Propylene polymer

Abstract

To provide a solid titanium catalyst component, a catalyst for olefin polymerization and a method for polymerizing an olefin, which can produce an olefin polymer having higher stereoregularity and excellent molecular weight distribution than conventional ones with high activity and further to provide a propylene polymer having properties different from those of the conventional one.SOLUTION: There is provided a solid titanium catalyst component for producing an olefin polymer (I) containing titanium, magnesium, a halogen and a cyclic polyvalent ester group-containing compound (a) represented by the formula (1). In addition, there is provided a propylene polymer which is preferably obtained by the olefin polymerization method and has particular thermal properties mainly specified by differential scanning calorimetry (DSC).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a solid titanium catalyst component, an olefin polymerization catalyst containing the solid titanium catalyst component, an olefin polymerization process using the olefin polymerization catalyst, and a propylene polymer. [Background technology]

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

[0003] Widely known examples of such olefin polymerization catalysts include catalysts called Ziegler-Natta catalysts, which contain titanium tetrachloride or titanium trichloride, and catalysts which consist of a solid titanium catalyst component consisting of magnesium, titanium, a halogen and an electron donor, and an organometallic compound.

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

[0005] Among the above catalysts, it has been reported that excellent polymerization activity and stereospecificity are exhibited when a catalyst consisting of a solid titanium catalyst component carrying an electron donor selected from carboxylate esters, typically phthalate esters, an aluminum-alkyl compound as a cocatalyst component, and a silicon compound having at least one Si-OR (wherein R is a hydrocarbon group) is used (e.g., Patent Document 1). In addition to phthalate esters, many other electron donors, such as polyvalent ether compounds, are being investigated.

[0006] As a study on using an ester compound as an electron donor, a catalyst containing a carboxylic acid ester having an ester group with two or more valences has been disclosed (for example, Patent Document 2). The present applicant has also reported that an ester compound having a special cyclic structure gives polyolefins with a wide molecular weight distribution with high activity (Patent Document 3).

[0007] As a catalyst for producing polyolefins with a wide molecular weight distribution, a catalyst using a substituted succinic acid ester as an electron donor has been reported. The present applicant has also reported a catalyst containing a polyvalent carboxylate ester having a special cyclic structure (Patent Document 4). [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 57-63310 [Patent Document 2] Special Publication No. 2005-517746 [Patent Document 3] International Publication No. 2008 / 010459 [Patent Document 4] International Publication No. 2006 / 077945 DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0009] Polypropylene (propylene polymer), a representative example of olefin polymers with three or more carbon atoms, is known to have the potential to exhibit heat resistance and rigidity comparable to general-purpose engineering plastics, despite its hydrocarbon structure. In addition, polyolefins, which have a hydrocarbon structure, are also materials with a relatively low environmental impact in that they emit little toxic gases when disposed of by combustion or during thermal recycling (a recycling method in which combustion heat energy is recovered as electricity, etc.).

[0010] The heat resistance of propylene polymers depends largely on their stereoregularity, and it is known that their rigidity is influenced by molecular weight distribution in addition to stereoregularity. Technologies have been developed that can control the stereoregularity to a fairly high degree, but with the recent advances in molding technology, it is thought that polymers with higher stereoregularity may exhibit unexpected physical properties. By combining this with a wider molecular weight distribution, the balance of physical properties may be further improved. On the other hand, from the viewpoints of environmental protection and economic efficiency, there is a demand for the development of catalysts that show higher activity.

[0011] From the above viewpoints, the object of the present invention is to provide a solid titanium catalyst component, an olefin polymerization catalyst, and an olefin polymerization method, which are capable of producing an olefin polymer having higher stereoregularity and excellent molecular weight distribution than conventional ones with high activity. Another object of the present invention is to provide a propylene polymer having physical properties different from conventional ones. [Means for solving the problem]

[0012] As a result of intensive research, the present inventors have found that a solid titanium catalyst component containing a polyvalent ester compound having a special alicyclic structure can produce a polymer having a wide molecular weight distribution and extremely high stereoregularity with high activity, and have completed the present invention. The present invention relates to, for example, the following [1] to

[13] .

[0013] [1] A solid titanium catalyst component (I) comprising titanium, magnesium, a halogen, and a cyclic polyvalent ester group-containing compound (a) represented by the following formula (1):

[0014] [ka] [In formula (1), m and n are integers of 1 to 5 and satisfy the relationship m+n≧4. R 1 and R 2 are each a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, 3 , multiple R 4 , R 5 ~R8 are each a group selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom; R 1 ~R 8 R may have a hydrogen atom, a carbon atom, or both substituted with at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom. 5 ~R 8 Two or more of R may be bonded to each other to form a monocyclic or polycyclic ring, or adjacent substituents may be directly bonded to each other to form a multiple bond. 3 is R 4 ~R 8 may be bonded to one or more of the substituents to form a monocyclic or polycyclic ring, or adjacent substituents may be directly bonded to form a multiple bond. 3 may be bonded to each other to form a monocyclic or polycyclic ring. 3 Although they are independent of each other, R bonded to adjacent carbons 3 R may be directly bonded to each other to form a multiple bond. 4 is R 3 and R 5 ~R 8 may be bonded to one or more of the substituents to form a monocyclic or polycyclic ring, or adjacent substituents may be directly bonded to form a multiple bond. 4 may be bonded to each other to form a monocyclic or polycyclic ring. 4 Although they are independent of each other, R bonded to adjacent carbons 4 may be directly bonded to each other to form a multiple bond.

[0015] [2] The solid titanium catalyst component (I) according to item [1], wherein m is 2 or more and n is 2 or more. [3] R 3 ~R 8 are independent substituents. The solid titanium catalyst component (I) according to item [1].

[0016] [4] R 1 and R2 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. The solid titanium catalyst component (I) according to item [1].

[0017] [5] R 3 ~R 8 are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted cycloalkenyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted heteroaryloxy group. The solid titanium catalyst component (I) according to item [1].

[0018] [6] An olefin polymerization catalyst comprising the solid titanium catalyst component (I) according to item [1] and an organometallic compound catalyst component (II) containing a metal element selected from Groups 1, 2 and 13 of the periodic table.

[0019] [7] The olefin polymerization catalyst according to item [6], further comprising an electron donor (III). [8] A method for olefin polymerization, comprising carrying out polymerization of olefins in the presence of the olefin polymerization catalyst according to item [6] or [7].

[0020] [9] A propylene polymer satisfying the following requirements (αH) to (δH): (αH)MFR≧10g / 10min (βH)ΔH≧80J / g (γH)ΔH(high)≧10% (δH)[ΔH(mid) / ΔH(low)]>[ΔH(high) / ΔH(mid)] [The definitions of each symbol in the above requirements (αH) to (δH) are as follows: MFR: Melt flow rate (g / 10 min) specified under the conditions of 230℃ and 2.16 kg load according to ASTM 1238; ΔH: Heat of fusion measured by DSC method / (J / g); ΔH(high): The percentage / % of the heat of fusion in the region above 165°C in the ΔH; ΔH(mid): the percentage of heat of fusion in the range of 160°C or more and 165°C or less in the ΔH range; ΔH(low): the percentage of the heat of fusion in the region below 160° C. in the ΔH; However, the sum of ΔH(high), ΔH(mid) and ΔH(low) is 100%.

[0021]

[10] The propylene polymer according to item [9], further satisfying the following (εH): (εH)ΔH(low)<61%

[0022]

[11] A propylene polymer satisfying the following requirements (αL) to (δL): (αL)MFR<10g / 10min (βL)ΔH≧80J / g (γL)ΔH(high)≧18.5%, and ΔH(mid)≧28%, and [ΔH(high)+ΔH(mid)]≦80% (δL)Tmf≧170.0℃ [The definitions of each symbol in the above requirements (αL) to (δL) are as follows: MFR: Melt flow rate (g / 10 min) specified under the conditions of 230℃ and 2.16 kg load according to ASTM 1238; ΔH: Heat of fusion measured by DSC method / (J / g); ΔH(high): The percentage / % of the heat of fusion in the region above 165°C in the ΔH; ΔH(mid): the percentage of heat of fusion in the range of 160°C or more and 165°C or less in the ΔH range; ΔH(low): the percentage of the heat of fusion in the region below 160° C. in the ΔH; However, the sum of ΔH(high), ΔH(mid) and ΔH(low) is 100%; Tmf: final melting point / °C determined by the following method using a differential scanning calorimeter (DSC) on a Seiko Instruments DSC220C device; 3 to 10 mg of sample was sealed in an aluminum pan. The temperature was increased from room temperature to 240°C at a rate of 80°C / min. Hold at 240°C for 1 minute. Cool to 0°C at a rate of 80°C / min. Hold at 0°C for 1 minute. Heat to 150°C at a rate of 80°C / min. Hold at 150°C for 5 minutes. 1. The temperature value at the intersection of the tangent to the inflection point on the high-temperature side of the peak that appears on the chart obtained by heating to 180°C at a rate of 35°C / min and the baseline.

[0023]

[12] The propylene polymer according to item

[11] , further satisfying the following (εL): (εL)Tmf-ΔH(high)≧149.0

[0024]

[13] A propylene polymer satisfying the following requirements (αS) to (εS): (αS) Decane soluble component content ≧5% (βS)ΔH≧80J / g (γS)Tmf≧169℃ (δS) ΔH(low)≧61%, and 20%≧ΔH(high)≧5% (εS) Content of structural units derived from olefins other than propylene in the decane insoluble portion ≦5 mol% [The definitions of each symbol in the above requirements (αS) to (εS) are as follows: ΔH: Heat of fusion measured by DSC method / (J / g); ΔH(high): The percentage / % of the heat of fusion in the region above 165°C in the ΔH; ΔH(mid): the percentage of heat of fusion in the range of 160°C or more and 165°C or less in the ΔH range; ΔH(low): the percentage of the heat of fusion in the region below 160° C. in the ΔH; However, the sum of ΔH(high), ΔH(mid) and ΔH(low) is 100%; Tmf: final melting point / °C determined by the following method using a differential scanning calorimeter (DSC) on a Seiko Instruments DSC220C device; 3 to 10 mg of sample was sealed in an aluminum pan. The temperature was increased from room temperature to 240°C at a rate of 80°C / min. Hold at 240°C for 1 minute. Cool to 0°C at a rate of 80°C / min. Hold at 0°C for 1 minute. Heat to 150°C at a rate of 80°C / min. Hold at 150°C for 5 minutes. 1. The temperature value at the intersection of the tangent to the inflection point on the high-temperature side of the peak that appears on the chart obtained by heating to 180°C at a rate of 35°C / min and the baseline. Effect of the Invention

[0025] According to the present invention, it is possible to produce, with high activity, an olefin polymer which has extremely high stereoregularity, a high melting point, a molecular weight-dependent heat of fusion, and a wide molecular weight distribution. In addition, it is also possible to produce a polymer which is expected to have excellent transparency when used for films, etc.

[0026] Furthermore, it is expected that the use of the solid titanium catalyst component, olefin polymerization catalyst, and olefin polymerization method of the present invention will enable the production of olefin polymers having not only excellent moldability and rigidity but also higher heat resistance. [Brief description of the drawings]

[0027] [Figure 1] 1 is a DSC measurement chart of the polymer of Example 2-1 (conditions during the second heating). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] The solid titanium catalyst component (I), the olefin polymerization catalyst, the process for producing an olefin polymer, and the propylene polymer according to the present invention will be described in detail below.

[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 polyvalent ester group-containing compound (a)").

[0030] <Cyclic polyvalent ester group-containing compound (a)> The cyclic polyvalent ester group-containing compound (a) is represented by the following formula (1).

[0031] [ka] In formula (1), m and n are integers of 1 to 5 and satisfy the relationship m+n≧4. R 1 and R 2 are each a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, 3 , multiple R 4 , R 5 ~R 8 are each a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom; R 1 ~R 8 R may have a hydrogen atom, a carbon atom, or both substituted with at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom. 5 ~R 8 Two or more of R may be bonded to each other to form a monocyclic or polycyclic ring, or adjacent substituents may be directly bonded to each other to form a multiple bond. 3 is R 4 ~R 8 may be bonded to one or more of the substituents to form a monocyclic or polycyclic ring, or adjacent substituents may be directly bonded to form a multiple bond. 3Adjacent R may be bonded to each other to form a monocyclic or polycyclic ring. 3 Although they are independent of each other, they may be directly bonded to each other to form multiple bonds. 4 is R 3 and R 5 ~R 8 may be bonded to one or more of the substituents to form a monocyclic or polycyclic ring, or adjacent substituents may be directly bonded to form a multiple bond. 4 Adjacent R may be bonded to each other to form a monocyclic or polycyclic ring. 4 Although they are in an independent relationship with each other, they may be directly bonded to each other to form a multiple bond.

[0032] The above m and n are selected from integers of 1 to 5 and satisfy the relationship m+n≧4. The above m and n are values ​​related to the size and balance of the cyclic structure. The lower limit of m and n is preferably 2. Furthermore, an embodiment in which both m and n are 2 or more is preferable.

[0033] The upper limit of m and n is 5, and preferably 4. The above numerical values ​​of m and n may be the same or different.

[0034] R 1 and R 2 are each a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Preferably, they are substituted or unsubstituted hydrocarbon groups having 6 to 20 carbon atoms and an aryl group, and may have a structure containing a heteroatom as described below. Examples of the heteroatom-containing aryl group include those having a basic skeleton in which the aryl structure itself contains a heteroatom, such as a pyrrole ring or a pyran ring, and those having a substituent such as a heteroatom-containing hydrocarbon group, such as an alkoxy group, bonded to a benzene ring.

[0035] The structure containing a heteroatom is typically a structure having a substituent containing a heteroatom. A preferred example of such a substituent is a heteroatom-containing aryl group, and a particularly preferred example is an aryl group containing oxygen.

[0036] R 3 ~R 8 and R are each a group selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom.

[0037] The above R 1 ~R 8 In the formula (I), hydrogen atoms, carbon atoms, or both may be partially substituted with at least one atom selected from the group consisting of nitrogen atoms, oxygen atoms, phosphorus atoms, halogen atoms, and silicon atoms. 1 ~R 8 includes embodiments of hydrocarbon radicals containing nitrogen, oxygen, phosphorus, halogens and silicon, which may be substituted at one or more positions.

[0038] In the present invention, the description of an "atom" such as a halogen atom or a hydrogen atom in the description of a substituent may of course refer to an embodiment having a bond, such as "H-" or "Cl-", as represented in a structural formula.

[0039] R 1 and R 2 may be bonded to each other to form a ring structure. 1 ,R 2 and a substituent selected from the group consisting of R 3 ~R 8 and the substituents selected from the group consisting of may be bonded to each other to form a ring structure.

[0040] Also, the above R 3 ~R 8 may be bonded directly to adjacent substituents to form a carbon-carbon double bond or a triple bond.

[0041] The above R 3 is R 4 ~R 8 may be bonded to one or more of the R 3They may be bonded to each other to form a monocyclic or polycyclic ring. The above R 3 R bonded to different carbons 3 Although they are independent of each other, R bonded to adjacent carbons 3 may be directly bonded to each other to form a multiple bond. Here, the independent relationship means that there are multiple R 3 This means that the structural formulas can be clearly distinguished from each other. Specifically, for example, there are multiple R 3 They do not bond to each other to form a ring structure with three or more members.

[0042] R 4 is R 3 and R 5 ~R 8 may be bonded to one or more of the substituents to form a monocyclic or polycyclic ring, or adjacent substituents may be directly bonded to form a multiple bond. 4 They may be bonded to each other to form a monocyclic or polycyclic ring.

[0043] R attached to different carbons 4 Although they are independent of each other, R bonded to adjacent carbons 4 They may be directly bonded to each other to form multiple bonds. This "independent relationship" means that R 3 This is similar to the content explained in .

[0044] Also, the above R 3 ~R 8 In terms of the balance of activity, stereoregularity, and other properties, it may be preferable that at least one of the substituents is a substituent other than hydrogen. Furthermore, it may be preferable that one or more of the carbon atoms forming the cyclic structure is a quaternary carbon.

[0045] In addition, as described later, it is believed that the basic cyclic structure represented by formula (1) has a large effect on the performance of the catalyst. 5 ~R 8In some cases, it may be preferable for R to be independent of each other in terms of manufacturing costs and ease of handling. 5 ~R 8 is R 3 Or R 4 and R are preferably independent of each other. On the other hand, as described above, they may be bonded to each other to form a cyclic structure. The portion forming the ring may be either a monocyclic structure or a polycyclic structure. The portion forming the ring may be a double structure or a structure further having a cyclic structure. It may be preferable that the cyclic structure formed by bonding the substituents to each other is a structure including a double bond. It is more preferable that the double bond is a carbon-carbon double bond. In addition, the carbon-carbon double bond includes an aromatic structure. Such a cyclic structure may be formed by bonding the R bonded to the carbon described later. 3 , R 4 The structure is similar to that containing

[0046] The above-mentioned hydrocarbon group is a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10, more preferably 2 to 8, even more preferably 3 to 8, still more preferably 4 to 8, and particularly preferably 4 to 6. Examples of this hydrocarbon group include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, such as substituted or unsubstituted aryl 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, and phenyl group, and substituted or unsubstituted cycloalkenyl groups. The above-mentioned alicyclic hydrocarbon groups and aromatic hydrocarbon groups may contain a substituent. Among these, n-butyl group, isobutyl group, hexyl group, octyl group, phenyl group, and the like are preferred, and n-butyl group, isobutyl group, and phenyl group are more preferred.

[0047] R 1 ~R 8may be a hydrocarbon group containing nitrogen, oxygen, phosphorus, halogen and silicon. Such a substituent can be selected from known structures. More specifically, preferred examples include a carboxylate group, an aldehyde group, an acetyl group, a carbonyl structure-containing group such as an oxycarbonylalkyl group, an alkoxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted cycloalkenyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted heteroaryloxy group, and a siloxy group. The heteroatom is preferably nitrogen and oxygen, more preferably oxygen.

[0048] Among the heteroatom-containing substituents, an aryl group containing an oxygen-containing substituent is preferred, and specifically, a structure in which an oxygen-containing substituent such as an alkoxy group, an aryloxy group, an alkoxyalkyl group, an aryloxyalkyl group, or a substituent in which the oxygen of the substituent is replaced by a carbonyl group or a carboxyl group is bonded to an aromatic group is preferred. Among the above, a substituent in which an alkoxy group or an aryloxy group is bonded to an aromatic skeleton is preferred, and a substituent in which an alkoxy group is bonded to an aromatic skeleton is more preferred. The number of carbon atoms of 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 above methoxyphenyl group, an ethoxyphenyl group, a propyloxyphenyl group, an isopropyloxyphenyl group, a butoxyphenyl group, a phenoxyphenyl group, and the like are preferred examples. Such an aryl group containing an oxygen-containing substituent can be represented by R 1 , R 2 In some cases, it is particularly preferable to use

[0049] R 1 ~R 8 At least one of these is preferably a substituent according to the above-mentioned preferred embodiment, and all of these are more preferably a substituent according to the above-mentioned preferred embodiment.

[0050] Among the above, R3 ~R 8 is preferably a hydrogen atom, a hydrocarbon group such as a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyloxy group, or a substituted or unsubstituted aryl group; a heteroatom-containing hydrocarbon group such as a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted cycloalkenyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted heteroaryloxy group. Among these, a hydrocarbon group is more preferable, and a substituted or unsubstituted alkyl group is particularly preferable.

[0051] CR of the above formula (1) 3 Structure and CR 4 The carbon chain structure may be a single bond, a double bond, or a triple bond, but preferably is mainly a single bond. A heteroatom may be connected between the carbon chain bonds. Such a chain structure may be exemplified by the following (divalent) structural formula:

[0052] [ka]

[0053] The above R 3 ~R 8 , especially R 4 ~R 8 It is preferable that one or more of the substituents are other than hydrogen. Furthermore, it may be preferable that two or more of the substituents are other than hydrogen. In that case, two or more types may be mixed, or all may be a single substituent. Examples of such a substituent include the above-mentioned R 1 ~R 8The substituent other than hydrogen can be selected from the substituents exemplified above. The substituent other than hydrogen is preferably a hydrocarbon group or an oxygen-containing hydrocarbon group, and more preferably a hydrocarbon group. More specifically, the substituent is selected from a substituted or unsubstituted alkyl group and a cycloalkyl group, and more preferably an unsubstituted alkyl group.

[0054] The above R 3 ~R 8 Among them, R 7 and R 8 It is preferred that one or more of the following are non-hydrogen substituents as described above. A solid titanium catalyst component containing a compound having the above structure tends to have an excellent balance of activity, stereospecificity, molecular weight controllability, reaction controllability, and the like.

[0055] Examples of such a cyclic polyvalent ester group-containing compound (a) include the following structures: The structural formulas of the following exemplary compounds may have stereoisomers, and although some of them specify isomeric structures, they may also include isomeric structures that are not exemplified.

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] In the above structural formulas, the methyl group is represented as "Me", the ethyl group as "Et", the butyl group as "Bu", and the phenyl group as "Ph". Additionally, "i" stands for "iso" and "t" stands for "tertiary".

[0067] The compound having the above diester structure includes OCOR in formula (1). 1 Groups and OCOR 2 There are isomers such as cis and trans derived from the group, but any structure has an effect that meets the object of the present invention. The cis form is more preferable. The higher the content of the cis form, the higher the activity and the stereoregularity of the obtained polymer tend to be.

[0068] These compounds may be used alone or in combination of two or more. Furthermore, these cyclic polyvalent ester group-containing compounds (a) may be used in combination with the catalyst component (b) or catalyst component (c) described below, as long as the object of the present invention is not impaired.

[0069] The cyclic polyvalent ester group-containing 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), a step is provided in which a carboxylic acid anhydride or carboxylic acid halide corresponding to the catalyst component (a) is substantially contacted with a corresponding polyol, so that the cyclic polyvalent ester group-containing compound (a) can be contained in the solid titanium catalyst component.

[0070] In the process for producing an olefin polymer of the present invention, there is a tendency that a polymer having a wide molecular weight distribution and high stereoregularity can be easily obtained at a high activity. The reason for this is unclear at present, but is presumed to be as follows.

[0071] The cyclic polyvalent ester group-containing compound (a) used in the present invention has a special polycyclic structure as described above, and is therefore presumed to have a moderate rigidity as a compound and relatively little structural displacement. On the other hand, it can be understood as a structure in which a portion having a somewhat flexible movement also exists. Therefore, when the cyclic polyvalent ester group-containing compound (a) is coordinated to a titanium compound or magnesium compound described later, it is considered that the compound maintains a stable structure and has little fluctuation in stereospecificity as a catalyst during an olefin polymerization reaction and in polymerization reaction activity. In addition, the flexible structural portion is expected to mitigate the occurrence of distortion derived from the cyclic structure, and may function like a buffer against changes in the reaction environment. From these viewpoints, it is considered that the compound gives a polymer with high stereoregularity with high activity. From this viewpoint, it can also be presumed that the compound has the potential to easily give a component with a high molecular weight.

[0072] On the other hand, in the case of a stable structure with little deformation of the structure, it was initially feared that the molecular weight distribution would be narrow, but as shown in the examples described below, the method of the present invention can produce a polymer with a wide molecular weight distribution.The inventors speculate that this is because, in the case of this cyclic polyvalent ester group-containing compound (a), the minute fluctuation of the cyclic structure and the combination of fluctuations of each ring structure have a high effect on the molecular weight of the obtained polymer, and the combination of stereoisomeric structures (e.g., chair type, boat type, etc.) that each ring can take may become more diverse due to the presence of multiple ring structures.

[0073] In preparing the solid titanium catalyst component (I) of the present invention, in addition to the above-mentioned cyclic polyvalent ester group-containing compound (a), a magnesium compound and a titanium compound are used.

[0074] <Magnesium compounds> Specific examples of such magnesium compounds include: Magnesium halides such as magnesium chloride and magnesium bromide; Alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, and phenoxy magnesium chloride; Alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, and 2-ethylhexoxymagnesium; Aryloxymagnesium such as phenoxymagnesium; Magnesium carboxylates, such as magnesium stearate Examples of known magnesium compounds include:

[0075] These magnesium compounds may be used alone or in combination of two or more kinds. Furthermore, these magnesium compounds may be complex compounds or complex compounds with other metals, or mixtures with other metal compounds.

[0076] Among these, magnesium compounds containing halogen are preferred. Magnesium halides, especially magnesium chloride, are preferably used. In addition, alkoxymagnesium such as ethoxymagnesium are also preferably used. The magnesium compound may be derived from other substances, for example, a compound obtained by contacting an organomagnesium compound such as a Grignard reagent with a titanium halide, a silicon halide, or a halogenated alcohol.

[0077] <Titanium compounds> Examples of titanium compounds include those represented by the general formula: Ti(OR') g X 4-g (R' is a hydrocarbon group, X is a halogen atom, and g is 0≦g≦4.) More specifically, the following tetravalent titanium compounds are available: Titanium tetrahalides such as TiCl4, TiBr4; Alkoxy titanium trihalides such as Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(On-C4H9)Cl3, Ti(OC2H5)Br3, Ti(O-iso-C4H9)Br3; Alkoxytitanium dihalides such as Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2; Alkoxy titanium monohalides such as Ti(OCH3)3Cl, Ti(On-C4H9)3Cl, Ti(OC2H5)3Br; Tetraalkoxytitanium such as Ti(OCH3)4, Ti(OC2H5)4, Ti(OC4H9)4, Ti(O-2-ethylhexyl)4 Some examples include:

[0078] Among these, titanium tetrahalides are preferred, and titanium tetrachloride is particularly preferred. These titanium compounds may be used alone or in combination of two or more. Examples of the magnesium compounds and titanium compounds described above include compounds described in detail in Patent Documents 1 and 2.

[0079] The solid titanium catalyst component (I) used in the present invention can be prepared by any known method without limitation, except for using the cyclic polyvalent ester group-containing compound (a).Specific preferred methods include the following methods (P-1) to (P-4).

[0080] (P-1) A method in which a solid adduct consisting of a magnesium compound and a catalyst component (b), a cyclic polyvalent ester group-containing compound (a), and a liquid titanium compound are contacted in a suspended state in the presence of an inert hydrocarbon solvent.

[0081] (P-2) A method in which a solid adduct consisting of a magnesium compound and a catalyst component (b) is contacted with a cyclic polyvalent ester group-containing compound (a) and a liquid titanium compound in separate batches.

[0082] (P-3) A method in which a solid adduct consisting of a magnesium compound and a catalyst component (b), a cyclic polyvalent ester group-containing compound (a), and a liquid titanium compound are contacted in a suspended state in the presence of an inert hydrocarbon solvent, and the contact is carried out in multiple batches.

[0083] (P-4) A method of contacting a liquid magnesium compound consisting of a magnesium compound and a catalyst component (b), a liquid titanium compound and a cyclic polyvalent ester group-containing compound (a).

[0084] The reaction temperature is preferably in the range of -30°C to 150°C, more preferably -25°C to 130°C, and further preferably -25°C to 120°C.

[0085] The production of the solid titanium catalyst component can be carried out in the presence of a known medium, if necessary. Examples of the medium include aromatic hydrocarbons having a slight polarity, such as toluene, and known aliphatic and alicyclic hydrocarbon compounds, such as heptane, octane, decane, and cyclohexane. Among these, aliphatic hydrocarbons are preferred.

[0086] When the reaction is carried out within the above range, it is possible to obtain a polymer having a broad molecular weight distribution, while at the same time achieving a higher level of activity and stereoregularity of the resulting polymer.

[0087] (Catalyst component (b)) The catalyst component (b) used to form the solid adduct or liquid magnesium compound is preferably a known compound capable of solubilizing the 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 these compounds include those described in detail in Patent Document 1 and Patent Document 2.

[0088] More specifically, the alcohol capable of solubilizing the magnesium compound is 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, methylcyclohexanol; Aromatic alcohols such as benzyl alcohol, methylbenzyl alcohol; Aliphatic alcohols with alkoxy groups, such as n-butyl cellosolve Some examples include:

[0089] Examples of the carboxylic acid include organic carboxylic acids having 7 or more carbon atoms, such as caprylic acid and 2-ethylhexanoic acid. Examples of the aldehyde include aldehydes having 7 or more carbon atoms, such as capric aldehyde and 2-ethylhexyl aldehyde.

[0090] Examples of the amine include amines having 6 or more carbon atoms, such as heptylamine, octylamine, nonylamine, laurylamine, and 2-ethylhexylamine.

[0091] As the above catalyst component (b), the above alcohols are preferred, with ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, decanol and the like being particularly preferred.

[0092] The amount of magnesium compound and catalyst component (b) used when preparing the solid adduct or liquid magnesium compound varies depending on the type, contact conditions, etc., but the magnesium compound is used in an amount of 0.1 to 20 mol / L, preferably 0.5 to 5 mol / L per unit volume of the catalyst component (b). If necessary, a medium inert to the solid adduct can also be used in combination. As the medium, known hydrocarbon compounds such as heptane, octane, and decane can be mentioned as preferred examples.

[0093] The composition ratio of magnesium to catalyst component (b) in the resulting solid adduct or liquid magnesium compound varies depending on the type of compound used and cannot be generally defined. However, the amount of catalyst component (b) relative to 1 mole of magnesium in the magnesium compound 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 is preferably in the range of 5 moles or less.

[0094] <Aromatic carboxylate and / or compound having two or more ether bonds via multiple carbon atoms> The solid titanium catalyst component (I) of the present invention may further contain an aromatic carboxylate and / or a compound having two or more ether bonds via a plurality of 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), the activity and stereoregularity may be increased and the molecular weight distribution may be broadened.

[0095] As this catalyst component (c), known aromatic carboxylic acid esters and polyether compounds that have been preferably used in conventional olefin polymerization catalysts, such as the compounds described in Patent Document 2 and JP-A-2001-354714, can be used without limitation.

[0096] Specific examples of the aromatic carboxylate include aromatic carboxylate monoesters such as benzoates and toluates, as well as aromatic polyvalent carboxylates such as phthalates. Among these, aromatic polyvalent carboxylates are preferred, and phthalates are more preferred. As the phthalates, alkyl phthalates such as ethyl phthalate, n-butyl phthalate, isobutyl phthalate, hexyl phthalate, and heptyl phthalate are preferred, and diisobutyl phthalate is particularly preferred.

[0097] More specifically, the polyether compound includes a compound represented by the following formula (3).

[0098] [ka]

[0099] 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 ~R 36are each a hydrogen atom or a substituent having at least one element selected from carbon, hydrogen, oxygen, fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron and silicon.

[0100] When m is 2 or more, there are multiple R 11 and R 12 may be the same or different. Any R 11 , R 12 , R 31 ~R 36 , preferably R 11 and R 12 may combine together to form a ring other than a benzene ring.

[0101] Specific examples of such compounds include: 2-Isopropyl-1 , 3-Dimethoxypropane, 2-s-butyl-1 , 3-Dimethoxypropane, 2-Cumyl-1 , 1-substituted dialkoxypropanes such as 3-dimethoxypropane; 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 , 2-substituted dialkoxypropanes such as 3-dimethoxypropane; 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 , Dialkoxycycloalkanes such as 3-dimethoxy-4-cyclohexenyl The following can be given as examples:

[0102] Of these, 1 , 3-Diethers are preferred, particularly 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 alone or in combination of two or more.

[0103] The above-mentioned cyclic polyvalent ester group-containing compound (a), catalyst component (b), and catalyst component (c) may be considered to belong to the components called electron donors by the relevant art. The above-mentioned electron donor components are known to have the effect of increasing the stereoregularity of the resulting polymer while maintaining high catalyst activity, the effect of controlling the composition distribution of the resulting copolymer, and the effect of acting as a flocculant to control the particle shape and particle size of the catalyst particles.

[0104] It is believed that the cyclic polyvalent ester group-containing compound (a) of the present invention also shows the effect of enabling the molecular weight distribution to be further controlled by the electron donor.

[0105] 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 desirably 2 to 100, preferably 4 to 90. The molar ratio of the cyclic polyvalent ester group-containing compound (a) / titanium (i.e., the number of moles of the cyclic polyvalent ester group-containing compound (a) / the number of moles of titanium atoms) is desirably 0.01 to 100, preferably 0.2 to 10. In the catalyst component (b) and the catalyst component (c), the catalyst component (b) / titanium atom (molar ratio) is desirably 0 to 100, preferably 0 to 10, and the catalyst component (c) / titanium atom (molar ratio) is desirably 0 to 100, preferably 0 to 10. It is desirable that the magnesium / titanium (atomic ratio) (ie, the number of moles of magnesium atoms / the number of moles of titanium atoms) is 2-100, preferably 4-50.

[0106] The content of components that may be contained other than the aforementioned cyclic polyvalent ester group-containing compound (a), such as catalyst component (b) and catalyst component (c), is preferably 20% by weight or less, more preferably 10% by weight or less, based on 100% by weight of the cyclic polyvalent ester group-containing compound (a).

[0107] As more detailed preparation conditions for the solid titanium catalyst component (I), the conditions described in, for example, EP585869A1 (European Patent Application Publication No. 0585869) and Patent Document 2 can be preferably used, except for using the cyclic polyvalent ester group-containing compound (a).

[0108] [Olefin polymerization catalyst] The olefin polymerization catalyst according to the present invention comprises The solid titanium catalyst component (I) according to the present invention, an organometallic compound catalyst component (II) containing a metal element selected from Groups 1, 2 and 13 of the periodic table; The present invention is characterized in that it includes:

[0109] <Organometallic compound catalyst component (II)> As the organometallic compound catalyst component (II), compounds containing a Group 13 metal, for example, organoaluminum compounds, complex alkylates of Group 1 metals and aluminum, organometallic compounds of Group 2 metals, etc. can be used. Among these, organoaluminum compounds are preferred. Specifically, as the organometallic compound catalyst component (II), the organometallic compound catalyst components described in known documents such as the above-mentioned EP585869A1 can be cited as preferred examples.

[0110] <Electron donor (III)> Further, the olefin polymerization catalyst of the present invention may contain an electron donor (III) as necessary together with the above-mentioned organometallic compound catalyst component (II). Preferably, the electron donor (III) is an organosilicon compound. As this organosilicon compound, for example, a compound represented by the following general formula (4) can be exemplified. R S n Si(OR”) 4-n ···(4) In formula (4), R S and R” are hydrocarbon groups, and n is an integer of 0 < n < 4.

[0111] Specific examples of the organosilicon compound represented by the general formula (4) as described 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, cyclopentyldimethylethoxysilane, etc.

[0112] Of these, vinyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, and dicyclopentyldimethoxysilane are preferably used.

[0113] Further, the silane compound represented by the following formula (5), which is described in WO 2004 / 016662, is also a preferred example of the organosilicon compound. Si(OR a )3(NR b R c ) ···(5)

[0114] In formula (5), R a is a hydrocarbon group having 1 to 6 carbon atoms, and R a Examples of the alkyl group include unsaturated or saturated aliphatic hydrocarbon groups having 1 to 6 carbon atoms, and particularly preferably hydrocarbon groups having 2 to 6 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, an n-pentyl group, an iso-pentyl group, a cyclopentyl group, an n-hexyl group, and a cyclohexyl group, and among these, an ethyl group is particularly preferred.

[0115] In formula (5), R b is a hydrocarbon group having 1 to 12 carbon atoms or hydrogen, and R b Examples of the aryl group include hydrogen and unsaturated or saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms. Specific examples include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, an n-pentyl group, an iso-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, and an octyl group. Among these, an ethyl group is particularly preferred.

[0116] In formula (5), R c is a hydrocarbon group having 1 to 12 carbon atoms, R cExamples of the aryl group include hydrogen and unsaturated or saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, an n-pentyl group, an iso-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, and an octyl group. Among these, an ethyl group is particularly preferred.

[0117] Specific examples of the compound 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, ethyl isopropylaminotriethoxysilane, and methylethylaminotriethoxysilane.

[0118] Further, another example of the organosilicon compound is a compound represented by the following formula (6). R N NSi(OR a )3···(6)

[0119] In formula (6), R N N is a cyclic amino group, and examples of this cyclic amino group include a perhydroquinolino group, a perhydroisoquinolino group, a 1,2,3,4-tetrahydroquinolino group, a 1,2,3,4-tetrahydroisoquinolino group, and an octamethyleneimino group.

[0120] Specific examples of the compound represented by the above formula (6) include (perhydroquinolino)triethoxysilane, (perhydroisoquinolino)triethoxysilane, (1,2,3,4-tetrahydroquinolino)triethoxysilane, (1,2,3,4-tetrahydroisoquinolino)triethoxysilane, and octamethyleneiminotriethoxysilane. These organosilicon compounds can also be used in combination of two or more.

[0121] Other preferred examples of compounds useful as the electron donor (III) include the above-mentioned aromatic carboxylates and / or the polyether compounds described as examples of the compounds having two or more ether bonds via a plurality of carbon atoms (the above-mentioned catalyst component (c)).

[0122] Among these polyether compounds, 1 , 3-Diethers are preferred, particularly 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 alone or in combination of two or more.

[0123] When the electron donor (III) is used in combination, it is often possible to adjust the stereoregularity and molecular weight. Specifically, when the ratio of the electron donor (III) to the organometallic compound catalyst component is increased, a polymer with high stereoregularity and a polymer with high molecular weight tend to be obtained. On the other hand, when the ratio of the electron donor (III) is decreased, a polymer with low stereoregularity (e.g., a polymer with a high content of decane-soluble components, which will be described later) and a polymer with low molecular weight tend to be obtained.

[0124] In addition to the above-mentioned components, the olefin polymerization catalyst of the present invention may contain other components useful for olefin polymerization as necessary, such as a carrier such as silica, an antistatic agent, a particle flocculant, a storage stabilizer, etc.

[0125] [Olefin polymerization method] The olefin polymerization method according to the present invention is characterized in that olefin polymerization is carried out using the olefin polymerization catalyst of the present invention. In the present invention, the term "polymerization" may include copolymerization such as random copolymerization and block copolymerization in addition to homopolymerization.

[0126] In the olefin polymerization method of the present invention, it is also possible to carry out main polymerization in the presence of a prepolymerization catalyst obtained by prepolymerizing an α-olefin in the presence of the olefin polymerization catalyst of the present invention. This prepolymerization is carried out 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.

[0127] In the preliminary polymerization, the catalyst can be used at a higher concentration than the catalyst concentration in the system in the main polymerization. The concentration of the solid titanium catalyst component (I) in the prepolymerization is desirably in the range of usually about 0.001 to 200 millimoles, preferably about 0.01 to 50 millimoles, and particularly preferably 0.1 to 20 millimoles, calculated as titanium atom per liter of liquid medium.

[0128] The amount of the organometallic compound catalyst component (II) in the prepolymerization may be an amount that produces 0.1 to 1000 g, preferably 0.3 to 500 g, of polymer per gram of the solid titanium catalyst component (I), and is generally about 0.1 to 300 mol, preferably about 0.5 to 100 mol, and particularly preferably 1 to 50 mol, per mol of titanium atom in the solid titanium catalyst component (I).

[0129] In the preliminary polymerization, the electron donor (III) and the like can be used as necessary, and in this case, these components are used in an amount of 0.1 to 50 mol, preferably 0.5 to 30 mol, and more preferably 1 to 10 mol, per mol of titanium atom in the solid titanium catalyst component (I). By adjusting the amount of the electron donor (III), the stereoregularity of the obtained olefin polymer can be adjusted in some cases.

[0130] The prepolymerization can be carried out under mild conditions by adding an olefin and the above-mentioned catalyst components to an inert hydrocarbon medium.

[0131] In this case, the inert hydrocarbon medium to be used is specifically, Aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cycloheptane, methylcycloheptane, 4-cycloheptane, methyl 4-cycloheptane; Aromatic hydrocarbons such as benzene, toluene, and xylene; Halogenated hydrocarbons such as ethylene chloride and chlorobenzene, Alternatively, a mixture of these may be used.

[0132] Among these inert hydrocarbon media, it is particularly preferable to use an aliphatic hydrocarbon. When an inert hydrocarbon medium is used, it is preferable to carry out the prepolymerization in a batch manner.

[0133] On the other hand, the prepolymerization can be carried out using the olefin itself as a solvent, or in the substantial absence of a solvent, in which case it is preferred to carry out the prepolymerization continuously.

[0134] The olefin used in the preliminary polymerization may be the same as or different from the olefin used in the main polymerization described below, and specifically, it is preferably propylene.

[0135] The temperature during the prepolymerization is usually within the range of about -20 to +100°C, preferably about -20 to +80°C, and more preferably 0 to +40°C.

[0136] Next, the main polymerization, which is carried out after the above-mentioned prepolymerization or without prepolymerization, will be described.

[0137] The olefins that can be used (i.e., polymerized) in this polymerization include α-olefins having 3 to 20 carbon atoms, such as linear olefins such as 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 such as 4-methyl-1-pentene, 3-methyl-1-pentene, and 3-methyl-1-butene, and propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and 3-methyl-1-butene are preferred. In addition, from the viewpoint that the merits of a polymer with a wide molecular weight distribution are easily manifested in a resin with high rigidity, propylene, 1-butene, 4-methyl-1-pentene, and 3-methyl-1-butene are particularly preferred.

[0138] Together 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 dienes and non-conjugated dienes, including dienes such as cyclopentene, cycloheptene, norbornene, tetracyclododecene, isoprene, and butadiene, can also be used as polymerization raw materials together with ethylene and α-olefins. These compounds may be used alone or in combination of two or more (hereinafter, olefins used together with the above-mentioned ethylene or "α-olefins having 3 to 20 carbon atoms" are also referred to as "other olefins").

[0139] Among the above other olefins, ethylene and aromatic vinyl compounds are preferred. In addition, other olefins such as ethylene may be used in combination in a small amount, for example, 10% by weight or less, preferably 5% by weight or less, based on 100% by weight of the total amount of olefins.

[0140] In the present invention, the preliminary polymerization and the main polymerization can be carried out by any of liquid phase polymerization methods such as bulk polymerization, solution polymerization and suspension polymerization, or gas phase polymerization methods.

[0141] When the main polymerization is carried out in the form of a slurry polymerization reaction, the reaction solvent may be the inert hydrocarbon used in the prepolymerization described above, or an olefin which is liquid at the reaction temperature.

[0142] In the main polymerization 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, calculated as titanium atoms per 1 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 prepolymerized catalyst component in the polymerization system. The electron donor (III), if used, 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 mentioned above, the stereoregularity and molecular weight can be adjusted by the amount of the electron donor (III) used.

[0143] If the polymerization is carried out in the presence of hydrogen, the molecular weight of the resulting polymer can be adjusted, and a polymer having a high melt flow rate can be obtained.

[0144] In the present invention, the polymerization temperature of the olefin is usually about 20 to 200°C, preferably about 30 to 100°C, more preferably 50 to 90°C. The pressure is usually set to normal pressure to 10 MPa, preferably 0.20 to 5 MPa. In the polymerization method of the present invention, the polymerization can be carried out by any of batch, semi-continuous, and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions. By carrying out such multi-stage polymerization, it is possible to further widen the molecular weight distribution of the olefin polymer.

[0145] The olefin polymer thus obtained may be any of a homopolymer, a random copolymer, a block copolymer, and the like. When olefin polymerization, particularly propylene polymerization, is carried out using the above-mentioned olefin polymerization catalyst, a highly stereoregular propylene polymer having a decane insoluble component content of 70% or more, preferably 85% or more, and particularly preferably 90% or more can be obtained.

[0146] Furthermore, according to the olefin polymerization method of the present invention, even if multi-stage polymerization is not performed, polyolefins, particularly polypropylene, having a wide molecular weight distribution can be obtained even with a small number of stages, for example, single-stage polymerization. The olefin polymerization method of the present invention is characterized in that it often produces olefin polymers having a higher ratio of high molecular weight components and a lower ratio of low molecular weight components (particularly called solid components) than conventional olefin polymers having the same melt flow rate (MFR). This characteristic can be confirmed by gel permeation chromatography (GPC) measurement described later, and polymers having both high Mw / Mn and Mz / Mw values ​​can be obtained.

[0147] Conventional polypropylene obtained using a solid titanium catalyst component containing magnesium, titanium, a halogen, and an electron donor generally has an Mw / Mn value of 5 or less and an Mz / Mw value of less than 4, which are indices of molecular weight distribution determined by GPC measurement, in the region of MFR of 1 to 10 g / 10 min. However, by using the olefin polymerization method of the present invention, an olefin polymer having an Mw / Mn value of 6 to 30, preferably 7 to 20, can be obtained under the same polymerization conditions as above. Also, an olefin polymer having an Mz / Mw value of 4 to 15, more preferably 4.5 to 10 can be obtained. In particular, according to the olefin polymerization method of the present invention, a polymer having a high Mz / Mw value can often be obtained.

[0148] It is common knowledge among those in the industry that polypropylene with a high Mw / Mn value has excellent moldability and rigidity. On the other hand, a high Mz / Mw value indicates a high content of high molecular weight components, and it is expected that the resulting polypropylene will have a high melt tension and excellent moldability.

[0149] By using the olefin polymerization method of the present invention, it is possible to obtain a polymer having a wide molecular weight distribution without performing multi-stage polymerization, which may allow the polymer production equipment to be simplified. In addition, it is expected that, when the method is applied to the conventional multi-stage polymerization method, a polymer having excellent melt tension and moldability can be obtained.

[0150] Other methods for obtaining polymers with a wide molecular weight distribution include dissolving and mixing polymers with different molecular weights or melt kneading them, but the polymers obtained by these methods may not have sufficient improvement in melt tension or moldability, despite the relatively complicated operation. This is presumably because polymers with different molecular weights are basically difficult to mix. On the other hand, the polymers obtained by the olefin polymerization method of the present invention are expected to have high melt tension and excellent moldability because polymers with extremely wide ranges of different molecular weights are mixed at the catalyst level, i.e., at the nano level.

[0151] As described above, the polymer obtained by the olefin polymerization method of the present invention has high stereoregularity. Therefore, the olefin polymer obtained by the method of the present invention tends to have a high melting point. The melting point is usually determined by differential scanning calorimetry (DSC).

[0152] As described above, the olefin polymer, particularly the propylene polymer, obtained by the method of the present invention has a tendency to have a wide molecular weight distribution, particularly a large Mz, and therefore a distribution that spreads toward the high molecular weight side. Since the molecular mobility of an olefin polymer varies depending on the molecular weight, in the case of a polymer with a wide molecular weight distribution, the chart obtained by DSC measurement may not have a single-peak shape but may have a multi-peak shape or a broad shape. That is, since the ultra-high molecular weight is more difficult to crystallize, it is possible that the wide shape toward the low temperature side in the DSC measurement method is due to the ultra-high molecular weight. For this reason, ΔH measured as the heat of fusion (heat of crystallization) may also tend to be low.

[0153] On the other hand, it was found that the DSC chart of the propylene polymer obtained by the method of the present invention shows a tendency of relatively small spread toward the low temperature side and high ΔH. This may be because the polymer obtained by the method of the present invention, especially the component in the ultra-high molecular weight region, has high stereoregularity, so it is easy to crystallize and shows a tendency of small spread toward the low temperature side.

[0154] It is said that the ultra-high molecular weight component may cause problems such as fish eyes in applications where transparency and visibility are important, such as film applications. As described above, the olefin polymer obtained by the method of the present invention tends to achieve a fine dispersion state at the catalytic active species level, that is, even at the nano level, so the above problems tend not to occur. In addition, by selecting the structure of the ester compound (a) used in the catalyst of the present invention, it is also possible to adjust the balance between the molecular weight and content of the ultra-high molecular weight component and the molecular weight and melt flow rate (MFR) of the entire polymer.

[0155] The reason why a polymer exhibiting such properties can be obtained is probably because the ester compound contained in the catalyst of the present invention has a special structure, as described above, and therefore the reaction environment is relatively stable. In other words, the inventors speculate that while having a high ability to control stereoregularity, the catalyst may also have the effect of preventing the highly stereospecific active sites from becoming in a special state where a chain transfer reaction occurs.

[0156] The polymer obtained by the method of the present invention has a molecular weight distribution that is somewhat broad on the low molecular weight side. The low molecular weight component has a weak crystalline structure due to its low molecular weight, and tends to have a low melting point. The propylene polymer obtained by the method of the present invention may possibly show a DSC chart with less spread on the low temperature side since the low molecular weight component has high stereoregularity. In addition, several other factors may be considered, such as the possibility of a nucleating agent effect occurring during the crystallization process.

[0157] From these viewpoints, it is considered that the propylene polymer obtained by the method of the present invention has high stereoregularity regardless of its molecular weight range, which is why it has a high heat of fusion and shows a relatively high degree of crystallinity.

[0158] [Propylene polymer] The propylene polymers of the present invention can be roughly classified into three categories (propylene polymer (H), propylene polymer (L) and propylene polymer (S)) described later mainly based on their molecular weights (melt flow rate (MFR) is one evaluation index) and stereoregularity (decane soluble content is one index).

[0159] The various requirements for defining the propylene polymer of the present invention are defined as follows. MFR: Melt flow rate (unit: g / 10 min) determined using the method specified in the ASTM 1238 standard at 230°C and a load of 2.16 kg. Tmf: Final melting point, determined by the conditions described in the Examples section (unit: °C) ΔH: Total heat of fusion determined by DSC measurement (second heating step) under the conditions described in the Examples section (unit: J / g) ΔH(high): Percentage of heat of fusion in the ΔH range above 165°C ΔH(mid): Percentage of heat of fusion in the range of 160℃ to 165℃ above ΔH ΔH(low): Heat of fusion in the region below 160℃ / %

[0160] The above ΔH(high), ΔH(mid), and ΔH(low) are values ​​when the heat quantity of ΔH is 100% (i.e., the sum of ΔH(high), ΔH(mid), and ΔH(low) is 100%), and can be calculated from the ratio of the heat absorption amounts in each temperature range determined by the corresponding DSC chart (corresponding to the area ratio of the DSC chart).

[0161] The propylene polymers of the present invention, which will be described in detail below, can be obtained by polymerizing propylene preferably using the above-mentioned olefin polymerization catalyst, but the production method thereof is not limited.

[0162] <Propylene polymer (H)> The propylene polymer (H) of the present invention is a polymer which tends to have a relatively low molecular weight, excellent moldability, and high rigidity, and which satisfies the following requirements. (αH)MFR≧10g / 10min (βH)ΔH≧80J / g (γH)ΔH(high)≧10% (δH)[ΔH(mid) / ΔH(low)]>[ΔH(high) / ΔH(mid)] Each requirement is explained below.

[0163] The propylene polymer (H) of the present invention satisfies the above requirement (αH): MFR≧10 g / 10 min. The MFR is well known as a simple evaluation index of the molecular weight of a propylene polymer and a simple evaluation index of the melt fluidity of a polymer. Specifically, as described above, it is determined by a method according to the ASTM1238 standard. The MFR of the propylene polymer (H) of the present invention is preferably 15 g / 10 min or more, more preferably 20 g / 10 min or more. The preferred upper limit is 1000 g / 10 min, more preferably 800 g / 10 min, and even more preferably 700 g / 10 min.

[0164] Since the propylene polymer (H) of the present invention has a relatively high MFR as described above, it is particularly suitable for injection molding among various known molding methods.

[0165] The propylene polymer (H) of the present invention satisfies the above requirement (βH): ΔH≧80 J / g. The ΔH is the heat of fusion of the propylene polymer (H), and it is believed that the higher this value is, the higher the crystallinity tends to be. In addition, a high value is also an indicator of excellent heat resistance, since a large amount of heat is required until melting ends even after the melting temperature is reached. The ΔH of the propylene polymer (H) of the present invention is preferably 83 J / g or more, more preferably 85 J / g or more, and even more preferably 88 J / g or more. On the other hand, the preferred upper limit is 150 J / g, more preferably 130 J / g, and even more preferably 110 J / g.

[0166] The propylene polymer (H) satisfying this requirement has high heat resistance and is therefore particularly suitable for use as an injection molded article.

[0167] The propylene polymer (H) of the present invention satisfies the above requirement (γH): ΔH(high) ≧ 10%. ΔH(high) can be considered as an index of heat resistance, particularly in the high melting temperature range (over 165°C). A high value of this index indicates excellent heat resistance, particularly at high temperatures. If this index is 10% or more, it is considered to have particularly high heat resistance, and is one of the important requirements characterizing the propylene polymer (H) of the present application.

[0168] The above requirement ΔH(high) is preferably 11% or more, more preferably 13% or more. The present inventors believe that the propylene polymer component corresponding to the ΔH(high) region indicates that it has extremely high stereoregularity or that the amount of ultra-high molecular weight components with high stereoregularity is relatively large. The present inventors also believe that the propylene polymer component corresponding to the ΔH(high) region may be a crystallization nucleating agent and may be a factor in increasing the crystallinity of the entire propylene polymer (H), in addition to simply having high heat resistance.

[0169] It is obvious that a higher ΔH(high) value is advantageous in terms of heat resistance, but taking into consideration the content of the requirement (ΔH) described later and the balance with the elastic modulus, moldability, and the like, the upper limit is preferably 35%, more preferably 30%, and even more preferably 28%.

[0170] The propylene polymer (H) of the present invention satisfies the above requirement (δH): [ΔH(mid) / ΔH(low)]>[ΔH(high) / ΔH(mid)]. Those skilled in the art will understand that this requirement (δH) is an index showing that not only ΔH(high) but also ΔH(mid) is relatively high. More specifically, it can be said that this requirement is an index showing that the content of the propylene polymer component corresponding to ΔH(high) and ΔH(mid) shows a relatively higher balance than the content of the propylene polymer component corresponding to ΔH(low).

[0171] The present inventors believe that the propylene polymer (H) satisfying such a relationship indicates that, for example, when a part of the above-mentioned ΔH(high) corresponding component functions as a crystallization nucleating agent component, the content of the component that is easily crystallized is relatively high, and thus a propylene polymer having a high crystallinity, melting point, and heat of fusion is easily obtained.

[0172] The above [ΔH(mid) / ΔH(low)] is preferably at least 0.03 higher than [ΔH(high) / ΔH(mid)], and more preferably at least 0.05 higher. There is no particular upper limit to the difference between [ΔH(mid) / ΔH(low)] and [ΔH(high) / ΔH(mid)], but it is preferably 0.50, more preferably 0.45, even more preferably 0.40, and particularly preferably 0.35.

[0173] The propylene polymer (H) of the present invention preferably has a ΔH(low) of less than 61% (requirement (εH)), more preferably 60% or less, further preferably 59% or less, particularly preferably 57% or less.

[0174] The present inventors consider that the propylene polymer (H) satisfying this requirement also represents an embodiment in which, as described above, when a part of the ΔH(high) corresponding component functions as a crystallization nucleating agent component, the content of the component that is easily crystallized is relatively high, and a propylene polymer having a high crystallinity, melting point, and heat of fusion is easily obtained.

[0175] The final melting point Tmf of the propylene polymer (H) of the present invention is preferably 169.0°C or higher, more preferably 169.5°C or higher, and even more preferably 170.0°C or higher. The propylene polymer (H) of the present invention has extremely high stereoregularity as described above, and the stereoregularity of the ultra-high molecular weight component is high, so the Tmf tends to be high. Such a polymer is also expected to exhibit high heat resistance. On the other hand, although the setting of the upper limit of Tmf is not very important, it is considered that a polymer with too high Tmf may require a special molding method or molding conditions to make the most of its properties, so the upper limit of Tmf is preferably 200°C, more preferably 195°C, and even more preferably 190°C.

[0176] The propylene polymer (H) of the present invention is expected to exhibit not only high heat resistance but also high rigidity. Therefore, it is suitable for use in applications requiring high rigidity and high heat resistance. In addition, since the propylene polymer (H) of the present invention is easy to increase in crystallinity as described above, a molding method that can apply orientation tends to easily give a molded product with higher performance. Therefore, it is expected to be suitable for applications such as injection molded products, stretched films (uniaxially stretched films, biaxially stretched films, etc.), and fibers.

[0177] <Propylene polymer (L)> The propylene polymer (L) of the present invention is a polymer which has a relatively high molecular weight and tends to be suitable for use in packaging materials such as sheets and films, and which satisfies the following requirements. (αL)MFR<10g / 10min (βL)ΔH≧80J / g (γL)ΔH(high)≧18.5%, and ΔH(mid)≧28%, and [ΔH(high)+ΔH(mid)]≦80% (δL)Tmf≧170.0℃ Each requirement is explained below.

[0178] The propylene polymer (L) of the present invention satisfies the above requirement (αL): MFR<10 g / 10 min. As described above, MFR is a well-known index. The MFR of the propylene polymer (L) of the present invention is preferably 8 g / 10 min or less, more preferably 6 g / 10 min or less, and even more preferably 5 g / 10 min or less. The preferred lower limit is 0.001 g / 10 min, more preferably 0.005 g / 10 min, and even more preferably 0.01 g / 10 min.

[0179] Since the propylene polymer (L) of the present invention has a relatively low MFR as described above, it is suitably used for, for example, extrusion sheets, T-die films, inflation films, blow molded articles, vacuum molded articles and the like.

[0180] The propylene polymer (L) of the present invention satisfies the above requirement (βL): ΔH≧80 J / g. ΔH is basically the same as the above requirement (βH).

[0181] The propylene polymer (L) of the present invention satisfies the requirements (γL): ΔH(high)≧18.5%, ΔH(mid)≧28%, and [ΔH(high)+ΔH(mid)]≦80%.

[0182] The lower limit of ΔH(high) is preferably 19.0%, more preferably 19.5%, and even more preferably 20.0%, while the upper limit is preferably 35%, more preferably 30%, and even more preferably 28%.

[0183] The lower limit of ΔH(mid) is preferably 28.4%, more preferably 29.0%, even more preferably 29.5%, particularly preferably 30.0%, and especially preferably 33.0%, while the upper limit is preferably 50.0%, more preferably 47.0%, and even more preferably 45.0%.

[0184] The upper limit of the [ΔH(high)+ΔH(mid)] is preferably 75%, more preferably 70%, even more preferably 65%, and particularly preferably 63%, while the lower limit is preferably 48.0%, more preferably 48.5%, and even more preferably 49.0%.

[0185] If ΔH(mid) is too high, the value of ΔH(high) may become small, and the heat resistance may also decrease. Also, if ΔH(mid) is too low, the crystal nucleating agent effect described in the ΔH(high) corresponding component may not be fully utilized, and the heat resistance may also become insufficient.

[0186] The propylene polymer (L) of the present invention has a particularly large amount of crystals that melt in a high temperature range (165°C or higher), i.e., it has excellent melting resistance (heat resistance) in a high temperature range, and further has a relatively large amount of components that melt in a medium temperature range (160°C to 165°C). As the molecular weight of a propylene polymer increases, the mobility of the molecular chain relatively decreases, making it difficult to crystallize, and the crystallization degree tends to decrease. However, as described above, the propylene polymer (L) of the present invention has a high content of propylene polymers corresponding to ΔH(high) and ΔH(low), and therefore, for the same presumed reason as above, it is considered that the crystallization degree is likely to be high even if the molecular weight is high, and the polymer has excellent heat resistance.

[0187] From the above, the propylene polymer (L) of the present invention is suitable for containers and packaging materials such as sheets, films, bottles, etc., and is expected to provide products with high heat resistance. In addition, it is expected that the heat resistance, rigidity, etc. can be appropriately adjusted by adjusting and devising the molding method.

[0188] The propylene polymer (L) of the present invention satisfies the requirement (δL): Tmf≧170.0°C. More preferably, it is 171.0°C or higher, and even more preferably, it is 171.5°C or higher. As described above, the propylene polymer (L) of the present invention has extremely high stereoregularity, and the stereoregularity of the ultra-high molecular weight component is high, so that the Tmf tends to be high. Such a polymer is also expected to exhibit high heat resistance. On the other hand, although the setting of a preferred upper limit of Tmf is not very important, it is considered that a polymer with too high Tmf may require a special molding method or molding conditions to utilize its properties, so that the upper limit of Tmf is preferably 200°C, more preferably 195°C, and even more preferably 190°C.

[0189] The propylene polymer (L) of the present invention preferably satisfies the following requirement (εL): Tmf-ΔH(high)≧149.0. This requirement can be considered as an index showing that Tmf tends to be high compared to the amount of the propylene polymer component corresponding to ΔH(high). The propylene polymer (L) satisfying this requirement is considered to have high stereoregularity, and perhaps the stereoregularity of the component in the ultra-high molecular weight region is particularly high. In addition, when it becomes a crystallization nucleating agent derived from the component in the ultra-high molecular weight region, it is likely to form strong crystals due to its influence, and as a result, the polymer will have a high Tmf compared to the value of ΔH(high). The present inventors consider the requirement (εL) to be an index suggesting that the polymer has the above-mentioned mode.

[0190] The "Tmf-ΔH(high)" is more preferably 149.5 or more, even more preferably 150.0 or more, particularly preferably 150.5 or more, and especially preferably 151.0 or more. Taking into consideration the preferred upper limit of Tmf and the lower limit of ΔH(high), the upper limit is preferably 180, more preferably 177, and even more preferably 175.

[0191] <Propylene polymer (S)> The propylene polymer (S) of the present invention is a polymer that is considered to have a relatively large amount of decane-soluble components and to be characterized by a balance of physical properties including flexibility and moldability. It can also be considered to be a polymer that tends to be suitable for use in the field of packaging materials such as sheets and films, and is a propylene polymer that satisfies the following requirements. (αS) Decane soluble content ≧5% by mass (βS)ΔH≧80J / g (γS)Tmf≧169℃ (δS) ΔH(low)≧61%, and 20%≧ΔH(high)≧5% (εS) Content of structural units derived from olefins other than propylene in the decane insoluble portion ≦5 mol% Each requirement is explained below.

[0192] The propylene polymer (S) of the present invention satisfies the requirement (αS): content of decane-soluble components ≧5 mass%. The decane-soluble components are the content of components soluble in decane at 23° C. in the propylene polymer (S) determined by the method described in the Examples below. This index is generally well known as an index of the stereoregularity of olefin polymers and the composition distribution of copolymers.

[0193] In applications where the heat resistance of propylene polymers is utilized, it is preferable that the decane soluble content is low, but in general applications such as containers and packaging materials, the balance between heat resistance and flexibility, transparency, etc. may be important. In particular, transparency may generally be superior when the decane soluble content is low. For this reason, there is a market for polymers with a relatively high decane soluble content.

[0194] The decane soluble content of the propylene polymer (S) of the present invention is 5% by mass or more, preferably 6% by mass or more, while the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 12% by mass or less, particularly preferably 11% by mass or less, taking into consideration the occurrence of stickiness of the molded product.

[0195] The propylene polymer (S) of the present invention satisfies the requirement (βS): ΔH≧80 J / g. The definition of this ΔH is basically the same as the requirement (βH) described above.

[0196] The propylene polymer (S) of the present invention is characterized by a relatively high ΔH value despite its relatively high content of decane-soluble components. The present inventors believe that this is because the component corresponding to ΔH(high) described below is contained in a specific range of amount, and the high value is due to the influence of the component (e.g., crystal nucleating agent effect, etc.). However, since this is not an index that means that the temperature at which melting occurs is high, as can be seen from the above-mentioned requirement (αS) and the below-mentioned requirement (δS), this is a polymer with different characteristics from the above-mentioned propylene polymer (H) and propylene polymer (L).

[0197] The propylene polymer (S) of the present invention is considered to have a relatively large amount of decane-soluble components, while having a high ΔH and a high degree of crystallinity. Therefore, for example, when molded into a film, it is expected to be advantageous in obtaining a film with a sense of stiffness (firmness).

[0198] The ΔH of the propylene polymer (S) of the present invention is preferably 83 J / g or more, more preferably 85 J / g or more, and even more preferably 86 J / g or more. On the other hand, the upper limit is preferably 100 J / g, more preferably 97 J / g, and even more preferably 95 J / g. If ΔH is too high, the flexibility and transparency described in the propylene polymer (S) of the present invention may become insufficient.

[0199] The propylene polymer (S) of the present invention satisfies the requirement (γS): Tmf≧169.0° C. The Tmf is preferably 169.2° C. or more, more preferably 169.3° C. or more. On the other hand, the upper limit is preferably 180.0° C., more preferably 177.0° C., and even more preferably 175.0° C.

[0200] The propylene polymer (S) of the present invention has a feature of exhibiting a high Tmf even though it has a relatively high content of decane soluble components. This is related to the requirement (δS) described later, and the present inventors believe that this is due to the presence of a relatively large amount of components corresponding to ΔH(high).

[0201] The propylene polymer (S) of the present invention satisfies the requirements (ΔS): ΔH(low)≧61% and 20%≧ΔH(high)≧5%.

[0202] The propylene polymer (S) of the present invention is an embodiment in which ΔH(high) and ΔH(low) satisfy the above-mentioned conditions, and thus, as explained in the above-mentioned requirement (βS), one of its characteristics is that ΔH is relatively high, even though the decane-soluble component is relatively high. The lower limit of the ΔH(high) is preferably 5.5%, more preferably 6.0%. On the other hand, the upper limit is preferably 15.0%, more preferably 12.0%, even more preferably 10.0%, and particularly 9.5%. The lower limit of the ΔH(low) is preferably 62%, more preferably 63%, and even more preferably 64%. On the other hand, the upper limit is preferably 90%, more preferably 80%, and even more preferably 70%. Within the above range, it would be advantageous to obtain a molded product having appropriate flexibility and transparency while also having appropriate rigidity (stiffness).

[0203] This requirement can be considered to indicate that the component corresponding to ΔH(high), i.e., the component having a high melting point, is contained in a specific range of content, while the polymer component having a low melting point is relatively abundant, that is, both components having extreme physical properties are contained in relatively large amounts.

[0204] The present inventors believe that the propylene polymer (S) of the present application has a relatively high ΔH because the component corresponding to ΔH(high) above probably acts as a trigger (e.g., a part of it exhibits the effect of a crystallization nucleating agent), which increases the crystallinity of the component corresponding to ΔH(low). The presumed reason why the component corresponding to ΔH(high) has the effect of increasing the crystallinity as described above is basically the same as that explained for the propylene polymer (H) and propylene polymer (L).

[0205] From the above, the propylene polymer (S) of the present invention is expected to be able to appropriately impart rigidity (such as stiffness) to existing containers and packaging products such as sheets, films, and bottles while maintaining their characteristics.

[0206] The propylene polymer (S) of the present invention satisfies the requirement (εS): the content of structural units derived from olefins other than propylene in the decane-insoluble portion is ≦5 mol %. The content of structural units derived from olefins other than propylene is preferably 4 mol % or less, more preferably 3 mol % or less.

[0207] The decane insoluble portion is a component obtained by removing the decane soluble component defined in the requirement (αS) from the propylene polymer (S) of the present invention. When the propylene polymer (S) is a homopolymer, it is self-evident that the above value is 0 mol%.

[0208] The above propylene polymer (H), propylene polymer (L), and propylene polymer (S) of the present invention may contain structural units derived from olefins other than propylene or polymerizable vinyl compounds, as long as such structural units are not contrary to the characteristics, purposes, and the like of each of the propylene polymers.

[0209] As the olefin, the olefins and dienes disclosed in the section on the method for producing an olefin polymer, and as the polymerizable vinyl compound, aromatic vinyl compounds such as styrene can be mentioned as preferred examples. As more preferred olefins, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-hexadecene, and 1-octadecene can be mentioned. Among these, ethylene, 1-butene, 1-hexene, 1-octene, and 1-decene are more preferred examples, and ethylene and 1-butene are further preferred examples. As a preferred example of the polymerizable vinyl compound, styrene can be mentioned.

[0210] The content of such other structural units, when the total content of the structural units derived from propylene is taken as 100 mol %, is preferably 5 mol % or less, more preferably 3 mol % or less, even more preferably 1 mol % or less, and particularly preferably 0.5 mol % or less.

[0211] The propylene polymer obtained by the method of the present invention can be used in various known applications. In particular, since it is expected to have high heat resistance and rigidity, it is suitable for various injection molded body applications, more specifically, automobile parts and home appliance parts. In addition, since it has a wide molecular weight distribution, it can be used for various sheets and films. In particular, it is suitable for use as a separator for lithium ion batteries and capacitors. It can also be publicly used for stamping molded bodies, calendar molded bodies, rotational molded bodies, etc. EXAMPLES

[0212] 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, amount of decane soluble (insoluble) components, molecular weight distribution, final melting point, melting point, crystallization temperature and heat of fusion of the propylene polymers were measured by the following methods.

[0213] (1) Bulk density: Measurements were performed in accordance with JIS K-6721. (2)Melt flow rate (MFR): The method was based on ASTM D1238E, and the measurement temperature was 230° C. for propylene polymers.

[0214] (3) Amount of decane soluble (insoluble) components: Approximately 3 grams (10 -4 The weight was measured to the nearest gram. This weight was represented as b (grams) in the formula below. ), 500 ml of decane, and a small amount of a heat-resistant stabilizer soluble in decane were added, and the temperature was raised to 150°C over 2 hours while stirring with a stirrer under a nitrogen atmosphere to dissolve the propylene polymer. The mixture was then held at 150°C for 2 hours and then slowly cooled to 23°C over 8 hours. The resulting liquid containing the precipitate of the propylene polymer was filtered under reduced pressure using a 25G-4 standard glass filter manufactured by Tokyo Glass Instruments Co., Ltd. 100 ml of the filtrate was collected and dried under reduced pressure to obtain a portion of the decane-soluble components, and the weight of this was calculated by multiplying the weight by 100 ml. -4 The weight was measured to the nearest gram (this weight is represented as a (gram) in the formula below). After this operation, the amount of decane soluble components was determined by the formula below. Decane soluble component content = 100 × (500 × a) / (100 × b) Decane insoluble content = 100 - 100 × (500 × a) / (100 × b)

[0215] (4)Molecular weight distribution: Gel permeation chromatograph: Tosoh Corporation HLC-8321 GPC / HT type Detector: Differential refractometer Columns: Two TSKgel GMH6-HT columns and two TSKgel GMH6-HTL columns manufactured by Tosoh Corporation were connected in series. Mobile phase medium: o-dichlorobenzene Flow rate: 1.0ml / min Measurement temperature: 140℃ Method for preparing the calibration curve: A standard polystyrene sample was used. Sample concentration: 0.1% (w / w) Sample volume: 0.4ml The measurement was performed under the above conditions, and the obtained chromatogram was analyzed by a known method to calculate the weight average molecular weight (Mw), number average molecular weight (Mn), Z average molecular weight (Mz), and the Mw / Mn and Mz / Mw values, which are indices of molecular weight distribution (MWD). The measurement time for one sample was 60 minutes.

[0216] (5) Melting point of polymer (Tm): The melting point (Tm), crystallization temperature (Tc), and heat of fusion (ΔH) of the polymer in the present invention were measured by differential scanning calorimetry (DSC) using a Seiko Instruments Inc. DSC220C device. 3 to 10 mg of 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 taken as the crystallization temperature (Tc), and the heat generation amount specified by the area of ​​the peak was taken as ΔH (1st-cool). 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 taken as the melting point (Tm) (if multiple peaks were observed, the two highest peaks were listed in the table).

[0217] The endothermic heat amount specified by the area of ​​the peak observed in the second heating test step was designated as ΔH (ΔH(2nd-heat)). Furthermore, the peak area results of ΔH(2nd-heat) were calculated separately for three temperature ranges: "less than 160°C", "160°C to 165°C", and "more than 165°C", and the ratios of the respective areas were designated as ΔH(low), ΔH(mid), and ΔH(high) (the sum of ΔH(low), ΔH(mid), and ΔH(high) was 100%). In this application, for the sake of convenience, all ΔH-related measurement values ​​are absolute values ​​(positive values).

[0218] The final melting point (Tmf) of the polymer in the present invention was measured by differential scanning calorimetry (DSC) using a Seiko Instruments DSC220C device. 3 to 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 and 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 of 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).

[0219] Tmf can be considered as one parameter for evaluating the crystal structure of a component exhibiting extremely high stereoregularity, and the ease of crystallization and crystal structure of a polymer in the ultra-high molecular weight range that is considered to have a tendency to be difficult to crystallize. More specifically, it can be considered that the higher the Tmf value, the easier it is for the ultra-high molecular weight polymer component to form crystals with high heat resistance.

[0220] The structural formulas of the compounds used in the following Examples and Comparative Examples include some that have stereoisomeric structures. The structural formulas showing the stereoisomers of the exemplified compounds show the isomers that are the main components of the compounds used in the Examples and Comparative Examples. In the present invention, the main component refers to more than 50 mol%, preferably 70 mol% or more.

[0221] [Example 1] (Example 1-1, Example 1-2) <Preparation of solid titanium catalyst component [α1]> After thoroughly replacing the atmosphere in a 1L glass container with nitrogen, 85.8g of anhydrous magnesium chloride, 321g of decane, and 352g of 2-ethylhexyl alcohol were added and reacted at 130°C for 3 hours to obtain a homogeneous solution. 241g of this solution and 6.43g of ethyl benzoate were added to the glass container and mixed with stirring at 50°C for 1 hour.

[0222] The homogeneous solution thus obtained was cooled to room temperature, and 38.3 ml of this homogeneous solution was added dropwise to 100 ml of titanium tetrachloride kept at -20°C over a period of 45 minutes while stirring at a stirring speed of 350 rpm. After the addition, the temperature of this mixture was raised to 80°C over a period of 3.8 hours, and when it reached 80°C, 1.26 g of the following compound 1 was added to the mixture. The temperature was raised again to 120°C over a period of 40 minutes, and the mixture was kept at the same temperature for 35 minutes while stirring. After the reaction was completed, the solid portion was collected by hot filtration, and the solid portion was resuspended in 100 ml of titanium tetrachloride, and then the reaction was again heated at 120°C for 35 minutes. After the reaction was completed, the solid portion was collected by hot filtration again, and thoroughly washed with decane at 100°C and decane at room temperature until no free titanium compound was detected in the washings. The solid titanium catalyst component [α1] prepared by the above operations was stored as a decane slurry, and a part of it was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component [α1] thus obtained was 0.28 mass % of titanium, 1.5 mass % of magnesium, and 0.13 mass % of 2-ethylhexyl alcohol residue.

[0223] [ka]

[0224] <Main Polymerization> After adding 500g of propylene and 1NL of hydrogen to a 2-liter polymerization vessel at room temperature, a mixture of 7ml of heptane, 0.35mmol of triethylaluminum, 0.07mmol of cyclohexylmethyldimethoxysilane, and 0.0028mmol of solid titanium catalyst component [α1] (titanium atom equivalent) mixed for 10 minutes at 25°C was added, and the temperature inside the polymerization vessel was quickly raised to 70°C. After polymerization at 70°C for 1.5 hours, the reaction was stopped with a small amount of methanol, and propylene was purged. The obtained polymer particles were further dried under reduced pressure at 80°C overnight. Activity, bulk density, MFR, amount of decane insoluble component, Tm, Tmf, MWD, etc. are shown in Table 1 (Example 1-1). In addition, polymerization was carried out in the same manner as above except that 5NL of hydrogen was used (Example 1-2). The results are shown in Table 1.

[0225] [Example 2] (Example 2-1, Example 2-2) <Preparation of solid titanium catalyst component [α2]> A solid titanium catalyst component [α2] was obtained in the same manner as in Example 1, except that 1.50 g of the following compound 2 was used instead of 1.26 g of compound 1.

[0226] [ka]

[0227] <Main Polymerization> Propylene polymerization was carried out in the same manner as in Example 1 (Example 2-1), except that 0.0024 mmol (titanium atom equivalent) of the solid titanium catalyst component [α2] was used instead of the solid titanium catalyst component [α1], the amount of triethylaluminum used was changed from 0.35 mmol to 0.3 mmol, and the amount of cyclohexylmethyldimethoxysilane used was changed from 0.07 mmol to 0.06 mmol. In addition, polymerization was also carried out in the same manner as above, except that 5 NL of hydrogen was used (Example 2-2). The results are shown in Table 1.

[0228] [Example 3] (Example 3-1, Example 3-2) <Preparation of solid titanium catalyst component [α3]> A solid titanium catalyst component [α3] was obtained in the same manner as in Example 1, except that 1.25 g of the following compound 3 was used instead of 1.26 g of compound 1.

[0229] [ka]

[0230] Propylene polymerization was carried out in the same manner as in Example 1 except that the solid titanium catalyst component [α3] was used instead of the solid titanium catalyst component [α1] (Example 3-1). In addition, polymerization was also carried out in the same manner as above except that 5NL of hydrogen was used (Example 3-2). The results are shown in Table 1.

[0231] [Example 4] (Example 4-1, Example 4-2) <Preparation of solid titanium catalyst component [α4]> A solid titanium catalyst component [α4] was obtained in the same manner as in Example 1, except that 1.42 g of the following compound 4 was used instead of 1.26 g of compound 1.

[0232] [ka]

[0233] Propylene polymerization was carried out in the same manner as in Example 1 except that the solid titanium catalyst component [α4] was used instead of the solid titanium catalyst component [α1] (Example 4-1). In addition, polymerization was also carried out in the same manner as above except that 5NL of hydrogen was used (Example 4-2). The results are shown in Table 1.

[0234] [Example 5] (Example 5-1, Example 5-2) <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 1.17 g of the following compound 5 was used instead of 1.26 g of compound 1.

[0235] [ka]

[0236] Propylene polymerization was carried out in the same manner as in Example 1 except that the solid titanium catalyst component [α5] was used instead of the solid titanium catalyst component [α1] (Example 5-1). In addition, polymerization was also carried out in the same manner as above except that 5NL of hydrogen was used (Example 5-2). The results are shown in Table 1.

[0237] [Example 6] (Example 6-1 Example 6-2) <Preparation of solid titanium catalyst component [α6]> A solid titanium catalyst component [α6] was obtained in the same manner as in Example 1, except that 1.01 g of the following compound 6 was used instead of 1.26 g of compound 1.

[0238] [ka]

[0239] Propylene polymerization was carried out in the same manner as in Example 1 except that the solid titanium catalyst component [α6] was used instead of the solid titanium catalyst component [α1] (Example 6-1). In addition, polymerization was also carried out in the same manner as above except that 5NL of hydrogen was used (Example 6-2). The results are shown in Table 1.

[0240] [Example 7] (Example 7-1, Example 7-2) <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 1.00 g of the following compound 7 was used instead of 1.26 g of compound 1.

[0241] [ka]

[0242] <Main Polymerization> Propylene polymerization was carried out in the same manner as in Example 1 (Example 7-1), except that 0.0032 mmol (titanium atom equivalent) of the solid titanium catalyst component [α7] was used instead of the solid titanium catalyst component [α1], the amount of triethylaluminum used was changed from 0.35 mmol to 0.4 mmol, and the amount of cyclohexylmethyldimethoxysilane used was changed from 0.07 mmol to 0.08 mmol. In addition, polymerization was also carried out in the same manner as above, except that 5 NL of hydrogen was used (Example 7-2). The results are shown in Table 1.

[0243] [Example 8] (Example 8-1, Example 8-2) <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 1.5 g of the following compound 8 was used instead of 1.26 g of compound 1.

[0244] [ka]

[0245] <Main Polymerization> Propylene polymerization 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] (Example 8-1). In addition, polymerization was also carried out in the same manner as above except that 5NL of hydrogen was used (Example 8-2). The results are shown in Table 1.

[0246] [Example 9] (Example 9-1, Example 9-2, Example 9-3) <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 1.35 g of the following compound 9 was used instead of 1.26 g of compound 1.

[0247] [ka]

[0248] <Main 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] (Example 9-1). In addition, polymerization was also carried out in the same manner as in Example 9-1 except that 5 NL of hydrogen was used (Example 9-2). Furthermore, polymerization was also carried out in the same manner as in Example 9-1 except that the amount of the solid titanium catalyst component [α9] used was changed from 0.0028 mmol (titanium atom equivalent) to 0.0020 mmol (titanium atom equivalent), the amount of triethylaluminum used was changed from 0.35 mmol to 0.25 mmol, and cyclohexylmethyldimethoxysilane was not used (Example 9-3). The results are shown in Table 1.

[0249] [Example 10] (Example 10-1, Example 10-2) <Preparation of solid titanium catalyst component [α10]> After thoroughly replacing the atmosphere in a 1L glass container with nitrogen, 85.8g of anhydrous magnesium chloride, 321g of decane, and 352g of 2-ethylhexyl alcohol were added and reacted at 130°C for 3 hours to obtain a homogeneous solution. 241g of this solution and 6.43g of ethyl benzoate were added to the glass container and mixed with stirring at 50°C for 1 hour.

[0250] The homogeneous solution thus obtained was cooled to room temperature, and then 30.7 ml of this homogeneous solution was added dropwise to 80 ml of titanium tetrachloride kept at -20°C over a period of 45 minutes while stirring at a rotation speed of 350 rpm. After the addition, the temperature of this mixture was raised to 80°C over a period of 3.8 hours, and when it reached 80°C, 1.07 g of the following compound 10 was added to the mixture. The temperature was raised again to 120°C over a period of 40 minutes, and the mixture was kept at the same temperature for 35 minutes while stirring. After the reaction was completed, the solid portion was collected by hot filtration, and the solid portion was resuspended in 80 ml of titanium tetrachloride, and then the heating reaction was carried out again at 120°C for 35 minutes. After the reaction was completed, the solid portion was collected again by hot filtration, and thoroughly washed with decane at 100°C and decane at room temperature until no free titanium compound was detected in the washings. The solid titanium catalyst component [α10] prepared by the above operations was stored as a decane slurry.

[0251] [ka]

[0252] <Main Polymerization> Propylene polymerization was carried out in the same manner as in Example 1 except that 0.0020 mmol (titanium atom equivalent) of the solid titanium catalyst component [α10] was used instead of the solid titanium catalyst component [α1], the amount of triethylaluminum used was changed from 0.35 mmol to 0.25 mmol, and the amount of cyclohexylmethyldimethoxysilane used was changed from 0.07 mmol to 0.05 mmol (Example 10-1). In addition, polymerization was also carried out in the same manner as in Example 10-1 except that the amount of the solid titanium catalyst component [α10] used was changed from 0.0020 mmol (titanium atom equivalent) to 0.0028 mmol (titanium atom equivalent), the amount of triethylaluminum used was changed from 0.25 mmol to 0.35 mmol, the amount of cyclohexylmethyldimethoxysilane used was changed from 0.05 mmol to 0.07 mmol, and the amount of hydrogen used was changed from 1 NL to 5 NL (Example 10-2). These results are shown in Table 1.

[0253] [Example 11] (Example 11-1) <Preparation of solid titanium catalyst component [α11]> A solid titanium catalyst component [α11] was obtained in the same manner as in Example 1, except that 1.48 g of the following compound 11 was used instead of 1.26 g of compound 1.

[0254] [ka]

[0255] <Main Polymerization> Propylene polymerization was carried out in the same manner as in Example 1 (Example 11-1), except that 0.0020 mmol (titanium atom equivalent) of the solid titanium catalyst component [α11] was used instead of the solid titanium catalyst component [α1], the amount of triethylaluminum used was changed from 0.35 mmol to 0.25 mmol, and the amount of cyclohexylmethyldimethoxysilane used was changed from 0.07 mmol to 0.05 mmol. The results are shown in Table 1.

[0256] [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 1.64 g of the following compound-c1 was used instead of 1.26 g of compound 1.

[0257] [ka]

[0258] <Main Polymerization> Propylene polymerization was carried out in the same manner as in Example 1, except that 0.0032 mmol (titanium atom equivalent) of the solid titanium catalyst component [β1] was used instead of the solid titanium catalyst component [α1], the amount of triethylaluminum used was changed from 0.35 mmol to 0.4 mmol, and the amount of cyclohexylmethyldimethoxysilane used was changed from 0.07 mmol to 0.08 mmol. The results are shown in Table 1.

[0259] [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 1.64 g of the following compound-c2 was used instead of 1.26 g of compound 1.

[0260] [ka]

[0261] <Main Polymerization> Propylene polymerization was carried out in the same manner as in Example 1, except that 0.0032 mmol (titanium atom equivalent) of the solid titanium catalyst component [β2] was used instead of the solid titanium catalyst component [α1], the amount of triethylaluminum used was changed from 0.35 mmol to 0.4 mmol, and the amount of cyclohexylmethyldimethoxysilane used was changed from 0.07 mmol to 0.08 mmol. The results are shown in Table 1.

[0262] [Table 1]

[0263] Comparison of the results shown in the above Examples and Comparative Examples reveals that propylene polymerization using the solid titanium catalyst component of the present invention can produce propylene polymers with high Tmf and ΔH with high activity.

[0264] Moreover, main experimental results for polymers having an MFR of 10 or more are summarized in Table 2, main experimental results for polymers having an MFR of less than 10 are summarized in Table 3, and main experimental results for polymers having a decane soluble content of 5 mass% or more are summarized in Table 4. From these results, it can be seen that the propylene polymers of the present invention are unique polymers that are mainly characterized by features related to the heat of fusion in the range of 165° C. or more. These polymers can be suitably used for various applications by making use of their properties.

[0265] [Table 2]

[0266] [Table 3]

[0267] [Table 4]

Claims

1. A solid titanium catalyst component (I) comprising titanium, magnesium, a halogen, and a cyclic polyvalent ester group-containing compound (a) represented by the following formula (1): 【Chemistry 1】 [In formula (1), m and n are integers of 1 to 5, and satisfy the relationship m+n≧4. R 1 and R 2 are each a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, 3 , multiple R 4 , R 5 ~R 8 are each a group selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom; R 1 ~R 8 The hydrogen atom, the carbon atom, or both of R may be substituted with at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom. 5 ~R 8 Two or more of may be bonded to each other to form a monocyclic or polycyclic ring, or adjacent substituents may be directly bonded to each other to form a multiple bond. 3 is R 4 ~R 8 may be bonded to one or more of the substituents bonded to the same carbon atom to form a monocyclic or polycyclic ring, or adjacent substituents may be bonded directly to form a multiple bond. 3 R may be bonded to each other to form a monocyclic or polycyclic ring. 3 Although they are independent of each other, R bonded to adjacent carbons 3 R may be directly bonded to each other to form a multiple bond. 4 is R 3 and R 5 ~R 8 may be bonded to one or more of the substituents bonded to the same carbon atom to form a monocyclic or polycyclic ring, or adjacent substituents may be bonded directly to form a multiple bond. 4 R may be bonded to each other to form a monocyclic or polycyclic ring. 4 Although they are independent of each other, R bonded to adjacent carbons 4 may be directly bonded to each other to form a multiple bond.

2. 2. The solid titanium catalyst component (I) according to claim 1, wherein said m is 2 or more and said n is 2 or more.

3. The R 3 ~R 8 The solid titanium catalyst component (I) according to claim 1, wherein are independent substituents.

4. The R 1 and R 2 The solid titanium catalyst component (I) according to claim 1, wherein is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

5. The R 3 ~R 8 are each a group selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted cycloalkenyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heteroaryloxy group.

6. 2. An olefin polymerization catalyst comprising the solid titanium catalyst component (I) according to claim 1 and an organometallic compound catalyst component (II) containing a metal element selected from Groups 1, 2 and 13 of the periodic table.

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

8. A process for olefin polymerization, comprising carrying out polymerization of an olefin in the presence of the olefin polymerization catalyst according to claim 6 or 7.

9. A propylene polymer satisfying the following requirements (αH) to (δH): (αH) MFR≧10g / 10min (βH) ΔH≧80J / g (γH)ΔH(high)≧10% (δH) [ΔH(mid) / ΔH(low)] > [ΔH(high) / ΔH(mid)] [The definitions of the symbols in the above requirements (αH) to (δH) are as follows: MFR: Melt flow rate (g / 10 min) specified under the conditions of ASTM 1238, 230°C and 2.16 kg load; ΔH: heat of fusion measured by DSC method / (J / g); ΔH(high): The ratio / % of the heat of fusion in the region above 165° C. in the ΔH; ΔH(mid): the ratio / % of the heat of fusion in the range of 160° C. or more and 165° C. or less in the ΔH; ΔH(low): the ratio / % of the heat of fusion in the region below 160° C. in the ΔH; However, the sum of ΔH(high), ΔH(mid) and ΔH(low) is 100%.

10. The propylene polymer according to claim 9, further satisfying the following (εH). (εH)ΔH(low)<61%

11. A propylene polymer satisfying the following requirements (αL) to (δL): (αL) MFR<10g / 10min (βL) ΔH≧80J / g (γL) ΔH(high)≧18.5%, and ΔH(mid)≧28%, and [ΔH(high)+ΔH(mid)]≦80% (δL) Tmf≧170.0℃ [The definitions of the symbols in the above requirements (αL) to (δL) are as follows: MFR: Melt flow rate (g / 10 min) specified under the conditions of ASTM 1238, 230°C and 2.16 kg load; ΔH: heat of fusion measured by DSC method / (J / g); ΔH(high): The ratio / % of the heat of fusion in the region above 165° C. in the ΔH; ΔH(mid): the ratio / % of the heat of fusion in the range of 160° C. or more and 165° C. or less in the ΔH; ΔH(low): the ratio / % of the heat of fusion in the region below 160° C. in the ΔH; where the sum of ΔH(high), ΔH(mid) and ΔH(low) is 100%; Tmf: final melting point / ° C. determined by the following method using a differential scanning calorimeter (DSC) with a DSC220C device manufactured by Seiko Instruments Inc.; 3-10 mg of sample was sealed in an aluminum pan, The temperature was increased from room temperature to 240° C. at a rate of 80° C. / min. Hold at 240°C for 1 minute, Cool to 0°C at a rate of 80°C / min. Hold at 0°C for 1 minute, Heat at a rate of 80°C / min to 150°C, Hold at 150°C for 5 minutes, 1. The temperature value of the intersection between the tangent to the inflection point on the high temperature side of the peak appearing in the chart obtained by heating to 180° C. at a rate of 35° C. / min and the baseline.

12. The propylene polymer according to claim 11, further satisfying the following (εL): (εL)Tmf-ΔH(high)≧149.0

13. A propylene polymer satisfying the following requirements (αS) to (εS): (αS) Decane soluble component content ≧5% (βS) ΔH≧80J / g (γS) Tmf≧169℃ (δS) ΔH(low)≧61%, and 20%≧ΔH(high)≧5% (εS) The content of structural units derived from olefins other than propylene in the decane insoluble portion is ≦5 mol% [The definitions of the symbols in the above requirements (αS) to (εS) are as follows: ΔH: heat of fusion measured by DSC method / (J / g); ΔH(high): The ratio / % of the heat of fusion in the region above 165° C. in the ΔH; ΔH(mid): the ratio / % of the heat of fusion in the range of 160° C. or more and 165° C. or less in the ΔH; ΔH(low): the ratio / % of the heat of fusion in the region below 160° C. in the ΔH; However, the sum of ΔH(high), ΔH(mid) and ΔH(low) is 100%; Tmf: final melting point / °C determined by the following method using a differential scanning calorimeter (DSC) with a DSC220C device manufactured by Seiko Instruments Inc.; 3-10 mg of sample was sealed in an aluminum pan, The temperature was increased from room temperature to 240° C. at a rate of 80° C. / min. Hold at 240°C for 1 minute, Cool to 0°C at a rate of 80°C / min. Hold at 0°C for 1 minute, Heat at a rate of 80°C / min to 150°C, Hold at 150°C for 5 minutes, 1. The temperature value of the intersection between the tangent to the inflection point on the high temperature side of the peak appearing in the chart obtained by heating to 180° C. at a rate of 35° C. / min and the baseline.

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