3-methyl-1-butene polymer, method for producing same, resin composition, pellet, and molded article

Abstract

Provided are: a 3-methyl-1-butene polymer which has high crystallinity and is capable of improving the mechanical strength of a molded article; a method for producing the 3-methyl-1-butene polymer; a resin composition; pellets; specifically, the 3-methyl-1-butene polymer is a 3-methyl-1-butene polymer having a melting enthalpy of 65 to 100 J / g as determined by differential scanning calorimetry (DSC), or the like.

Description

Technical Field

[0001] The present invention relates to a 3-methyl-1-butene polymer, a method for producing the same, a resin composition, pellets, and a molded article. Background Art

[0002] Conventionally, a large number of various α-olefin polymers have been produced. Among them, regarding the 3-methyl-1-butene polymer known as a high melting point polyolefin, there are few reported examples of its production.

[0003] Among them, as documents reporting the production of 3-methyl-1-butene polymers, there are documents produced using Ziegler-Natta catalysts (for example, refer to Patent Document 1), documents produced using metallocene catalysts (for example, refer to Patent Document 2), and the like.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 61-272205

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 2009-542874 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] In the case of 3-methyl-1-butene polymers, the higher the melting enthalpy, the more excellent the crystallinity, and thus the mechanical strength such as the rigidity of the molded article of the 3-methyl-1-butene polymer is improved. However, the melting enthalpy of the conventionally produced 3-methyl-1-butene polymer is 63 J / g even when it is high, and a 3-methyl-1-butene polymer having a higher melting enthalpy is unknown. In addition, there has been no attempt to produce such a 3-methyl-1-butene polymer. Therefore, there is room for further improvement in the mechanical strength of the molded article of the 3-methyl-1-butene polymer.

[0010] Therefore, an object of the present invention is to provide a 3-methyl-1-butene polymer having high crystallinity and capable of improving the mechanical strength of a molded article, a method for producing the same, a resin composition, pellets, and a molded article.

[0011] Means for Solving the Problems

[0012] As a result of intensive studies to solve the above problems, the present inventors have found that the invention of the present application including the following embodiments can solve the above problems.

[0013] [1] A 3-methyl-1-butene polymer having a melting enthalpy of 65 to 100 J / g obtained by differential scanning calorimetry (DSC).

[0014] [2] The 3-methyl-1-butene polymer described in [1] above has a melting point of 280 to 310 °C.

[0015] [3] A 3-methyl-1-butene polymer, which is an unprocessed 3-methyl-1-butene polymer, has a crystallinity of 80 to 100% determined by the following method.

[0016] (Calculation method of crystallinity)

[0017] The maximum peak intensity and the amorphous peak intensity are obtained from the curve obtained by X-ray diffraction method, and the crystallinity is calculated according to the following calculation formula. Here, the above maximum peak intensity is the intensity of the peak with a diffraction angle 2θ of 17.2 to 17.3 degrees at the peak top, and the above amorphous peak intensity is the intensity between the valleys of the peak with a diffraction angle 2θ of 10.1 to 10.3 degrees at the peak top and the peak with a diffraction angle 2θ of 11.4 to 11.6 degrees at the peak top.

[0018] <Calculation formula>

[0019] Crystallinity (%) = 100 × (maximum peak intensity - amorphous peak intensity) / maximum peak intensity

[0020] [4] A 3-methyl-1-butene polymer, which is a processed 3-methyl-1-butene polymer, has a crystallinity of 95 to 100% determined by the following method.

[0021] (Calculation method of crystallinity)

[0022] The maximum peak intensity and the amorphous peak intensity are obtained from the curve obtained by X-ray diffraction method, and the crystallinity is calculated according to the following calculation formula. Here, the above maximum peak intensity is the intensity of the peak with a diffraction angle 2θ of 17.2 to 17.3 degrees at the peak top, and the above amorphous peak intensity is the intensity between the valleys of the peak with a diffraction angle 2θ of 10.1 to 10.3 degrees at the peak top and the peak with a diffraction angle 2θ of 11.4 to 11.6 degrees at the peak top.

[0023] <Calculation formula>

[0024] Crystallinity (%) = 100 × (maximum peak intensity - amorphous peak intensity) / maximum peak intensity

[0025] [5] The 3-methyl-1-butene polymer described in [1] to [4] above is a 3-methyl-1-butene homopolymer or a copolymer of 3-methyl-1-butene and ethylene or an α-olefin.

[0026] [6] The 3-methyl-1-butene polymer described in any one of [1] to [5] above, wherein the above α-olefin is an α-olefin having 3 to 20 carbon atoms.

[0027] [7] A resin composition comprising the 3-methyl-1-butene polymer described in any one of [1] to [6] above.

[0028] [8] A pellet comprising the 3-methyl-1-butene polymer described in any one of [1] to [6] above or the resin composition described in [7] above.

[0029] [9] A molded article comprising the 3-methyl-1-butene polymer described in any one of [1] to [6] above or the resin composition described in [7] above.

[0030]

[10] A method for producing a 3-methyl-1-butene polymer, which is the method for producing the 3-methyl-1-butene polymer described in any one of [1] to [6] above, and is carried out by polymerizing 3-methyl-1-butene alone or copolymerizing 3-methyl-1-butene with ethylene or an α-olefin in the presence of a catalyst formed from a composition of a ligand (1) represented by the following formula (I) or (II) and a metal compound (2) represented by the formula M(L) n [M is titanium, hafnium or zirconium. L is a component that forms a covalent bond, a coordination bond or an ionic bond with the above M. n is an integer from 2 to 6.], to produce a 3-methyl-1-butene polymer.

[0031] [Chemical formula 1]

[0032]

[0033] [Each ligand represented by formula (I) or (II) has at least 2 hydrogen atoms that can be removed in the bonding reaction with a metal atom, the above metal compound (2) or a base. Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. B is a crosslinking group having 1 to 50 atoms (wherein hydrogen atoms are not included in the count). X and X' are both oxygen atoms. X'' and X''' are each independently a hydroxyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group. Y and Y' are each independently a hydroxyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group.]

[0034]

[11] According to the method for producing a 3-methyl-1-butene polymer described in

[10] above, wherein the ligand (1) has the following structure.

[0035] [Chemical formula 2]

[0036]

[0037] (wherein, B, Y and Y' are as defined above. R 1 ~R 4 are each independently a substituent selected from the group consisting of an alkyl group, an aryl group, a heteroaryl group, and a group formed by combining them. n1 to n4 are each independently an integer of 1 to 4.)

[0038]

[12] The method for producing a 3-methyl-1-butene-based polymer according to

[10] or

[11] above, wherein the above polymerization or copolymerization is carried out in the presence of an activator (3).

[0039]

[13] The method for producing a 3-methyl-1-butene-based polymer according to any one of

[10] to

[12] above, wherein the polymerization temperature is 10 to 180 °C.

[0040] Advantages of the Invention

[0041] According to the present invention, it is possible to provide a 3-methyl-1-butene-based polymer having high crystallinity and capable of improving the mechanical strength of a molded body, a method for producing the same, a resin composition, pellets, and a molded body containing the above 3-methyl-1-butene-based polymer. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 is a curve obtained by measuring the 3-methyl-1-butene-based polymer without melt treatment obtained in Example 1 by X-ray diffraction method.

[0043] Figure 2 is a curve obtained by measuring the 3-methyl-1-butene-based polymer with melt treatment obtained in Example 1 by X-ray diffraction method.

[0044] Figure 3 is a curve obtained by measuring the 3-methyl-1-butene-based polymer without melt treatment obtained in Example 4 by X-ray diffraction method.

[0045] Figure 4 is a curve obtained by measuring the 3-methyl-1-butene-based polymer with melt treatment obtained in Example 4 by X-ray diffraction method.

[0046] Figure 5 is a curve obtained by measuring the 3-methyl-1-butene-based polymer without melt treatment obtained in Comparative Example 4 by X-ray diffraction method. DETAILED DESCRIPTION OF THE INVENTION

[0047] Hereinafter, an example of an embodiment of the present invention will be described. However, the embodiments shown below are examples for embodying the technical idea of the present invention, and the present invention is not limited to the following description.

[0048] In this specification, preferred embodiments are shown. However, embodiments formed by combining two or more of these preferred embodiments are also preferred. Regarding matters shown for numerical ranges, when there are several numerical ranges, preferred embodiments can be formed by selectively combining their lower limit values and upper limit values.

[0049] In this specification, when a numerical range of "XX to YY" is recited, it means "XX or more and YY or less".

[0050] In this specification, Me represents methyl, Et represents ethyl, i Pr represents isopropyl, Ph represents phenyl, and Bz represents benzyl. In addition, THF represents tetrahydrofuran.

[0051] In addition, in this specification, "polymerization activity" refers to the activity of a catalyst that directly or indirectly promotes the homopolymerization of 3-methyl-1-butene or the copolymerization of 3-methyl-1-butene with ethylene or an α-olefin to produce a 3-methyl-1-butene-based polymer. The polymerization activity is expressed as the mass of the polymer produced by the polymerization reaction relative to the mass of the catalyst used, and specifically, it is calculated by the method described in the examples.

[0052] [3-Methyl-1-butene-based polymer]

[0053] The melt enthalpy of the 3-methyl-1-butene-based polymer obtained by differential scanning calorimetry (DSC) in this embodiment is 65 to 100 J / g. A method for manufacturing such a 3-methyl-1-butene-based polymer will be described later.

[0054] The melt enthalpy of the 3-methyl-1-butene-based polymer being 65 to 100 J / g is related to the very high crystallinity of the 3-methyl-1-butene-based polymer. As a result, the mechanical strength such as the rigidity of the molded body of the 3-methyl-1-butene-based polymer is improved. From the same viewpoint, the melt enthalpy of the 3-methyl-1-butene-based polymer is preferably 67 to 100 J / g, more preferably 70 to 100 J / g, further preferably 72 to 100 J / g, particularly preferably 74 to 100 J / g, and most preferably 77 to 100 J / g. As the upper limit value of the melt enthalpy of the 3-methyl-1-butene-based polymer, there is no particular limitation, and it can be 95 J / g or less, or 90 J / g or less, or 85 J / g or less, or 82 J / g or less.

[0055] It should be noted that the melt enthalpy of the 3-methyl-1-butene-based polymer is measured by differential scanning calorimetry (DSC) as described above. The measurement conditions of DSC are as described in the examples.

[0056] The 3-methyl-1-butene polymer of the present embodiment has a high melting point. Specifically, the melting point is preferably 280 to 310 °C, more preferably 285 to 310 °C, further preferably 290 to 310 °C, and particularly preferably 295 to 310 °C. The 3-methyl-1-butene polymer of the present embodiment having a high melting point has excellent heat resistance. If it is 280 °C or higher, the heat resistance of the 3-methyl-1-butene polymer becomes sufficient. On the other hand, if it is 310 °C or lower, the processing temperature of the 3-methyl-1-butene polymer can be suppressed low, so it is easy to suppress thermal deterioration during processing.

[0057] By using the production method described below to produce the 3-methyl-1-butene polymer, a 3-methyl-1-butene polymer having the above melting point can be obtained.

[0058] It should be noted that the above melting point is measured by differential scanning calorimetry (DSC). The measurement conditions of DSC are as described in the examples.

[0059] The 3-methyl-1-butene polymer of the present embodiment is a 3-methyl-1-butene homopolymer or a copolymer of 3-methyl-1-butene and ethylene or an α-olefin. The above copolymer is not particularly limited. From the viewpoint of mechanical strength such as the rigidity of the molded body, the content of the structural unit derived from 3-methyl-1-butene is preferably 50 mol% or more (including 100 mol%). The content of the structural unit derived from 3-methyl-1-butene is more preferably 80 mol% or more (including 100 mol%). The content of the structural unit derived from 3-methyl-1-butene is further preferably 90 mol% or more (including 100 mol%). From the viewpoint of mechanical strength such as the rigidity of the molded body, the 3-methyl-1-butene polymer is preferably the above copolymer or 3-methyl-1-butene homopolymer in which the content of the structural unit derived from 3-methyl-1-butene is 50 mol% or more, and more preferably 3-methyl-1-butene homopolymer.

[0060] The above α-olefin is an α-olefin other than 3-methyl-1-butene. From the viewpoint of copolymerizability, it is preferably an α-olefin having 3 to 20 carbon atoms. A more preferred α-olefin is an α-olefin having 3 to 16 carbon atoms, and a further preferred α-olefin is an α-olefin having 3 to 12 carbon atoms. The above α-olefin can be linear or branched.

[0061] The above copolymer can be a random copolymer, a block copolymer, or an alternating copolymer.

[0062] As the above α-olefins, for example, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexene, vinylnorbornane, etc. can be cited.

[0063] The above α-olefins can be one kind or two or more kinds.

[0064] [Manufacturing method of 3-methyl-1-butene-based polymer]

[0065] The manufacturing method of the 3-methyl-1-butene-based polymer of this embodiment is not particularly limited. From the viewpoint of manufacturing a 3-methyl-1-butene-based polymer having the above characteristics, the following method is effective.

[0066] That is, based on the presence of a catalyst formed from a composition of a ligand (1) represented by the following formula (I) or (II) and a metal compound (2) represented by the formula M(L) n [M is titanium, hafnium or zirconium. L is a component that forms a covalent bond, a coordination bond or an ionic bond with the above M. n is an integer of 2 to 6.] The manufacturing method of a 3-methyl-1-butene-based polymer in which 3-methyl-1-butene is homopolymerized or 3-methyl-1-butene is copolymerized with ethylene or an α-olefin is effective.

[0067] [Chemical formula 3]

[0068]

[0069] [Each ligand represented by formula (I) or (II) has at least 2 hydrogen atoms that can be removed in the bonding reaction with a metal atom, the above metal compound (2) or a base. Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. B is a crosslinked group having 1 to 50 atoms (wherein hydrogen atoms are not included in the count). X and X' are both oxygen atoms. X'' and X''' are each independently a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyloxy group. Y and Y' are each independently a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyloxy group.]

[0070] The α-olefin copolymerized with 3-methyl-1-butene is the same as the above α-olefin.

[0071] The 3-methyl-1-butene-based polymer obtained by the production method of the present embodiment is the same as the above-mentioned 3-methyl-1-butene-based polymer.

[0072] (Ligand (1))

[0073] In the ligand (1) represented by the formula (I) or formula (II), there are two hydrogen atoms that can be removed in the bonding reaction (coordination reaction) with the metal atom, metal compound (2), or base. In the present embodiment, it is preferable that at least two of X, X', Y, and Y', or at least two of X', X''', Y, and Y' have at least one hydrogen atom.

[0074] As the above-mentioned metal atom, the same metal atoms as those of the above-mentioned M can be mentioned. The above-mentioned metal compound (2) will be described later. As the above-mentioned base, for example, cesium carbonate, potassium tert-butoxide, butyllithium, sodium hydride, etc. can be mentioned.

[0075] In the formulas (I) and (II), Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

[0076] Ar 1 ~Ar 4 The aryl group represented is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, further preferably an aryl group having 6 to 12 carbon atoms, and may also be an aryl group having 6 carbon atoms. As such an aryl group, for example, a phenyl group, a naphthyl group, etc. can be mentioned.

[0077] As substituents that the aryl group can have, for example, a halogen atom (F, Cl, Br, I), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a substituted or unsubstituted heteroaryl group having 3 to 30 ring-forming carbon atoms, etc. can be mentioned.

[0078] The alkyl group having 1 to 6 carbon atoms as the above-mentioned substituent may be an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 3 carbon atoms. As such an alkyl group, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, etc. can be mentioned.

[0079] The alkoxy group having 1 to 6 carbon atoms as the above-mentioned substituent may be an alkoxy group having 1 to 4 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. As such an alkoxy group, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a tert-butoxy group, a n-pentyloxy group, an isopentyloxy group, etc. can be mentioned.

[0080] The heteroaryl group having 3 to 30 ring carbon atoms as the above-mentioned substituent may be a heteroaryl group having 3 to 20 ring carbon atoms, may be a heteroaryl group having 5 to 15 ring carbon atoms, or may be a heteroaryl group having 10 to 15 ring carbon atoms. For example, pyridyl, thienyl, furyl, thiazolyl, dibenzofuryl, dibenzothienyl, 9-carbazolyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl, etc. may be mentioned. The heteroaryl group may have a substituent, and as the substituent, for example, a halogen atom (F, Cl, Br, I), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, etc. may be mentioned. The heteroaryl group having 3 to 30 ring carbon atoms as the above-mentioned substituent is preferably a substituted or unsubstituted 9-carbazolyl group.

[0081] Ar 1 ~Ar 4 The aryl group shown is not particularly limited, and is preferably an aryl group substituted with a substituted or unsubstituted heteroaryl group having 3 to 30 ring carbon atoms. The preferred form of this aryl group is as described above.

[0082] As Ar 1 ~Ar 4 The heteroaryl group shown is preferably a substituted or unsubstituted heteroaryl group having 3 to 30 ring carbon atoms, and is described in the same manner as the heteroaryl group having 3 to 30 ring carbon atoms of the above-mentioned substituent, and the preferred form is also the same.

[0083] In formulas (I) and (II), B is a crosslinking group having 1 to 50 atoms (wherein hydrogen atoms are not included in the count), and the number of the atoms (wherein hydrogen atoms are not included in the count) is preferably 1 to 30, more preferably 1 to 10, further preferably 1 to 8, and particularly preferably 3 to 6. As the crosslinking group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydrocarbon group containing a heteroatom, etc. may be mentioned, and among them, a substituted or unsubstituted hydrocarbon group is preferred.

[0084] As the hydrocarbon group, an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, an arylene group having 6 to 20 ring carbon atoms, a heteroarylene group having 3 to 20 ring carbon atoms, and a group formed by combining them, etc. may be mentioned.

[0085] The alkylene group having 1 to 10 carbon atoms is preferably an alkylene group having 1 to 7 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and still more preferably an alkylene group having 3 to 5 carbon atoms. Examples of the alkylene group include methylene, ethylene, trimethylene, 1-methyltrimethylene, 1,3-dimethyltrimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and decamethylene. Among them, methylene, ethylene, trimethylene, 1-methyltrimethylene, 1,3-dimethyltrimethylene, tetramethylene, and pentamethylene are preferred, trimethylene, 1-methyltrimethylene, 1,3-dimethyltrimethylene, and tetramethylene are more preferred, and 1,3-dimethyltrimethylene is still more preferred.

[0086] The alkenylene group having 2 to 10 carbon atoms is preferably an alkenylene group having 2 to 7 carbon atoms, and more preferably an alkenylene group having 2 to 5 carbon atoms. Examples of the alkenylene group include vinylene, 1-propylene-1,3-diyl, 2-propylene-1,3-diyl, 1-hexene-1,4-diyl, 2-pentene-1,5-diyl, 1-octene-1,8-diyl, 1,6-octadiene-1,8-diyl, and 2,6-octadiene-1,8-diyl.

[0087] The alkynylene group having 2 to 10 carbon atoms is preferably an alkynylene group having 2 to 7 carbon atoms, and more preferably an alkynylene group having 2 to 5 carbon atoms. Examples of the alkynylene group include ethynediyl, 1-propyn-1,3-diyl, 1-butyn-1,3-diyl, 1-hexyn-1,4-diyl, 2-pentyn-1,5-diyl, and 1-octyne-1,8-diyl.

[0088] The arylene group having 6 to 20 ring carbon atoms is preferably an arylene group having 6 to 12 ring carbon atoms, more preferably an arylene group having 6 to 10 ring carbon atoms, and still more preferably an arylene group having 6 ring carbon atoms. Examples of the arylene group include 1,2-phenylene, 1,3-phenylene, biphenyl-2,2'-diyl, and 1,4-phenylene.

[0089] The heteroarylene group having 3 to 20 ring carbon atoms is preferably a heteroarylene group having 3 to 15 ring carbon atoms, and more preferably a heteroarylene group having 5 to 15 ring carbon atoms. Examples of the heteroarylene group include 2,6-pyridyl, xanthendiyl, and the following divalent groups.

[0090] [Chemical formula 4]

[0091]

[0092] ( Indicates the bonding area. )

[0093] Examples of the above-mentioned "group formed by their combination" include groups formed by combining an alkylene group having 1 to 10 carbon atoms with an arylene group having 6 to 20 ring carbon atoms, groups formed by combining an alkylene group having 1 to 10 carbon atoms with a heteroarylene group having 3 to 20 ring carbon atoms, groups formed by combining an alkenylene group having 2 to 10 carbon atoms with an arylene group having 6 to 20 ring carbon atoms, groups formed by combining an alkynylene group having 2 to 10 carbon atoms with an arylene group having 6 to 20 ring carbon atoms, groups formed by combining an alkenylene group having 2 to 10 carbon atoms with a heteroarylene group having 3 to 20 ring carbon atoms, groups formed by combining an alkynylene group having 2 to 10 carbon atoms with a heteroarylene group having 3 to 20 ring carbon atoms, groups formed by combining an arylene group having 6 to 20 ring carbon atoms with a heteroarylene group having 3 to 20 ring carbon atoms, and the like. Among them, groups formed by combining an alkylene group having 1 to 10 carbon atoms with an arylene group having 6 to 20 ring carbon atoms and groups formed by combining an alkylene group having 1 to 10 carbon atoms with a heteroarylene group having 3 to 20 ring carbon atoms are preferred.

[0094] Examples of the group formed by combining an alkylene group having 1 to 10 carbon atoms with an arylene group having 6 to 20 ring carbon atoms include the following divalent groups and the like.

[0095] [Chemical formula 5]

[0096]

[0097] ( Indicates the bonding site.)

[0098] Examples of the group formed by combining an alkylene group having 1 to 10 carbon atoms with an arylene group having 6 to 20 ring carbon atoms, the following divalent groups are preferred.

[0099] [Chemical formula 6]

[0100]

[0101] ( Indicates the bonding site.)

[0102] In addition, examples of the group formed by combining an alkylene group having 1 to 10 carbon atoms with a heteroarylene group having 3 to 20 ring carbon atoms include the following divalent groups and the like.

[0103] [Chemical formula 7]

[0104]

[0105] ( Indicates the bonding site.)

[0106] The above-mentioned hydrocarbon group may have substituents. For example, there is no particular limitation on the alkylene group having 1 to 10 carbon atoms, and it may have substituents such as halogen atoms (F, Cl, Br, I), hydroxyl groups, etc. There is no particular limitation on the arylene group having 6 to 20 ring carbon atoms, and it may be substituted with halogen atoms (F, Cl, Br, I), hydroxyl groups, alkyl groups having 1 to 10 carbon atoms, etc. There is no particular limitation on the heteroarylene group having 3 to 20 ring carbon atoms, and it may be substituted with halogen atoms (F, Cl, Br, I), hydroxyl groups, alkyl groups having 1 to 10 carbon atoms, etc.

[0107] As the above-mentioned substituted or unsubstituted hydrocarbon group containing a heteroatom, a group in which a part of the above-mentioned "substituted or unsubstituted hydrocarbon group" is replaced by a heteroatom can be cited. As the heteroatom, an oxygen atom, a nitrogen atom, a sulfur atom, etc. can be cited.

[0108] As the above-mentioned substituted or unsubstituted alkoxy group represented by X'' and X''', it may be an alkoxy group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. As the alkoxy group, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, etc. can be cited.

[0109] As the substituents that the alkoxy group may have, for example, halogen atoms (F, Cl, Br, I), hydroxyl groups, etc. can be cited.

[0110] As the above-mentioned substituted or unsubstituted aryloxy group represented by X'' and X''', it may be an aryloxy group having 6 to 30 ring carbon atoms, or an aryloxy group having 6 to 20 ring carbon atoms, or an aryloxy group having 6 to 12 ring carbon atoms. As the aryloxy group, phenoxy group, naphthyloxy group, biphenyloxy group, etc. can be cited.

[0111] As the substituents that the aryloxy group may have, for example, halogen atoms (F, Cl, Br, I), alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, hydroxyl groups, etc. can be cited.

[0112] As the above-mentioned substituted or unsubstituted aralkyloxy group represented by X'' and X''', it may be an aralkyloxy group having 6 to 30 ring carbon atoms, or an aralkyloxy group having 6 to 20 ring carbon atoms, or an aralkyloxy group having 6 to 12 ring carbon atoms, or an aralkyloxy group having 6 ring carbon atoms. As the aralkyloxy group, for example, benzyloxy group, etc. can be cited.

[0113] As the substituents that the aralkyloxy group may have, for example, halogen atoms (F, Cl, Br, I), alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, hydroxyl groups, etc. can be cited.

[0114] As the above-mentioned substituted or unsubstituted alkoxy groups represented by Y and Y', groups same as those represented by X'' and X''' can be mentioned, and the preferred modes are also the same.

[0115] Groups same as those represented by X'' and X''' as the above-mentioned substituted or unsubstituted aryloxy groups represented by Y and Y' can be mentioned, and the preferred modes are also the same.

[0116] As the above-mentioned substituted or unsubstituted aralkyloxy groups represented by Y and Y', groups same as those represented by X'' and X''' can be mentioned, and the preferred modes are also the same.

[0117] As Y and Y', a hydroxyl group is preferred.

[0118] As the ligand (1), the ligand represented by the above formula (I) is preferred.

[0119] In addition, a preferred mode of the above ligand (1) may have the following structure.

[0120] [Chemical formula 8]

[0121]

[0122] (In the formula, B, Y and Y' are as defined above. R 1 ~R 4 Each independently represents a substituent selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl and groups formed by their combination. n1 to n4 each independently represents an integer from 1 to 4.)

[0123] As the above R 1 ~R 4 The alkyl group represented is not particularly limited, and it may be an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and the like.

[0124] As the above R 1 ~R 4 The alkenyl group represented is not particularly limited, and it may be an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms. Examples of the alkenyl group include vinyl, 1-propenyl, allyl, 1-hexenyl, 2-pentenyl, 1-octenyl, 1,6-octadienyl, 2,6-octadienyl and the like.

[0125] As the above R 1 ~R 4The alkynyl group shown is not particularly limited and may be an alkynyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 7 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. Examples of such alkynyl groups include ethynyl, 1-propynyl, propargyl, 1-butynyl, 1-hexynyl, 2-pentynyl, 1-octynyl, and the like.

[0126] As the above-mentioned R 1 ~R 4 The aryl group shown is not particularly limited and may be an aryl group having 6 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl group having 6 carbon atoms. Examples of such aryl groups include phenyl, naphthyl, and the like.

[0127] As the above-mentioned R 1 ~R 4 The heteroaryl group shown is not particularly limited and may be a heteroaryl group having 3 to 20 ring carbon atoms, a heteroaryl group having 5 to 15 ring carbon atoms, or a heteroaryl group having 10 to 15 ring carbon atoms. Examples thereof include pyridyl, thienyl, furyl, thiazolyl, dibenzofuryl, dibenzothienyl, 9-carbazolyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl, and the like.

[0128] As the above-mentioned R 1 ~R 4 Examples of the "group formed by their combination" shown as the above-mentioned R

[0129] ~R 1 ~R 4 include combinations of an alkyl group and an aryl group such as alkylaryl and arylalkyl; combinations of an alkenyl group and an aryl group such as alkenylaryl; combinations of an alkynyl group and an aryl group such as alkynylaryl; combinations of an alkyl group and a heteroaryl group such as alkylheteroaryl and heteroarylalkyl; combinations of an alkenyl group and a heteroaryl group such as alkenylheteroaryl; combinations of an alkynyl group and a heteroaryl group such as alkynylheteroaryl; combinations of an aryl group and a heteroaryl group such as heteroaryl-aryl, and the like.

[0130] As R 1 ~R 4 , there is no particular limitation, and an alkyl group and a heteroaryl group are preferred.

[0131] n1 to n4 are each independently an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0132] Specific examples of the ligand (1) include the following examples, but are not particularly limited thereto.

[0133] [Chemical formula 9]

[0134]

[0135] [Chemical Formula 10]

[0136]

[0137] [Chemical Formula 11]

[0138]

[0139] [Chemical Formula 12]

[0140]

[0141] [Chemical Formula 13]

[0142]

[0143] [Chemical Formula 14]

[0144]

[0145] As the ligand (1), there is no particular limitation, and a ligand having the following structure is preferred.

[0146] [Chemical Formula 15]

[0147]

[0148] [Chemical Formula 16]

[0149]

[0150] (Metal compound (2))

[0151] As described above, the above metal compound (2) is represented by the formula M(L) n In the above formula, M is titanium, hafnium or zirconium. From the viewpoints of the melting point and melting enthalpy of the obtained 3-methyl-1-butene-based polymer and the catalytic activity, hafnium and zirconium are preferred, and hafnium is more preferred.

[0152] In the metal compound (2), L is a component that forms a covalent bond, a coordination bond, or an ionic bond with M. L may be ionically bonded to M. For example, L is a non-coordinating anion, a loosely coordinated anion, or a weakly coordinated anion (for example, L may be selected from anions described below with respect to activators). For details of these weak interactions, reference may be made to Marks et al., Chem. Rev. 2000, 100, pp. 1391-1434. Examples of L include halogen atoms (F, Cl, Br, I), alkyl groups having 1 to 6 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, alkynyl groups having 2 to 6 carbon atoms, heteroalkyl groups having 1 to 6 carbon atoms, heteroalkenyl groups having 2 to 6 carbon atoms, heteroalkynyl groups having 2 to 6 carbon atoms, aryl groups having 6 to 20 ring carbon atoms, heteroaryl groups having 3 to 20 ring carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aryloxy groups having 6 to 20 substituents, substituted silyl groups (such as trimethylsilyl groups), borane groups, phosphino groups, amino groups, thioxyl groups, alkylthio groups, arylthio groups, hydride groups, allyl groups, dienes, phosphines, carboxyl esters, 1,3-diketonates, oxalates, carbonates, nitrates, sulfates, ethers, thioethers, and combinations thereof.

[0153] In the above metal compound (2), n is an integer of 2 to 6, and may be 3 to 5 or 4.

[0154] Specific examples of the metal compound (2) include TiCl4, Ti(CH2Ph)4, Ti(CH2CMe3)4, Ti(CH2SiMe3)4, Ti(CH2Ph)3Cl, Ti(CH2CMe3)3Cl, Ti(CH2SiMe3)3Cl, Ti(CH2Ph)2Cl2, Ti(CH2CMe3)2Cl2, Ti(CH2SiMe3)2Cl2, Ti(NMe2)4, Ti(NEt2)4, Ti(O iPr)4, Ti(N(SiMe3)2)2Cl2; HfCl4, Hf(CH2Ph)4, Hf(CH2CMe3)4, Hf(CH2SiMe3)4, Hf(CH2Ph)3Cl, Hf(CH2CMe3)3Cl, Hf(CH2SiMe3)3Cl, Hf(CH2Ph)2Cl2, Hf(CH2CMe3)2Cl2, Hf(CH2SiMe3)2Cl2, Hf(NMe2)4, Hf(NEt2)4, Hf(N(SiMe3)2)2Cl2; ZrCl4, Zr(CH2Ph)4, Zr(CH2CMe3)4, Zr(CH2SiMe3)4, Zr(CH2Ph)3Cl, Zr(CH2CMe3)3Cl, Zr(CH2SiMe3)3Cl, Zr(CH2Ph)2Cl2, Zr(CH2CMe3)2Cl2, Zr(CH2SiMe3)2Cl2, Zr(NMe2)4, Zr(NEt2)4, Zr(NMe2)2Cl2, Zr(NEt2)2Cl2, Zr(N(SiMe3)2)2Cl2.

[0155] The Lewis base adducts of the above specific examples are also preferably used as the metal compound (2). For example, ethers, amines, thioethers, phosphines, etc. are suitable as the above Lewis bases. That is, as the metal compound (2), HfCl4(THF)2, HfCl4(SMe2)2, Hf(CH2Ph)2Cl2(OEt2), etc. can also be preferably selected.

[0156] The metal compound (2) can be an ionic compound or an amphoteric ionic compound. As the ionic compound and amphoteric ionic compound, for example, (M(CH2Ph)3 ＋ )(B(C6F5)4 - ), (M(CH2Ph)3 ＋ )(PhCH2B(C6F5)3 - ) etc. [M is as described above.].

[0157] In one mode of the method for producing a 3-methyl-1-butene-based polymer of the present embodiment, 3-methyl-1-butene is homopolymerized or 3-methyl-1-butene is copolymerized with an α-olefin in the presence of a catalyst formed from a composition containing the above ligand (1) and the above metal compound (2).

[0158] In the above composition, the content ratio of the ligand (1) to the metal compound (2) [ligand (1) / metal compound (2)] is not particularly limited, and is preferably 0.01 / 1 to 100 / 1, more preferably 0.1 / 1 to 10 / 1, and still more preferably 0.5 / 1 to 2 / 1 in terms of molar ratio.

[0159] The composition containing the above ligand (1) and the above metal compound (2) in an organic solvent is preferably stirred in the organic solvent at 10 to 80 °C, and then the organic solvent is removed and concentrated under an inert gas atmosphere such as argon or nitrogen to obtain a catalyst. As the above organic solvent, there is no particular limitation, and examples thereof include saturated hydrocarbons such as pentane, cyclopentane, hexane, cyclohexane, heptane, isoheptane, and isooctane; aromatic hydrocarbons such as benzene and toluene. The organic solvent can be used alone or in combination of two or more.

[0160] It should be noted that regarding the catalyst and its manufacturing method, reference can also be made to Japanese Patent Application Laid-Open No. 2005-523921.

[0161] As specific examples of the catalyst formed from the composition containing the ligand (1) and the metal compound (2), the following examples are given, but are not particularly limited thereto.

[0162] [Chemical formula 17]

[0163]

[0164] [Chemical formula 18]

[0165]

[0166] [Chemical formula 19]

[0167]

[0168] (Activator (3))

[0169] The above polymerization or copolymerization (hereinafter, collectively referred to as polymerization.) is preferably carried out in the presence of an activator (3).

[0170] As the activator (3), the usual activators used in the polymerization of α-olefins (sometimes also referred to as cocatalysts or co-catalysts.) can be used.

[0171] As the activator (3), there is no particular limitation, and examples thereof include boron compounds, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), boron compound-organoaluminum, etc.

[0172] As the above boron compound, there is no particular limitation, and examples thereof include trisubstituted ammonium salts, dialkylammonium salts, trisubstituted phosphonium salts, trisubstituted methylonium salts (Japanese: trisubstituted methylium salts), etc.

[0173] As the above trisubstituted ammonium salt, for example, trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, etc. can be cited.

[0174] Examples of the above-mentioned dialkylammonium salts include bis(isopropyl)ammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, and the like.

[0175] Examples of the above-mentioned trisubstituted phosphonium salts include triphenylphosphonium tetrakis(pentafluorophenyl)borate, tris(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, tris(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, and the like.

[0176] Examples of the above-mentioned trisubstituted methylammonium salts include trityl tetrakis(pentafluorophenyl)borate, tris(o-tolyl)methylammonium tetrakis(pentafluorophenyl)borate, tris(2,6-dimethylphenyl)methylammonium tetrakis(pentafluorophenyl)borate, and the like.

[0177] As the above-mentioned methylaluminoxane (MAO) and the above-mentioned modified methylaluminoxane (MMAO), known MAO or MMAO used in the polymerization of α-olefins can be used. It should be noted that in order to adjust the activity of MAO or MMAO, a hindered phenol compound such as 2,6-di-tert-butyl-p-cresol (BHT) can be used in combination with MAO or MMAO.

[0178] Examples of the organoaluminum in the above-mentioned boron compound-organoaluminum include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, and trioctylaluminum; alkenylaluminums such as prenylaluminum; dialkylhaloaluminums such as dimethylaluminum chloride and diethylaluminum chloride; alkyl sesquihaloaluminums such as methyl sesquichloride, isopropyl sesquichloride, and butyl sesquichloride; alkyldihaloaluminums such as methyl dichloride, isopropyl dichloride, and ethyl dibromide; alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, and the like.

[0179] It should be noted that the above-mentioned organoaluminum can be a hydrolyzed polymer.

[0180] There is no particular limitation on the above-mentioned boron compound-organoaluminum. Examples include trityl tetrakis(pentafluorophenyl)borate-triisobutylaluminum and the like.

[0181] There is no particular limitation on the activator (3), and MAO and boron compound-trialkylaluminum are preferred.

[0182] The above polymerization is usually carried out in an organic solvent. Examples of the above-mentioned organic solvent include saturated hydrocarbons such as pentane, cyclopentane, hexane, cyclohexane, heptane, isoheptane, and isooctane; aromatic hydrocarbons such as benzene and toluene. There is no particular limitation on the above-mentioned organic solvent, and aromatic hydrocarbons such as toluene are preferred from the viewpoint of the solubility of α-olefins and the catalyst. The organic solvent can be used alone or in combination of two or more.

[0183] At the time of polymerization, the concentration of the catalyst in the solution is not particularly limited, and from the viewpoint of reaction efficiency, it is preferably 0.0001 to 0.1 mol / L, more preferably 0.001 to 0.05 mol / L, and further preferably 0.001 to 0.01 mol / L.

[0184] At the time of polymerization, the concentration of the activator (3) in the solution is not particularly limited, and from the viewpoint of reaction efficiency, it is preferably 0.001 to 1.0 mol / L, more preferably 0.01 to 0.5 mol / L, and further preferably 0.05 to 0.3 mol / L.

[0185] <Polymerization conditions>

[0186] Polymerization can be carried out by any of batch, semi - continuous, and continuous methods. In addition, polymerization can also be carried out in two or more stages by changing the reaction conditions.

[0187] The polymerization temperature is preferably 10 to 180 °C, more preferably 30 to 160 °C, and further preferably 50 to 160 °C. If the polymerization temperature is within the above range, the catalytic activity can be maintained well, the polymerization can be promoted, and the productivity becomes good. Especially when M is, for example, hafnium (Hf) other than zirconium (Zr), by adopting the above temperature range, a 3 - methyl - 1 - butene - based polymer with a specified melting enthalpy can be easily obtained. On the other hand, when M is zirconium (Zr), from the viewpoint of obtaining a 3 - methyl - 1 - butene - based polymer with a specified melting enthalpy, the polymerization temperature is preferably 10 to 145 °C, more preferably 30 to 140 °C, further preferably 50 to 140 °C, and particularly preferably 50 to 135 °C.

[0188] (Polymerization pressure)

[0189] The polymerization pressure is preferably atmospheric pressure to 5 MPa (gauge pressure), more preferably 0.05 to 4 MPa (gauge pressure). If the polymerization pressure is within the above range, devices such as high - pressure - resistant reactors and exhaust pumps are not required, which is economically advantageous.

[0190] (Polymerization time)

[0191] The polymerization time can be 1 minute to 10 hours, can also be 3 minutes to 5 hours, or can also be 3 minutes to 3 hours. If the polymerization time is within the above range, the deterioration of the physical properties of the polymer caused by thermal degradation is not likely to occur, and it is easy to manufacture a polymer with good physical properties.

[0192] (Termination of polymerization)

[0193] The polymerization can be terminated by removing the monomers by distillation or filtration, or by adding any polymerization terminator as required. As the polymerization terminator, a compound that reacts with a catalyst containing a compound having a transition metal atom of Group 4 of the periodic table is preferred. Examples of the polymerization terminator include compounds having active protons such as water, alcohols, primary amines, secondary amines, mercaptans, and Bronsted acids; ethers, phosphines, tertiary amines, thioethers, carbon dioxide, oxygen molecules, and the like.

[0194] The polymerization terminator may be used alone or in combination of two or more.

[0195] (Removal of catalyst components)

[0196] The method for producing 3-methyl-1-butene polymers of the present embodiment can, after the polymerization reaction is completed, carry out an operation of removing the catalyst components contained in the generated polymer as needed. There is no particular limitation on the method for removing the catalyst components, and a known method can be used. For example, (A) a method of adding alcohols such as isobutyl alcohol and 2-propanol to the crude 3-methyl-1-butene polymer obtained by polymerization, stirring at a temperature of about 10 to 100°C, and separating the 3-methyl-1-butene polymer; (B) a method of adding a crude 3-methyl-1-butene polymer obtained by polymerization, an alcohol such as isobutyl alcohol and 2-propanol, and an inorganic acid such as hydrochloric acid and nitric acid, and treating at a temperature of about 10 to 100°C, and separating the 3-methyl-1-butene polymer.

[0197] The above-mentioned removal operation of the catalyst component may be carried out in the state of the polymer slurry immediately after the polymerization reaction is completed, or may be carried out after removing the unreacted monomers and the reaction solvent from the polymer slurry by distillation or filtration.

[0198] The 3-methyl-1-butene polymer obtained as described above may be subjected to a drying step.

[0199] The drying process is not particularly limited, and a known method can be used. The drying process can be performed, for example, by scattering volatile components under the conditions of 133 Pa to normal pressure and 20 to 200° C. In addition, during the drying process, the 3-methyl-1-butene polymer can be left to stand, or can be flowed by the action of air or an inert gas, or can be flowed by mechanical methods such as a stirring rotary wing type drying device, a rotary type drying device, a continuous box type (Japanese: continuous shed type) drying device, and a flow type drying device.

[0200] The drying step can be carried out in multiple stages by changing the temperature. It should be noted that when heating is performed, it is sometimes referred to as a thermal annealing treatment.

[0201] It should be noted that in the above drying process, the 3-methyl-1-butene-based polymer of the present embodiment does not melt.

[0202] The 3-methyl-1-butene-based polymer of the present embodiment may or may not be subjected to a melting treatment. Even if the 3-methyl-1-butene-based polymer of the present embodiment is not subjected to a melting treatment, its crystallinity (crystallinity degree) is high. However, by performing the above melting treatment, the crystallinity (crystallinity degree) can be further improved.

[0203] In the above melting treatment, it is sufficient that at least a part of the 3-methyl-1-butene-based polymer melts. Preferably, 50% by mass or more of the 3-methyl-1-butene-based polymer melts, more preferably 80% or more of the 3-methyl-1-butene-based polymer melts, still more preferably 90% or more of the 3-methyl-1-butene-based polymer melts, and particularly preferably 100% of the 3-methyl-1-butene-based polymer melts.

[0204] The melting treatment is preferably carried out at the melting point of the 3-methyl-1-butene-based polymer of the present embodiment to 380 °C, more preferably at the melting point to 350 °C, still more preferably at the melting point to 320 °C. The holding time after the 3-methyl-1-butene-based polymer starts to melt is not particularly limited, preferably 1 to 30 minutes, more preferably 1 to 15 minutes, still more preferably 1 to 10 minutes.

[0205] The temperature rising conditions during the melting treatment are not particularly limited. Preferably, the temperature is raised to the melting of the 3-methyl-1-butene-based polymer at 3 to 15 °C per minute, more preferably raised at 5 to 15 °C per minute, still more preferably raised at 10 °C per minute.

[0206] After the above melting treatment, it is solidified again by cooling. The temperature during cooling is not particularly limited as long as it is lower than the melting point of the 3-methyl-1-butene-based polymer of the present embodiment. Preferably, it is 250 °C or lower, more preferably -30 to 100 °C, still more preferably -20 to 40 °C.

[0207] The temperature decreasing conditions during cooling are not particularly limited. Preferably, the temperature is decreased to the above temperature at 3 to 15 °C per minute, more preferably decreased to the above temperature at 5 to 15 °C per minute, still more preferably decreased to the above temperature at 10 °C per minute.

[0208] One mode of the present embodiment is the following 3-methyl-1-butene-based polymer, but it is not particularly limited to these.

[0209] (X) A 3-methyl-1-butene-based polymer that has not been subjected to a melting treatment, and its crystallinity determined by the following method is 80 to 100% (hereinafter, sometimes referred to as 3-methyl-1-butene-based polymer (X)).

[0210] (Y) A 3-methyl-1-butene polymer subjected to a melting treatment, having a crystallinity of 95 to 100% as determined by the following method (hereinafter sometimes referred to as 3-methyl-1-butene polymer (Y)).

[0211] (Calculation method of crystallinity)

[0212] The maximum peak intensity and the amorphous peak intensity are obtained from the curve obtained by the X-ray diffraction method, and the crystallinity is calculated according to the following calculation formula. Here, the above maximum peak intensity is the intensity of the peak with a diffraction angle 2θ of 17.2 to 17.3 degrees at the peak top, and the above amorphous peak intensity is the intensity between the valleys of the peak with a diffraction angle 2θ of 10.1 to 10.3 degrees at the peak top and the peak with a diffraction angle 2θ of 11.4 to 11.6 degrees at the peak top.

[0213] It should be noted that the above X-ray diffraction method may be based on JIS K0131 (1996), and more specifically, it may be based on the method described in the examples.

[0214] <Calculation formula>

[0215] Crystallinity (%) = 100 × (maximum peak intensity - amorphous peak intensity) / maximum peak intensity

[0216] (3-methyl-1-butene polymer (X))

[0217] As described above, the 3-methyl-1-butene polymer (X) is a 3-methyl-1-butene polymer that has not been subjected to a melting treatment and has a crystallinity of 80 to 100%, and its crystallinity is very high. This means that the 3-methyl-1-butene polymer just obtained by the above polymerization reaction has high crystallinity.

[0218] By making the crystallinity of the 3-methyl-1-butene polymer (X) within the above range, the mechanical strength such as the rigidity of the molded body and the solvent resistance are excellent. From the same viewpoint, the crystallinity of the 3-methyl-1-butene polymer (X) is preferably 85 to 100%, more preferably 55 to 75%, further preferably 88 to 100%, particularly preferably 89 to 100%, and most preferably 91 to 100%. The upper limit value of the crystallinity of the 3-methyl-1-butene polymer (X) may be 99% or less, may be 96% or less, or may be 94% or less.

[0219] (3-methyl-1-butene polymer (Y))

[0220] As described above, the 3-methyl-1-butene polymer (Y) is a 3-methyl-1-butene polymer that has been melt-treated and has a tendency to have a higher crystallinity than the above-mentioned 3-methyl-1-butene polymer (X), with a crystallinity of 95 to 100%. By making the crystallinity of the 3-methyl-1-butene polymer (Y) within the above range, the mechanical strength such as the rigidity of the molded body and the solvent resistance are excellent. From the same viewpoint, the crystallinity of the 3-methyl-1-butene polymer (Y) is preferably 96 to 100%, more preferably 97 to 100%, further preferably 98 to 100%, and particularly preferably 99 to 100%. The upper limit value of the crystallinity of the 3-methyl-1-butene polymer (Y) can be 99% or less, can be 98% or less, can also be 97% or less, and can also be 96% or less.

[0221] [Resin composition containing 3-methyl-1-butene polymer]

[0222] One embodiment of the present invention is a resin composition containing the 3-methyl-1-butene polymer of the present embodiment. Due to the high crystallinity of the 3-methyl-1-butene polymer of the present embodiment, the mechanical strength of the molded body can be improved. In addition, the resin composition of the present embodiment can also be expected to have characteristics such as a high melting point and high heat resistance.

[0223] In addition to the 3-methyl-1-butene polymer of the present embodiment, the resin composition of the present embodiment may contain additives such as antioxidants, alkyl radical scavengers, antacids, fillers, light stabilizers, antistatic agents, flame retardants, pigments, polymerization inhibitors, heavy metal passivators, ultraviolet absorbers, nucleating agents, clarifying agents, lubricants, fluorescent brighteners, rust inhibitors, etc. according to need; various other polymers; and other components.

[0224] They can be used alone or in combination of two or more.

[0225] The resin composition of the present embodiment can be produced by melt-kneading the 3-methyl-1-butene polymer and the above other components as needed at 280 to 380°C using a known mixer. Examples of the mixer include a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, a roll, etc.

[0226] [Pellets containing 3-methyl-1-butene polymer, pellets containing resin composition]

[0227] One embodiment of the present invention is pellets containing the 3-methyl-1-butene polymer of the present embodiment and pellets containing the resin composition of the present embodiment.

[0228] The pellets of the present embodiment can be obtained by cutting the resin composition of the present embodiment obtained in the form of an ejecta from a mixer by using a cutting machine or the like.

[0229] Due to the high crystallinity of the 3-methyl-1-butene polymer of the present embodiment, the mechanical strength of the molded article can be improved. In addition, the pellets of the present embodiment can also be expected to have characteristics such as a high melting point and high heat resistance.

[0230] [Molded article containing 3-methyl-1-butene polymer, molded article containing resin composition]

[0231] One mode of the present embodiment is a molded article containing the 3-methyl-1-butene polymer of the present embodiment and a molded article containing the resin composition of the present embodiment. The molded article of the present embodiment is obtained by molding the resin composition of the present embodiment.

[0232] The shape of the molded article of the present embodiment is not particularly limited, and examples thereof include a film, a sheet, a plate, a pipe, a tube, a rod-shaped body, a granular body, etc. It should be noted that the above-mentioned pellets can also be included in the concept of the molded article.

[0233] The manufacturing method of the molded article of the present embodiment is not particularly limited, and various conventional molding methods can be adopted. For example, in addition to injection molding, blow molding, compression molding, extrusion molding, calendering molding, a method of forming a film by blowing powder can also be adopted.

[0234] Due to the high crystallinity of the 3-methyl-1-butene polymer of the present embodiment, the mechanical strength of the molded article can be improved. In addition, the molded article of the present embodiment can also be expected to have characteristics such as a high melting point and high heat resistance.

[0235] The uses of the 3-methyl-1-butene polymer, resin composition and molded article of the present embodiment are not particularly limited, and examples thereof include coatings, substrate materials for copper-clad laminates, insulating films for film capacitors, insulating films for motor coils, insulators for motor coils, connectors for electrical equipment, fibers, power socket housings for EV (Electric Vehicle), millimeter-wave antenna housings, tableware such as chopsticks, dishes and rice spoons, housings for home appliances, chemical-resistant pipes and containers, coating materials for fibers or molded articles, etc.

[0236] Examples

[0237] Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited thereto.

[0238] 〈1〉Manufacture of catalyst

[0239] As the catalysts used in each example, the following Catalysts 1 to 2 were prepared.

[0240] In addition, as the catalysts used in each comparative example, the following Comparative Catalysts 3 to 6 were prepared.

[0241] Catalyst 1: Referring to International Publication No. 2005 / 108406, a complex having the following structure was prepared and used as Catalyst 1.

[0242] [Chemical Formula 20]

[0243]

[0244] Catalyst 2: Referring to International Publication No. 2005 / 108406, a complex having the following structure was prepared and used as Catalyst 2.

[0245] [Chemical Formula 21]

[0246]

[0247] Comparative Catalyst 3: Referring to the specification of European Patent Application Publication No. 834514, a metallocene complex having the following structure was prepared and used as Comparative Catalyst 3.

[0248] [Chemical Formula 22]

[0249]

[0250] Comparative Catalyst 4: Referring to the specification of European Patent Application Publication No. 669340, a metallocene complex having the following structure was prepared and used as Comparative Catalyst 4.

[0251] [Chemical Formula 23]

[0252]

[0253] Comparative Catalyst 5: Referring to Journal of the American Chemical Society (2021), 143(20), pages 7641 - 7647, a metallocene complex having the following structure was prepared and used as Comparative Catalyst 5.

[0254] [Chemical Formula 24]

[0255]

[0256] Comparative catalyst 6: A titanium catalyst (solid catalyst) was prepared according to the following production method and used as Comparative catalyst 6. It should be noted that Comparative catalyst 6 was used in the form of a heptane solution at a concentration of 4.0 g / L, and the content of Comparative catalyst 6 was 500 μL (equivalent to 1.67 μmol in terms of titanium atoms).

[0257] 47.6 g (500 mmol) of anhydrous magnesium chloride, 250 mL of decane, and 234 mL (1.5 mo1) of 2-ethylhexanol were heated and reacted at 130 °C for 2 hours to form a homogeneous solution. After cooling the thus obtained homogeneous solution to room temperature, it was added dropwise to 2 L (18 mol) of titanium tetrachloride maintained at -20 °C over 1 hour. After the addition was completed, the temperature of the resulting mixture was raised to 110 °C over 2 hours. When the temperature reached 110 °C, 42.4 mL (160 mmol) of dibutyl phthalate was added, and the mixture was stirred for 2 hours while maintaining the same temperature. After the reaction was completed, the supernatant was removed by standing. Decane and hexane were added thereto, and the solid component was washed 3 times. Then, it was resuspended in 2 L of titanium tetrachloride and heated again at 110 °C for 2 hours. Then, the steps of standing again using decane and hexane and removing the supernatant were repeated, and the washing was continued until no free titanium compound was detected in the washing liquid. The resulting suspended component was dried under reduced pressure at room temperature for 6 hours to obtain a titanium catalyst. The composition of the titanium catalyst thus obtained was analyzed by ICP (inductively coupled plasma) emission spectroscopy, anion chromatography, and 1 1H NMR analysis, and the results were 4.0 mass% of titanium atoms, 56.0 mass% of chlorine atoms, 17.0 mass% of magnesium atoms, and 11.0 mass% of ethyl benzoate.

[0258] 〈2〉3-Methyl-1-butene-based polymer

[0259] For the 3-methyl-1-butene-based polymers obtained in the examples and comparative examples, various physical properties were measured or evaluated by the following methods.

[0260] 〔Melting point and melting enthalpy〕

[0261] For the 3-methyl-1-butene-based copolymers obtained in the examples and comparative examples, a differential scanning calorimeter (TA Instrument "DSC25") was used. Under a nitrogen flow rate (100 mL / min), the temperature was raised from 30 °C to 320 °C at a rate of 10 °C / min [first heating]. After maintaining at 320 °C for 5 minutes, the temperature was lowered to -70 °C at a rate of 10 °C / min. After maintaining at -70 °C for 5 minutes, the temperature was raised to 320 °C at a rate of 10 °C / min [second heating], and the melting point and melting enthalpy at this time were measured.

[0262] 〔Polymerization activity〕

[0263] The polymerization activity is calculated by the following formula.

[0264] Polymerization activity = (mass (g) of the 3-methyl-1-butene polymer obtained by the polymerization reaction) ÷ (moles (mol) of the metal atoms in the catalyst added to the polymerization reaction system) ÷ (polymerization time (hr))

[0265] The larger the value of the polymerization activity, the less catalyst dosage is required to produce the polymer, which is economically advantageous.

[0266] 〔Crystallinity〕

[0267] For the 3-methyl-1-butene copolymers obtained in Example 1, Example 4, and Comparative Example 4, the crystallinity was calculated by the following method based on the results of X-ray diffraction under the following apparatus and conditions.

[0268] (1. Preparation of the measurement sample)

[0269] 〈3-Methyl-1-butene polymer without melt treatment〉

[0270] The 3-methyl-1-butene polymers obtained in Example 1, Example 4, and Comparative Example 4 were each subjected to heat annealing treatment by standing in an environment of a vacuum of 10 mmHg and 200 °C for 2 hours, and then cooled to 30 °C over 4 hours.

[0271] 10 mg of the measurement sample (3-methyl-1-butene polymer without melt treatment) that had undergone this heat annealing treatment was placed on a measurement plate to prepare for the measurement.

[0272] 〈3-Methyl-1-butene polymer with melt treatment〉

[0273] On the other hand, for the 3-methyl-1-butene polymers obtained in Example 1 and Example 4, a differential scanning calorimeter “Q2000” (manufactured by TA Instrument) was used, and under a nitrogen flow rate (100 mL / min), the temperature was raised from 30 °C to 320 °C at 10 °C / min, then held at 320 °C for 5 minutes to melt the 3-methyl-1-butene polymer, and then cooled to 30 °C at 10 °C / min.

[0274] 10 mg of the measurement sample that had undergone this melt treatment was placed on a measurement plate to prepare for the measurement.

[0275] (2. Measurement apparatus and conditions)

[0276] For the measurement samples prepared by the above method, the measurement based on X-ray diffraction was carried out under the following measurement apparatus and conditions, and a curve was obtained ( Figure 1~6).

[0277] Measuring device: NANOPIX (manufactured by Rigaku Corporation)

[0278] Measuring method: Wide-angle X-ray diffraction method

[0279] Detector: Semiconductor two-dimensional detector "HyPix-6000"

[0280] X-ray source: Cu

[0281] Current: 30 mA

[0282] Voltage: 40 kV

[0283] Exposure time: 300 seconds

[0284] Incident optical system: 2PHF

[0285] Measurement mode: Repeated measurement (4 sheets)

[0286] Camera length: 87.38 mm

[0287] Measurement temperature: 30 °C

[0288] Beam limiter diameter: 4 mm

[0289] Analysis software for curve conversion of two-dimensional images: 2DP (manufactured by Rigaku Corporation)

[0290] 2θ-INT conversion conditions: 2θ = 3 to 36 degrees, β = 0 to 360 degrees, step size = 0.02 degrees

[0291] (3. Method for calculating crystallinity)

[0292] The maximum peak intensity and the amorphous peak intensity are obtained from the curve obtained by the X-ray diffraction method using the above-mentioned measuring device, and the crystallinity is calculated according to the following calculation formula. Here, the above-mentioned maximum peak intensity is the intensity of the peak with a diffraction angle 2θ = 17.2 to 17.3 degrees at the peak top, and the above-mentioned amorphous peak intensity is the intensity at the valley between the peak with a diffraction angle 2θ = 10.1 to 10.3 degrees at the peak top and the peak with a diffraction angle 2θ = 11.4 to 11.6 degrees at the peak top.

[0293] <Calculation formula>

[0294] Crystallinity (%) = 100 × (maximum peak intensity - amorphous peak intensity) / maximum peak intensity

[0295] It should be noted that for the 3-methyl-1-butene-based copolymers obtained in Example 1, Example 4, and Comparative Example 4, the curves of the 3-methyl-1-butene-based copolymers without melt treatment are respectively shown in Figure 1 (Example 1),Figure 3 (Example 4), Figure 5 (Comparative Example 4). For the 3-methyl-1-butene copolymers obtained in Example 1 and Example 4, the curves of the melt-treated 3-methyl-1-butene copolymers are shown respectively in Figure 2 (Example 1), Figure 4 (Example 4).

[0296] <Manufacture of 3-methyl-1-butene copolymer>

[0297] [Example 1]

[0298] The manufacture of the 3-methyl-1-butene polymer was carried out using PPR48 for olefin polymerization (PPR: Parallel Pressure Reactor) (manufactured by Freeslate Co., Ltd.). The above PPR48 was provided with 48 reactors in a triple glove box isolated from the outside. The polymerization steps are as follows.

[0299] 3-Methyl-1-butene (3.5 mL), a toluene solution of triphenylmethyltetrakis(pentafluorophenyl)borate {[Ph3C][B(C6F5)4], TTB} [concentration: 0.005 mol / L, TTB content: 60 μL (equivalent to 300 nmol)] and a toluene solution of triisobutylaluminum (TIBA) [concentration: 0.1 mol / L, TIBA content: 850 μL (equivalent to 85 μmol)] were pumped into one of the above reactors and maintained at 70 °C.

[0300] Then, a toluene solution of Catalyst 1 [concentration: 0.005 mol / L, Catalyst 1 content: 30 μL (equivalent to 150 nmol)] and heptane were pumped into the above reactor. The total amount of heptane and toluene used was 5.0 mL.

[0301] After polymerizing 3-methyl-1-butene for 120 minutes, quenching was carried out by overpressurizing the reactor with dry air. After quenching, the reactor was cooled and vented. While distilling off the volatile components in the obtained reaction solution using a Genevac EZ2-Plus centrifugal evaporator, the 3-methyl-1-butene polymer was dried overnight.

[0302] The same operation was carried out twice, and as a result, the average mass of the obtained 3-methyl-1-butene polymer was 1.47 g.

[0303] In addition, for the obtained 3-methyl-1-butene polymer, each measurement was carried out by the above method. The results are shown in Table 1.

[0304] [Example 2]

[0305] In Example 1, the polymerization temperature was changed from 70 °C to 120 °C, and the polymerization time was changed from 120 minutes to 30 minutes. Except for this, a 3-methyl-1-butene polymer was produced by the same method. Each measurement was performed on the obtained 3-methyl-1-butene polymer by the above method. The results are shown in Table 1.

[0306] [Example 3]

[0307] In Example 1, the polymerization temperature was changed from 70 °C to 150 °C, and the polymerization time was changed from 120 minutes to 5 minutes. Except for this, a 3-methyl-1-butene polymer was produced by the same method. Each measurement was performed on the obtained 3-methyl-1-butene polymer by the above method. The results are shown in Table 1.

[0308] [Example 4]

[0309] In Example 1, the activator (3) was changed from TTB and TIBA to a toluene solution of methylaluminoxane (MAO) [concentration: 0.2 mol / L, MAO content: 550 μL (equivalent to 110 μmol)] and a toluene solution of 2,6-di-tert-butyl-p-cresol (BHT) [concentration: 0.1 mol / L, BHT content: 450 μL (equivalent to 45 μmol)]. Except for this, a 3-methyl-1-butene polymer was produced by the same method. Each measurement was performed on the obtained 3-methyl-1-butene polymer by the above method. The results are shown in Table 1.

[0310] [Example 5]

[0311] In Example 2, the catalyst was changed from Catalyst 1 to Catalyst 2, and the polymerization time was changed from 30 minutes to 10 minutes. Except for this, a 3-methyl-1-butene polymer was produced by the same method. Each measurement was performed on the obtained 3-methyl-1-butene polymer by the above method. The results are shown in Table 1.

[0312] [Example 6]

[0313] In Example 5, the polymerization temperature was changed from 120 °C to 135 °C. Except for this, a 3-methyl-1-butene polymer was produced by the same method. Each measurement was performed on the obtained 3-methyl-1-butene polymer by the above method. The results are shown in Table 1.

[0314] [Comparative Example 1]

[0315] In Example 1, the catalyst was changed from Catalyst 1 to Comparative Catalyst 3, and otherwise, a 3-methyl-1-butene polymer was produced by the same method. Each measurement was performed on the obtained 3-methyl-1-butene polymer by the above method. The results are shown in Table 1.

[0316] [Comparative Example 2]

[0317] In Example 1, the catalyst was changed from Catalyst 1 to Comparative Catalyst 4, and otherwise, a 3-methyl-1-butene polymer was produced by the same method. Each measurement was performed on the obtained 3-methyl-1-butene polymer by the above method. The results are shown in Table 1.

[0318] [Comparative Example 3]

[0319] In Example 1, the catalyst was changed from Catalyst 1 to Comparative Catalyst 5, and otherwise, a 3-methyl-1-butene polymer was produced by the same method. Each measurement was performed on the obtained 3-methyl-1-butene polymer by the above method. The results are shown in Table 1.

[0320] [Comparative Example 4]

[0321] In Example 1, the catalyst was changed from Catalyst 1 to Comparative Catalyst 6, and the activator was changed from TTB and TIBA to a heptane solution of triethylaluminum (TEA) [concentration: 0.1 mol / L, TEA content: 600 μL (equivalent to 60 μmol)], and otherwise, a 3-methyl-1-butene polymer was produced by the same method. Each measurement was performed on the obtained 3-methyl-1-butene polymer by the above method. The results are shown in Table 1.

[0322] [Table 1]

[0323]

[0324] According to Table 1, in Examples 1 to 6, a 3-methyl-1-butene-based polymer having a melting enthalpy of 65 to 100 J / g can be obtained. Since the 3-methyl-1-butene-based polymer has a high melting enthalpy, it has high crystallinity and can improve the mechanical strength of the molded article.

[0325] On the other hand, in Comparative Examples 1 to 4, a 3-methyl-1-butene-based polymer having a melting enthalpy of 65 to 100 J / g could not be obtained.

[0326] In Example 1 and Example 4, it was demonstrated that the crystallinity was higher than that in Comparative Example 4. In addition, when comparing Figure 1 and Figure 2 , it can be seen that compared with Figure 1 , Figure 2The peak is sharper. A sharp peak means high crystallinity. That is, the 3-methyl-1-butene-based polymer subjected to the melting treatment shows higher crystallinity than the 3-methyl-1-butene-based polymer not subjected to the melting treatment. According to Figure 3 With Figure 4 The comparison is also the same case.

[0327] In addition, in the production of the 3-methyl-1-butene-based polymer, the catalyst used in Example 1 has higher polymerization activity compared to the homogeneous catalysts (metallocene catalysts) used in Comparative Examples 1 to 3 and the solid catalyst used in Comparative Example 4, which is economically advantageous.

Claims

1. A 3-methyl-1-butene polymer having a melting enthalpy of 65 J / g to 100 J / g as determined by differential scanning calorimetry (DSC).

2. The 3-methyl-1-butene polymer according to claim 1, having a melting point of 280 °C to 310 °C.

3. A 3-methyl-1-butene polymer which is an un-melted 3-methyl-1-butene polymer and has a crystallinity of 80% to 100% determined by the following method, Calculation method of crystallinity: The maximum peak intensity and the amorphous peak intensity are obtained from the curve obtained by X-ray diffraction method, and the crystallinity is calculated according to the following calculation formula. Here, the maximum peak intensity is the intensity of the peak with a diffraction angle 2θ = 17.2 degrees to 17.3 degrees at the peak top, and the amorphous peak intensity is the intensity between the valleys of the peak with a diffraction angle 2θ = 10.1 degrees to 10.3 degrees at the peak top and the peak with a diffraction angle 2θ = 11.4 degrees to 11.6 degrees at the peak top. Calculation formula: Crystallinity (%) = 100 × (maximum peak intensity - amorphous peak intensity) / maximum peak intensity.

4. A 3-methyl-1-butene polymer which is a melted 3-methyl-1-butene polymer and has a crystallinity of 95% to 100% determined by the following method, Calculation method of crystallinity: The maximum peak intensity and the amorphous peak intensity are obtained from the curve obtained by X-ray diffraction method, and the crystallinity is calculated according to the following calculation formula. Here, the maximum peak intensity is the intensity of the peak with a diffraction angle 2θ = 17.2 degrees to 17.3 degrees at the peak top, and the amorphous peak intensity is the intensity between the valleys of the peak with a diffraction angle 2θ = 10.1 degrees to 10.3 degrees at the peak top and the peak with a diffraction angle 2θ = 11.4 degrees to 11.6 degrees at the peak top. Calculation formula: Crystallinity (%) = 100 × (maximum peak intensity - amorphous peak intensity) / maximum peak intensity.

5. The 3-methyl-1-butene polymer according to any one of claims 1 to 4 is a 3-methyl-1-butene homopolymer or a copolymer of 3-methyl-1-butene and ethylene or an α-olefin.

6. The 3-methyl-1-butene polymer according to any one of claims 1 to 5, wherein The α-olefin is an α-olefin having 3 to 20 carbon atoms.

7. A resin composition comprising the 3-methyl-1-butene polymer according to any one of claims 1 to 6.

8. A pellet comprising the 3-methyl-1-butene polymer according to any one of claims 1 to 6 or the resin composition according to claim 7.

9. A molded article comprising the 3-methyl-1-butene polymer according to any one of claims 1 to 6 or the resin composition according to claim 7.

10. A method for producing a 3-methyl-1-butene polymer, which is the method for producing a 3-methyl-1-butene polymer according to any one of claims 1 to 6, and which produces a 3-methyl-1-butene polymer by homopolymerizing 3-methyl-1-butene or copolymerizing 3-methyl-1-butene with ethylene or an α-olefin in the presence of a catalyst formed from a composition containing a ligand 1 represented by the following formula (I) or (II) and a metal compound 2 represented by the formula M(L) n wherein the metal compound 2 is represented by the formula M(L), and the ligand 1 is represented by the formula (I) or (II). Each ligand represented by formula (I) or (II) has at least two hydrogen atoms that can be removed in the bonding reaction with a metal atom, the metal compound 2, or a base, Ar 1 ~Ar 4 are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, B is a crosslinking group having 1 to 50 atoms other than hydrogen atoms, X and X' are both oxygen atoms, X'' and X''' are each independently a hydroxyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group, Y and Y' are each independently a hydroxyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group, In the formula M(L) n , M is titanium, hafnium or zirconium, L is a component that forms a covalent bond, a coordination bond or an ionic bond with the said M, and n is an integer from 2 to 6.

11. The method for producing a 3-methyl-1-butene polymer according to claim 10, wherein, The ligand 1 has the following structure, Wherein, B, Y and Y' are as defined above, and R 1 ~R 4 are each independently a substituent selected from the group consisting of alkyl, aryl, heteroaryl, and combinations thereof, and n1 to n4 are each independently an integer from 1 to 4.

12. The method for producing a 3-methyl-1-butene polymer according to claim 10 or 11, wherein, The polymerization or copolymerization is carried out in the presence of an activator 3.

13. The method for producing a 3-methyl-1-butene polymer according to any one of claims 10 to 12, wherein, The polymerization temperature is 10 °C to 180 °C.

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