron donor (III) is used in combination, the stereoregularity and the molecular weight can be adjusted, in particular. Specifically, if the use ratio of the electron donor (III) to the organometallic compound catalyst component is increased, there is a tendency that a polymer having high stereoregularity is easily obtained, and a polymer having high molecular weight is easily obtained. On the other hand, if the use ratio of the above-mentioned electron donor (III) is decreased, there is a tendency that a polymer having low stereoregularity (for example, a polymer having a high content of the decane-soluble component described later) is easily obtained, and a polymer having low molecular weight is easily obtained.

[0284] Note that, in addition to the above-mentioned components, the olefin polymerization catalyst of the present application can contain other components useful for olefin polymerization as needed. As the other components, for example, a carrier such as silica, an antistatic agent, a particle coagulation agent, a storage stabilizer, and the like can be given.

[0285] [Method for polymerizing olefin]

[0286] The olefin polymerization method of the present application is characterized in that the olefin is polymerized using the olefin polymerization catalyst of the present application. In the present application, the meaning of "polymerization" includes, in addition to homopolymerization, sometimes the meaning of copolymerization such as random copolymerization, block copolymerization, and the like.

[0287] In the olefin polymerization method of the present application, an α-olefin can also be prepolymerized in the presence of the olefin polymerization catalyst of the present application to obtain a prepolymerization catalyst, and the formal polymerization is performed in the presence of the prepolymerization catalyst. The prepolymerization is performed by prepolymerizing an α-olefin in an amount of 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g, per 1 g of the olefin polymerization catalyst.

[0288] In the prepolymerization, the catalyst can be used at a higher concentration than the catalyst concentration in the system in the formal polymerization.

[0289] As for the concentration of the above-mentioned solid titanium catalyst component (I) in the prepolymerization, it is desirable to set it to a range of about 0.001 to 200 millimoles, preferably about 0.01 to 50 millimoles, particularly preferably 0.1 to 20 millimoles, per 1 liter of the liquid medium, in terms of titanium atoms.

[0290] As for the amount of the above-mentioned organometallic compound catalyst component (II) in the prepolymerization, it is an amount that generates 0.1 to 1000 g, preferably 0.3 to 500 g, of a polymer per 1 g of the solid titanium catalyst component (I), and it is desirable to set it to a range of about 0.1 to 300 moles, preferably about 0.5 to 100 moles, particularly preferably 1 to 50 moles, per 1 mole of titanium atoms in the solid titanium catalyst component (I).

[0291] In the prepolymerization, the above-mentioned electron donor (III) or the like can also be used as needed, and in this case, these components are used in an amount of 0.1 to 50 moles, preferably 0.5 to 30 moles, further preferably 1 to 10 moles, per 1 mole of titanium atoms in the above-mentioned solid titanium catalyst component (I). By adjusting the amount of the above-mentioned electron donor (III), it is sometimes possible to adjust the stereoregularity of the obtained olefin polymer.

[0292] The prepolymerization can be performed under mild conditions by adding an olefin and the above-mentioned catalyst components to a non-activated hydrocarbon medium.

[0293] In this case, as the non-activated hydrocarbon medium used, specifically, there can be mentioned:

[0294] propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, and the like aliphatic hydrocarbons;

[0295] cycloheptane, methylcycloheptane, 4-cycloheptane, methyl-4-cycloheptane, and the like alicyclic hydrocarbons;

[0296] benzene, toluene, xylene, and the like aromatic hydrocarbons;

[0297] chlorinated ethylene, chlorobenzene and the like halogenated hydrocarbons, or a mixture thereof, and the like.

[0298] Among these non-active hydrocarbon media, aliphatic hydrocarbons are particularly preferred. Thus, in the case of using a non-active hydrocarbon medium, the prepolymerization is preferably performed in a batch mode.

[0299] On the other hand, the prepolymerization can be performed using the olefin itself as a solvent, or can be performed in a substantially solvent-free state. In this case, the prepolymerization is preferably performed continuously.

[0300] The olefin used in the prepolymerization can be the same as or different from the olefin used in the following main polymerization, and is specifically preferably propylene.

[0301] The temperature during the prepolymerization is desirably generally preferably in the range of about -20 to +100°C, more preferably in the range of about -20 to +80°C, and further preferably in the range of 0 to +40°C.

[0302] Next, the main polymerization performed after the above prepolymerization or without the prepolymerization will be described.

[0303] As the olefin which can be used in the main polymerization (i.e., which can be polymerized), α-olefins having 3 to 20 carbon atoms can be mentioned, such as straight-chain olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like; branched-chain olefins such as 4-methyl-1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene, and the like, and propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-butene are preferred. From the viewpoint of the advantage that a polymer having a wide molecular weight distribution can be easily exhibited in a resin having high rigidity, propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene are particularly preferred.

[0304] Ethylene, styrene, allylbenzene and the like aromatic vinyl compounds; alicyclic vinyl compounds such as vinylcyclohexane, vinylcycloheptane, and the like can also be used together with these α-olefins. Furthermore, compounds having multiple unsaturated bonds such as conjugated dienes such as cyclopentene, cycloheptene, norbornene, tetracyclododecene, isoprene, butadiene, and the like, and non-conjugated dienes can also be used together with ethylene and α-olefins as a polymerization raw material. These compounds can be used singly in one kind, or two or more kinds can be used in combination (hereinafter, the above ethylene or the olefin used together with "α-olefin having 3 to 20 carbon atoms" is also referred to as "other olefin").

[0305] Of the above other olefins, ethylene and aromatic vinyl compounds are preferred. In addition, other olefins such as ethylene can be used in a small amount, for example, 10% by weight or less, preferably 5% by weight or less, in the total amount of 100% by weight of the olefins.

[0306] In the present application, the prepolymerization and the main polymerization can be carried out by any one of the bulk polymerization method, the solution polymerization, the liquid phase polymerization method such as the suspension polymerization, or the gas phase polymerization method.

[0307] In the case where the main polymerization is carried out by the slurry polymerization, as the reaction solvent, the above inactive hydrocarbon used in the prepolymerization can be used, or an olefin which is liquid at the reaction temperature can be used.

[0308] In the main polymerization in the polymerization method of the present application, the above solid titanium catalyst component (I) is generally used in an amount of about 0.0001 to 0.5 mmol, preferably about 0.005 to 0.1 mmol, per 1 liter of the polymerization volume in terms of the titanium atom. In addition, the above organometallic compound catalyst component (II) is generally used in an amount of about 1 to 2000 moles, preferably about 5 to 500 moles, more preferably 10 to 350 moles, further preferably 30 to 350 moles, particularly preferably 50 to 350 moles, per 1 mole of the titanium atom in the prepolymerization catalyst component in the polymerization system. In the case where the above electron donor (III) is used, it is used in an amount of 0.001 to 50 moles, preferably 0.01 to 30 moles, particularly preferably 0.05 to 20 moles, per 1 mole of the metal atom of the above organometallic compound catalyst component (II). As described above, depending on the amount of the electron donor (III) used, it is sometimes possible to adjust the stereoregularity and the molecular weight.

[0309] If the main polymerization is carried out in the presence of hydrogen, it is possible to adjust the molecular weight of the obtained polymer, and a polymer having a large melt flow rate can be obtained.

[0310] In the main polymerization in the present application, the polymerization temperature of the olefin is generally about 20 to 200°C, preferably about 30 to 100°C, more preferably 50 to 90°C. The pressure is generally set to be about 0.1 MPa to 10 MPa, preferably 0.20 to 5 MPa. In the polymerization method of the present application, the polymerization can be carried out by any one of the batch method, the semi-continuous method, and the continuous method. Furthermore, the polymerization can be carried out by dividing the polymerization into two or more steps by changing the reaction conditions. If such a multi-step polymerization is carried out, it is possible to further widen the molecular weight distribution of the olefin polymer.

[0311] The polymer of the olefin thus obtained can be any one of a homopolymer, a random copolymer, and a block copolymer.

[0312] If polymerization of an olefin, particularly polymerization of propylene, is carried out using the above-mentioned catalyst for polymerization of an olefin, a propylene-based polymer having a content of decane-insoluble components of 70% or more, preferably 85% or more, particularly preferably 90% or more, and high stereoregularity can be obtained.

[0313] Further, according to the olefin polymerization method of the present application, even if multi-step polymerization is not carried out, even if polymerization with a small number of steps, for example, single-step polymerization, is carried out, a polyolefin, particularly polypropylene, having a wide molecular weight distribution can be obtained. The olefin polymerization method of the present application is characterized in that, in most cases, an olefin polymer having a higher ratio of components having a high molecular weight and a lower ratio of components having a low molecular weight (particularly, components referred to as sticky components) than conventional olefin polymers having the same melt flow rate (MFR) can be obtained. This characteristic can be confirmed by the gel permeation chromatography (GPC) measurement described later, and a polymer having both a high Mw / Mn value and a high Mz / Mw value can be obtained.

[0314] Polypropylene obtained using a conventional solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor generally has, for example, in the region where the MFR is 1 to 10 g / 10 minutes, an index of the molecular weight distribution, i.e., a Mw / Mn value, of 5 or less and a Mz / Mw value of less than 4, as determined by GPC measurement, but if the olefin polymerization method of the present application is used, an olefin polymer having a Mw / Mn value of 6 to 30, preferably 7 to 20, can be obtained under the same polymerization conditions as described above. In addition, an olefin polymer having a Mz / Mw value of preferably 4 to 15, more preferably 4.5 to 10, can be obtained. In particular, according to the olefin polymerization method of the present application, an olefin polymer having a high Mz / Mw value can be obtained in most cases.

[0315] It is common knowledge to those skilled in the art that a polypropylene having a high Mw / Mn value has excellent moldability and rigidity. On the other hand, a high Mz / Mw value indicates a high ratio of components having a high molecular weight, and it is predicted that the resulting polypropylene has a high melt tension and is highly likely to have excellent moldability.

[0316] If the olefin polymerization method of the present application is used, a polymer having a wide molecular weight distribution can be obtained even if multi-step polymerization is not carried out, and thus it is possible to simplify the polymer production apparatus. In addition, if it is applied to a conventional multi-step polymerization method, it is predicted that a polymer having a higher melt tension and more excellent moldability can be obtained.

[0317] As other methods for obtaining a polymer having a wide molecular weight distribution, there are methods of dissolving and mixing polymers having different molecular weights, and melt kneading, but polymers obtained by these methods are sometimes still unable to sufficiently improve the melt tension, moldability, although the operation is more complicated. It is presumed that this is because polymers having different molecular weights are not substantially mixed. On the other hand, the polymer obtained by the polymerization method of the present application has a very wide range of polymers having different molecular weights mixed at the catalyst level, i.e., at the nanometer level, and thus it is predicted that the melt tension is high and the moldability is excellent.

[0318] The polymer obtained by the polymerization method of the present application has a high stereoregularity as described above. Therefore, the olefin polymer obtained by the method of the present application has a tendency to have a high melting point. The melting point is generally determined by a differential scanning calorimetry (DSC) method.

[0319] As described above, the olefin polymer, particularly the propylene polymer, obtained by the method of the present application has a tendency to have a wide molecular weight distribution, particularly a large Mz, and thus has a tendency to have a distribution widened on the high molecular weight side. The molecular mobility of the olefin polymer differs depending on the molecular weight, and thus in the case of a polymer having a wide molecular weight distribution, the graph obtained by DSC measurement sometimes has a shape that is not unimodal but multimodal, or a wide shape. That is, since the more the ultrahigh molecular weight component, the more difficult it is to crystallize, it is considered that the wide shape on the low temperature side in the DSC measurement method can be caused by the ultrahigh molecular weight component. Therefore, ΔH measured as the heat of fusion (crystallization heat) also sometimes shows a tendency to be low.

[0320] On the other hand, it is known that the DSC graph of the propylene polymer obtained using the method of the present application shows a tendency to have less widening toward the lower temperature side and a high ΔH. This is because the component in the ultrahigh molecular weight region of the polymer obtained by the method of the present application has a high stereoregularity, and thus it is likely to show a tendency to easily crystallize and have less widening toward the low temperature side.

[0321] In applications such as film applications where transparency and see-through properties are valued, the component in the ultrahigh molecular weight region described above is considered to possibly cause problems such as fish eyes. The olefin polymer obtained by the method of the present application has a tendency to achieve a fine dispersion state that can also be referred to as the catalyst active species level, i.e., the nanometer level, as described above, and thus has a tendency to be less likely to cause the above problems. In addition, by selecting the structure of the ester compound (a) used in the catalyst of the present application, it is also possible to adjust the balance between the molecular weight and the content of the component in the ultrahigh molecular weight region and the molecular weight and the melt flow rate (MFR) of the entire polymer.

[0322] The reason why a polymer exhibiting such properties can be obtained is that the compound (a) included in the catalyst of the present application has a specific structure, and thus the reaction environment field is stable as described above. That is, the present inventors et al. presume that the active site having high stereoregularity control ability can have an effect of preventing from becoming a specific state that causes chain transfer reaction, while having high stereospecificity.

[0323] The polymer obtained by the method of the present application sometimes exhibits a molecular weight distribution that is somewhat broadened also on the low molecular weight side. The low molecular weight component has a tendency to have a weak crystal structure and a low melting point due to the low molecular weight.

[0324] The propylene polymer obtained by the method of the present application is considered to exhibit a DSC chart in which the broadening on the low temperature side is small, because the low molecular weight component has high stereoregularity.

[0325] In addition, various factors such as the possibility of exhibiting a nucleating agent effect in the crystallization step can be considered.

[0326] From these viewpoints, the propylene polymer obtained by the method of the present application is considered to have high stereoregularity regardless of the molecular weight region. Therefore, the heat of fusion is high, and the propylene polymer is considered to exhibit a relatively high crystallinity.

[0327] The propylene polymer obtained using the solid titanium catalyst component of the present application can include structural units derived from an olefin other than propylene and a polymerizable vinyl compound, as long as the characteristics, objects, and the like thereof are not violated.

[0328] As the above-mentioned olefin, the olefins and dienes disclosed in the column of the method for producing the above-mentioned olefin polymer can be mentioned as preferable examples, and as the polymerizable vinyl compound, aromatic vinyl compounds exemplified by styrene and the like can be mentioned as preferable examples. As a more preferable olefin, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-hexadecene, and 1-octadecene can be mentioned. Among them, ethylene, 1-butene, 1-hexene, 1-octene, and 1-decene are more preferable examples, and ethylene and 1-butene are further preferable examples. Styrene can be mentioned as a preferable example of the polymerizable vinyl compound.

[0329] In the case where the total of the content ratio of the structural units derived from propylene is set to 100 mol%, the content ratio of such other structural units is preferably 5 mol% or less, more preferably 3 mol% or less, further preferably 1 mol% or less, and particularly preferably 0.5 mol% or less.

[0330] The propylene polymer obtained by the method of the present application can be used for various uses known in the art. In particular, its high heat resistance, rigidity, and thus suitability for various injection-molded articles, more specifically for automobile members, members of home electric appliances, and the like are expected. In addition, depending on the magnitude of the molecular weight distribution, it can also be used for various sheets, films, and the like. It is particularly suitable for the use as a separator for lithium ion batteries, capacitors, and the like. In addition, it can also be suitably used for press-molded articles, calender-molded articles, rotational-molded articles, and the like.

[0331] Examples

[0332] Hereinafter, the present application will be described by way of examples, but the present application is not limited to these examples.

[0333] In the following examples, the bulk specific gravity, melt flow rate, amount of decane-soluble (insoluble) component, molecular weight distribution, final melting point, melting point, crystallization temperature, heat of fusion of the propylene polymer were measured by the following methods.

[0334] (1) Bulk specific gravity:

[0335] It was measured in accordance with JIS K-6721.

[0336] (2) Melt flow rate (MFR):

[0337] It was measured in accordance with ASTM D1238E, with the temperature set to 230°C and the load set to 2.16 kg in the case of the propylene polymer.

[0338] (3) Amount of decane-soluble (insoluble) component:

[0339] A glass-made measuring vessel was charged with about 3 g (measured to the unit of 10 -4 g) of the propylene polymer, 500 ml of decane, and a small amount of a heat-resistant stabilizer soluble in decane, and, under a nitrogen atmosphere, the propylene polymer was dissolved by raising the temperature to 150°C over 2 hours while stirring with a stirrer, and, after maintaining at 150°C for 2 hours, it was slowly cooled to 23°C over 8 hours. The liquid containing the precipitate of the obtained propylene polymer was subjected to reduced-pressure filtration using a 25G-4 standard glass filter manufactured by Tokyo Rikakiki Co., Ltd. 100 ml of the filtrate was collected, and it was reduced-pressure dried to obtain a part of the decane-soluble component, and the weight was measured to the unit of 10 -4 g) (the weight is represented as a (g) in the following formula). After this operation, the amount of the decane-soluble component was determined using the following formula.

[0340] Decane-soluble component content rate = 100 x (500 x a) / (100 x b)

[0341] Decane-insoluble content rate = 100 - 100 x (500 x a) / (100 x b)

[0342] (4) Molecular weight distribution (MWD):

[0343] Gel permeation chromatography: HLC-8321 GPC / HT manufactured by Tosoh Corporation

[0344] Detector: Differential refractometer

[0345] Column: TSKgel GMH6-HT x 2 manufactured by Tosoh Corporation and TSKgel GMH6-HTL x 2 were connected in series.

[0346] Mobile phase medium: o-dichlorobenzene

[0347] Flow rate: 1.0 ml / min

[0348] Measurement temperature: 140°C

[0349] Method for preparing standard curve: Standard polystyrene samples were used.

[0350] Sample concentration: 0.1% (w / w)

[0351] Sample solution amount: 0.4 ml

[0352] The measurement was performed under the above conditions, and the obtained chromatogram was analyzed by a known method, whereby the weight average molecular weight (Mw), the number average molecular weight (Mn), the Z average molecular weight (Mz), and the index of the molecular weight distribution (MWD) i.e. the Mw / Mn value, the Mz / Mw value were calculated. The measurement time for each 1 sample was 60 minutes.

[0353] (5) Melting point (Tm) of the polymer:

[0354] The melting point (Tm), the crystallization temperature (Tc), and the heat of fusion (ΔH) of the polymer in the present application were measured using a differential scanning calorimeter (DSC) in a DSC8000 device manufactured by PerkinElmer. A sample of 3 to 10 mg 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 set as the crystallization temperature (Tc), and the heat generation determined from the peak area was set as ΔH (1st-cool (first cooling)). Subsequently, after being left at 30°C for 5 minutes, the sample was heated to 200°C at 10°C / min for the 2nd time. The peak temperature observed in this 2nd heating test was set as the melting point (Tm) (in the case where multiple peaks were observed, the 2 points on the high temperature side were recorded in the table).

[0355] The final melting point (Tmf) of the polymer in the present application was measured using a differential scanning calorimeter (DSC) in a DSC8000 apparatus manufactured by PerkinElmer. A sample of 3 to 10 mg 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 being held 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 line of the peak on the high temperature side in the final heating test with the baseline was taken as the final melting point (Tmf).

[0356] The Tmf can be considered as a parameter for evaluating the ease of crystallization of a polymer having a very high stereoregularity, a crystal structure, and a tendency to be difficult to crystallize, of a super high molecular weight region. More specifically, it can be considered that the higher the value of the Tmf, the more easily a super high molecular weight polymer component forms a crystal having a high heat resistance.

[0357] In addition, the compounds used in the following examples and comparative examples have a stereoisomer structure. The structural formula of the stereoisomer of the compound illustrated shows an isomer that is a main component of the compound used in the examples and comparative examples. In addition, in the present application, the main component refers to greater than 50 mol%, and preferably 70 mol% or more.

[0358] [Example 1]

[0359] <Preparation of solid titanium catalyst component [α1]>

[0360] After sufficiently performing nitrogen substitution on a 1L glass container, 85.8 g of anhydrous magnesium chloride, 321 g of decane, and 352 g of 2-ethylhexanol were added, and a uniform solution was prepared by heating the reaction at 130°C for 3 hours. 241 g of the solution and 6.43 g of ethyl benzoate were added to the glass container, and the mixture was stirred at 50°C for 1 hour.

[0361] After the thus obtained homogeneous solution was cooled to room temperature, the homogeneous solution was added dropwise to 100 ml of titanium tetrachloride kept at -20°C at a rate of 38.3 ml over 45 minutes while stirring. After the addition was completed, the temperature of the mixture was raised to 80°C over 3.8 hours, and at the time of reaching 80°C, 1.83 g of the following Compound 1 was added to the mixture. The temperature was again raised to 120°C over 40 minutes, and the reaction was carried out at the same temperature for 35 minutes while stirring. After the reaction was completed, the solid fraction was collected by hot filtration, and after the solid fraction was resuspended in 100 ml of titanium tetrachloride, the reaction was again carried out at 120°C for 35 minutes while stirring. After the reaction was completed, the solid fraction was again collected by hot filtration, and washed with 100°C decane and room temperature decane until no free titanium compound was detected in the washings. The solid titanium catalyst component [αl] prepared by the above procedure was stored as a decane slurry, but a portion thereof was dried for the purpose of investigating the catalyst composition. The composition of the thus obtained solid titanium catalyst component [αl] was 0.42 mass% of titanium, 1.4 mass% of magnesium, and 0.11 mass% of 2-ethylhexanol residues.

[0362] [Chemical Formula 50]

[0363] Compound 1

[0364] <Official Polymerization>

[0365] In a polymerizer having a content volume of 2 liters, after 500 g of propylene and 1 NL of hydrogen were added at room temperature, a mixed solution obtained by mixing heptane 7 ml, triethylaluminum 0.5 mmol, cyclohexylmethyldimethoxysilane 0.1 mmol, and solid titanium catalyst component [αl] 0.004 mmol (in terms of titanium atoms) at 25°C for 10 minutes was added, and the polymerizer was rapidly heated to 70°C while stirring. After the polymerization was carried out at 70°C for 1.5 hours, the reaction was stopped with a small amount of ethanol, and the propylene was removed. Further, the obtained polymer particles were dried at 80°C under reduced pressure for one night. The activity, bulk specific gravity, MFR, amount of decane-insoluble component, Tm, Tmf, MWD, and the like are shown in Table 1.

[0366] [Example 2]

[0367] <Preparation of Solid Titanium Catalyst Component [α2]>

[0368] After a 1 L glass container was sufficiently replaced with nitrogen, anhydrous magnesium chloride 85.8 g, decane 321 g, and 2-ethylhexanol 352 g were added, and the mixture was heated to react at 130°C for 3 hours to prepare a homogeneous solution. The solution 241 g and ethyl benzoate 6.43 g were added to the glass container, and the mixture was stirred and mixed at 50°C for 1 hour.

[0369] After the thus obtained homogeneous solution was cooled to room temperature, the homogeneous solution was added dropwise all at once over 45 minutes to titanium tetrachloride 80 ml kept at -20°C while stirring. After the addition was completed, the temperature of the mixture was raised to 80°C over 3.8 hours, and at the time of reaching 80°C, 1.22 g of the following Compound 2 was added to the mixture. The temperature was again raised to 120°C over 40 minutes, and the heating was continued at the same temperature for 35 minutes with stirring. After the reaction was completed, the solid fraction was collected by hot filtration, and after the solid fraction was resuspended in 80 ml of titanium tetrachloride, the heating reaction was again carried out at 120°C with stirring for 35 minutes. After the reaction was completed, the solid fraction was again collected by hot filtration, and washed with 100°C decane and room temperature decane until no free titanium compound was detected in the washing liquid. The solid titanium catalyst component [α2] prepared by the above operation was stored as a decane slurry, but a part of it was dried for the purpose of investigating the catalyst composition. The composition of the thus obtained solid titanium catalyst component [α2] was 0.40 mass% of titanium, 1.6 mass% of magnesium, and 0.12 mass% of 2-ethylhexanol residue.

[0370] [Compound 51]

[0371] Compound 2

[0372] <Official polymerization>

[0373] Instead of the solid titanium catalyst component [αl], 0.004 mmol (in terms of titanium atoms) of the solid titanium catalyst component [α2] was used, and otherwise, the polymerization of propylene was carried out in the same manner as in Example 1. The result thereof is shown in Table 1.

[0374] [Example 3]

[0375] <Preparation of solid titanium catalyst component [α3]>

[0376] Instead of 1.83 g of Compound 1, 1.97 g of the following Compound 3 was used, and otherwise, the operation was carried out in the same manner as in Example 1 to obtain the solid titanium catalyst component [α3].

[0377] [Compound 52]

[0378] Compound 3

[0379] <Official polymerization>

[0380] The polymerization of propylene was carried out in the same manner as in Example 1, except that 0.0032 millimoles (in terms of titanium atoms) of the solid titanium catalyst component [α3] was used instead of the solid titanium catalyst component [αl], the amount of triethylaluminum was changed from 0.5 millimoles to 0.4 millimoles, and the amount of cyclohexylmethyldimethoxysilane was changed from 0.1 millimoles to 0.08 millimoles. The results are shown in Table 1.

[0381] [Example 4]

[0382] Preparation of solid titanium catalyst component [α4]

[0383] The solid titanium catalyst component [α4] was obtained by operating in the same manner as in Example 2, except that 1.52 g of the following compound 4 was used instead of 1.22 g of compound 2.

[0384] [Compound 53]

[0385] Compound 4

[0386] <Official polymerization>

[0387] The polymerization of propylene was carried out in the same manner as in Example 1, except that 0.0028 millimoles (in terms of titanium atoms) of the solid titanium catalyst component [α4] was used instead of the solid titanium catalyst component [αl], the amount of triethylaluminum was changed from 0.5 millimoles to 0.35 millimoles, and the amount of cyclohexylmethyldimethoxysilane was changed from 0.1 millimoles to 0.07 millimoles. The results are shown in Table 1.

[0388] [Example 5]

[0389] Preparation of solid titanium catalyst component [α5]

[0390] The solid titanium catalyst component [α5] was obtained by operating in the same manner as in Example 1, except that 0.91 g of the following compound 5 was used instead of 1.83 g of compound 1.

[0391] [Compound 54]

[0392] Compound 5

[0393] <Official polymerization>

[0394] The polymerization of propylene was carried out in the same manner as in Example 3, except that the solid titanium catalyst component [α5] was used instead of the solid titanium catalyst component [α3]. The results are shown in Table 1.

[0395] [Example 6]

[0396] Preparation of solid titanium catalyst component [α6]

[0397] Using 1.74 g of the following compound 6 instead of 1.83 g of compound 1, the same operation as in Example 1 was conducted to obtain a solid titanium catalyst component [α6].

[0398] [Compound 55]

[0399] Compound 6

[0400] <Official polymerization>

[0401] Using the solid titanium catalyst component [α6] instead of the solid titanium catalyst component [αl], the polymerization of propylene was conducted in the same manner as in Example 1. The results thereof are shown in Table 1.

[0402] [Example 7]

[0403] Preparation of solid titanium catalyst component [α7]

[0404] Using 1.81 g of the following compound 7 instead of 1.83 g of compound 1, the same operation as in Example 1 was conducted to obtain a solid titanium catalyst component [α7].

[0405] [Compound 56]

[0406] Compound 7

[0407] <Official polymerization>

[0408] Using 0.0028 mmol (in terms of titanium atom) of the solid titanium catalyst component [α7] instead of the solid titanium catalyst component [α4], the polymerization of propylene was conducted in the same manner as in Example 4. The results thereof are shown in Table 1.

[0409] [Example 8]

[0410] Preparation of solid titanium catalyst component [α8]

[0411] Using 1.16 g of the following compound 8 instead of 1.22 g of compound 2, the same operation as in Example 2 was conducted to obtain a solid titanium catalyst component [α8].

[0412] [Compound 57]

[0413] Compound 8

[0414] <Official polymerization>

[0415] The polymerization of propylene was carried out in the same manner as in Example 1 except that the solid titanium catalyst component [α8] was used instead of the solid titanium catalyst component [α1]. The results are shown in Table 1.

[0416] [Comparative Example 1]

[0417] <Preparation of Solid Titanium Catalyst Component [β1]>

[0418] A solid titanium catalyst component [β1] was obtained in the same manner as in Example 1 except that 1.86 g of the following compound c1 was used instead of 1.83 g of the compound 1.

[0419] [Chemistry 58]

[0420] Compound c1

[0421] <Formal Gathering>

[0422] The polymerization of propylene was carried out in the same manner as in Example 1 except that 0.004 mmol (in terms of titanium atoms) of the solid titanium catalyst component [β1] was used instead of the solid titanium catalyst component [α1].

[0423] [Comparative Example 2]

[0424] <Preparation of Solid Titanium Catalyst Component [β2]>

[0425] A solid titanium catalyst component [β2] was obtained in the same manner as in Example 1 except that 1.32 g of the following compound c2 was used instead of 1.83 g of the compound 1.

[0426] [Chemistry 59]

[0427] Compound c2

[0428] <Formal Gathering>

[0429] The polymerization of propylene was carried out in the same manner as in Example 1 except that 0.004 mmol (in terms of titanium atoms) of the solid titanium catalyst component [β2] was used instead of the solid titanium catalyst component [α1].

[0430] [Comparative Example 3]

[0431] <Preparation of Solid Titanium Catalyst Component [β3]>

[0432] A solid titanium catalyst component [β3] was obtained in the same manner as in Example 1 except that 1.57 g of the following compound c3 was used instead of 1.83 g of the compound 1 and the stirring speed of titanium tetrachloride was changed to 350 rpm.

[0433] [Compound 60]

[0434] Compound c3

[0435] [Formal polymerization]

[0436] A polymerization of propylene was conducted in the same manner as in Example 1, except that 0.0032 mmol (in terms of titanium atom) of the solid titanium catalyst component [β3] was used instead of the solid titanium catalyst component [αl]. The results thereof are shown in Table 1.

[0437] [Example 9]

[0438] Preparation of solid titanium catalyst component [α9]

[0439] A solid titanium catalyst component [α9] was obtained by operating in the same manner as in Example 2, except that 1.57 g of the following Compound 9 was used instead of 1.22 g of Compound 2.

[0440] [Compound 61]

[0441] Compound 9

[0442] [Formal polymerization]

[0443] A polymerization of propylene was conducted in the same manner as in Example 3, except that the solid titanium catalyst component [α9] was used instead of the solid titanium catalyst component [α3]. The results thereof are shown in Table 1.

[0444] [Example 10]

[0445] Preparation of solid titanium catalyst component [α10]

[0446] A solid titanium catalyst component [α10] was obtained by operating in the same manner as in Example 1, except that 2.03 g of the following Compound 10 was used instead of 1.83 g of Compound 1.

[0447] [Compound 62]

[0448] Compound 10

[0449] [Formal polymerization]

[0450] A polymerization of propylene was conducted in the same manner as in Example 3, except that the solid titanium catalyst component [α10] was used instead of the solid titanium catalyst component [α3]. The results thereof are shown in Table 1.

[0451] [Example 11]

[0452] Preparation of solid titanium catalyst component [α11]

[0453] Using 1.86 g of the following compound 11 instead of 1.83 g of compound 1, the same operation as in Example 1 was conducted to obtain a solid titanium catalyst component [α11].

[0454] [Compound 63]

[0455] Compound 11

[0456] <Official polymerization>

[0457] Using the solid titanium catalyst component [α11] instead of the solid titanium catalyst component [α1], the same polymerization of propylene as in Example 1 was conducted. The result thereof is shown in Table 1.

[0458] [Example 12]

[0459] Preparation of solid titanium catalyst component [α12]

[0460] Using 1.79 g of the following compound 12 instead of 1.83 g of compound 1, the same operation as in Example 1 was conducted to obtain a solid titanium catalyst component [α12].

[0461] [Compound 64]

[0462] Compound 12

[0463] <Official polymerization>

[0464] Using the solid titanium catalyst component [α12] instead of the solid titanium catalyst component [α1], the same polymerization of propylene as in Example 1 was conducted. The result thereof is shown in Table 1.

[0465] [Table 1]

[0466]

[0467] From the results of the above Examples and Comparative Examples, it was found that if propylene is polymerized in the presence of an olefin polymerization catalyst using the solid titanium catalyst component of the present application, a propylene polymer having a high value of Mw / Mn and / or Mz / Mw can be produced. This is also clear in a comparison in which the sum of the "Mw / Mn" value and the "Mz / Mw" value is used as an index.

[0468] Further, it was found that the propylene polymer of the Examples of the present application has a tendency to have a high melting point, a high crystallization temperature, and particularly a high heat of fusion. Such a propylene polymer is expected to be a molding material that is excellent in both moldability and heat resistance.

Claims

1. A solid titanium catalyst component (I) characterized in that, a compound represented by the following formula (1) (a), [Chemical Formula 1] In formula (1), A is a substituent having a "-CR2-R 100 -CR2-” structure, R 1 and R 2 Each has "R 10 -CR2-" structure substituents, R 3 is a hydrogen atom or a substituent having a "R 10 -CR2-” structure, R 4 R 10 R 10 R 16 R 10 R 15 R At 15 At is an atom of group 15 of the periodic table 16 Rn is an atom of group 16 of the periodic table R and R 10 each is a group comprising atoms selected from carbon, hydrogen, and elements of group 15, 16, 17 of the periodic table, R 100 each is a group comprising atoms selected from carbon, hydrogen, and elements of group 15, 16, 17 of the periodic table, or is a bond selected from single, double, triple bond, R 1 ~R 4 and A can be linked to each other to form a monocyclic or polycyclic ring, R in A 100 may be bonded to each other to form a single ring or multiple rings, and may form multiple bonds.

2. The solid titanium catalyst component (I) according to claim 1, wherein R 100 is a group comprising atoms selected from carbon, hydrogen and elements of group 15, 16, 17 of the periodic table.

3. The solid titanium catalyst component (I) according to claim 1, wherein the A is a cyclic structure.

4. The solid titanium catalyst component (I) according to claim 1, wherein the A is an aromatic structure.

5. The solid titanium catalyst component (I) according to claim 1, wherein said R 3 is a substituent having a "R 10 -CR2-” structure.

6. The solid titanium catalyst component (I) according to claim 1, wherein said R 4 is a substituent having a "R 10 -CR2-” structure.

7. The solid titanium catalyst component (I) according to claim 1, wherein the At 15 is a nitrogen atom.

8. The solid titanium catalyst component (I) according to claim 1, wherein the At 16 is an oxygen atom.

9. A catalyst for the polymerization of olefins, characterized in that, an organometallic compound catalyst component (II) containing a metal element selected from Group 1, Group 2 and Group 13 of the periodic table.

10. The catalyst for the polymerization of an olefin according to claim 9, further comprising an electron donor (III).

11. A process for the polymerization of olefins, characterized in that, The polymerization of an olefin is performed in the presence of the catalyst for the polymerization of an olefin according to claim 9 or 10.

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