Fluorine-containing cyclic olefin (CO)polymer and method for producing the same

Abstract

To provide a fluorine-containing cyclic olefin (co)polymer with high content of fluorinated norbornene.SOLUTION: Provided is a fluorine-containing cyclic olefin (co)polymer that contains a fluorinated norbornene constitutional unit with a specific structure, and a C2-10 α-olefin-derived constitutional unit. The content of the fluorinated norbornene constitutional unit with the specific structure is more than 40 mol%, and the content of the α-olefin-derived constitutional unit is 0 mol% or more and less than 60 mol%.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a fluorine-containing cyclic olefin (co)polymer and a method for producing the same. [Background technology]

[0002] Cyclic olefin (co)polymers have properties such as high heat resistance, high transparency, and low dielectric properties, and are used in a variety of applications, including in the field of optical materials such as optical disk substrates, optical films, and optical fibers, as well as resin layers in metal-clad laminates (printed circuit boards, etc.). Representative cyclic olefin copolymers include copolymers of cyclic olefins and α-olefins, which are widely used as transparent resins.

[0003] On the other hand, fluororesins such as PTFE (Polytetrafluoroethylene) and ETFE (Ethylene tetrafluoroethylene) have various excellent properties such as high heat resistance, chemical resistance, low dielectric properties, water repellency, mold releasability, low friction, and high insulation. Therefore, they are used in various applications by taking advantage of their respective properties. However, fluororesins are not easy to mold, and it is difficult to obtain molded products. On the other hand, since cyclic olefin (co)polymers are generally easy to mold, if the advantages of fluororesins can be imparted to cyclic olefin (co)polymers, they can become a substitute for fluororesins and a new material that is easy to mold.

[0004] Therefore, by fluorinating norbornene and homopolymerizing or copolymerizing it with an α-olefin, a fluorine-rich cyclic olefin (co)polymer can be obtained, and it is expected that a material having both the properties of a cyclic olefin (co)polymer and that of a fluororesin can be obtained (see Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2019-131658 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, the fluorine-containing cyclic olefin copolymer described in Patent Document 1 has a low fluorine-containing cyclic olefin content of 20 mol% to 40 mol%, and is not expected to have properties equivalent to those of fluororesins. If the content of the fluorine-containing cyclic olefin could be increased, this problem could be solved, but fluorinated norbornene (hereinafter referred to as "fluorinated norbornene") has a low reactivity and is difficult to polymerize, so it is not easy to increase the content of the fluorine-containing cyclic olefin.

[0007] The present invention has been made in consideration of the above-mentioned conventional problems, and an object of the present invention is to provide a fluorine-containing cyclic olefin (co)polymer having a high content of fluorinated norbornene. Another object of the present invention is to provide a method for producing a fluorine-containing cyclic olefin (co)polymer, which is capable of producing a fluorine-containing cyclic olefin (co)polymer having a high content of fluorinated norbornene. [Means for solving the problem]

[0008] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems and have found that in polymerization of a cyclic olefin (co)polymer using fluorinated norbornene as a monomer, the content of fluorinated norbornene can be increased by using fluorinated norbornene not only as a monomer but also as a solvent, thereby completing the present invention.

[0009] One aspect of the present invention that solves the above problems is as follows. (1) A structural unit represented by the following general formula (1) and a structural unit derived from an α-olefin having 2 to 10 carbon atoms, A fluorine-containing cyclic olefin (co)polymer, in which the content of the structural unit represented by the general formula (1) is more than 40 mol %, and the content of the structural unit derived from the α-olefin having 2 to 10 carbon atoms is from 0 mol % to less than 60 mol %.

[0010] [ka] [In general formula (1), R 1 ~R 8 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group; R 9 ~R 12 each independently represents a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, an alkyl group having a fluorine atom, an alkoxy group having a fluorine atom, an ether bond-containing alkyl group having a fluorine atom, or 13 Or -OCOR 13 R represents a substituent represented by the formula: 9 ~R 12 At least one fluorine atom is contained therein, and R 9 or R 10 And, R 11 or R 12 may form a ring together. R 13 is a substituted or unsubstituted alkyl group, or an alkyl group having a fluorine atom. In addition, m represents 0 or a positive integer, and when m is 2 or more, R 5 ~R 8 may be the same or different in each repeating unit. When m=0, R 1 ~R 4 and R 9 ~R 12 At least one of the is not a hydrogen atom.

[0011] (2) The fluorine-containing cyclic olefin (co)polymer according to (1) above, which is amorphous.

[0012] (3) The fluorine-containing cyclic olefin (co)polymer according to (1) or (2) above, wherein a DSC curve obtained by measuring with a differential scanning calorimeter under a nitrogen atmosphere at a heating rate of 20°C / min according to the method described in JIS K7121 does not have a melting point peak within a range of 25 to 350°C.

[0013] (4) a charging step of charging at least a monomer represented by the following general formula (2) and a monomer containing an α-olefin having 2 to 10 carbon atoms, a catalyst, and a solvent into a polymerization vessel; and a polymerization step of polymerizing the monomer in the polymerization vessel in the presence of the catalyst, A method for producing a fluorine-containing cyclic olefin (co)polymer, wherein in the charging step, the amount of the monomer represented by the general formula (2) charged is more than 40 mol %, the amount of the α-olefin having 2 to 10 carbon atoms charged is 0 mol % or more and less than 60 mol %, and the monomer represented by the general formula (2) is also used as a solvent, and the amount of the monomer represented by the general formula (2) charged in the solvent is more than 50 mass %.

[0014] [ka] [In general formula (2), R 1 ~R 12 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted or unsubstituted alkyl group, an alkyl group having a fluorine atom, an alkoxy group having a fluorine atom, an ether bond-containing alkyl group having a fluorine atom, or 13 Or -OCOR 13 R represents a substituent represented by the formula: 1 ~R 12 At least one fluorine atom is contained therein, and R 9 or R 10 And, R 11 or R 12 may form a ring together. R 13 is a substituted or unsubstituted alkyl group, or an alkyl group having a fluorine atom. In addition, m represents 0 or a positive integer, and when m is 2 or more, R 5 ~R 8 may be the same or different in each repeating unit. When m=0, R 1 ~R 4 and R 9 ~R12 At least one of the is not a hydrogen atom.

[0015] (5) The method for producing a fluorine-containing cyclic olefin (co)polymer according to (4) above, wherein at least one of the catalysts is a catalyst containing a metal element of Group 10 of the periodic table or a catalyst containing a metal element of Group 4 of the periodic table.

[0016] (6) The method for producing a fluorine-containing cyclic olefin (co)polymer according to (5) above, wherein when at least one of the catalysts contains a metal element of Group 10 of the periodic table, the catalyst does not contain an aluminoxane.

[0017] (7) The method for producing a fluorine-containing cyclic olefin (co)polymer according to (5) above, wherein when at least one of the catalysts contains a metal element of Group 10 of the periodic table, the catalyst does not contain an organoboron compound. Effect of the Invention

[0018] According to the present invention, it is possible to provide a fluorine-containing cyclic olefin (co)polymer having a high content of fluorinated norbornene. In addition, it is possible to provide a method for producing a fluorine-containing cyclic olefin (co)polymer, which is capable of producing a fluorine-containing cyclic olefin (co)polymer having a high content of fluorinated norbornene. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] <Fluorine-containing cyclic olefin (co)polymer> The fluorine-containing cyclic olefin (co)polymer of this embodiment contains a constitutional unit represented by the following general formula (1) and a constitutional unit derived from an α-olefin having 2 to 10 carbon atoms. The content of the constitutional unit represented by general formula (1) is more than 40 mol %, and the content of the constitutional unit derived from an α-olefin having 2 to 10 carbon atoms is 0 mol % or more and less than 60 mol %.

[0020] [ka] [In general formula (1), R 1 ~R 8 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group; R 9 ~R 12 each independently represents a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, an alkyl group having a fluorine atom, an alkoxy group having a fluorine atom, an ether bond-containing alkyl group having a fluorine atom, or 13 Or -OCOR 13 R represents a substituent represented by the formula: 9 ~R 12 At least one fluorine atom is contained therein, and R 9 or R 10 And, R 11 or R 12 may form a ring together. R 13 is a substituted or unsubstituted alkyl group, or an alkyl group having a fluorine atom. In addition, m represents 0 or a positive integer, and when m is 2 or more, R 5 ~R 8 may be the same or different in each repeating unit. When m=0, R 1 ~R 4 and R 9 ~R 12 At least one of the is not a hydrogen atom.

[0021] The fluorine-containing cyclic olefin (co)polymer of this embodiment has a high fluorine content because the content of the structural unit represented by the general formula (1), i.e., the content of fluorinated norbornene, is more than 40 mol %, and can enjoy the properties of fluororesin (high heat resistance, chemical resistance, low dielectric properties, water repellency, low friction, high insulation, etc.) to a certain extent. Therefore, the fluorine-containing cyclic olefin (co)polymer of this embodiment can be a substitute for fluorine resins and ionomers such as Nafion. In addition, it also has the property that the cyclic olefin (co)polymer can be easily molded. Therefore, the fluorine-containing cyclic olefin (co)polymer of this embodiment is expected to be a new material that has the properties of a cyclic olefin (co)polymer and a fluororesin. When the content of the constitutional units derived from an α-olefin having 2 to 10 carbon atoms is 0 mol %, it is a homopolymer containing only constitutional units represented by the above general formula (1). When the content of the constitutional units derived from an α-olefin having 2 to 10 carbon atoms is more than 0 mol %, it is a copolymer containing constitutional units represented by the above general formula (1) and constitutional units derived from an α-olefin having 2 to 10 carbon atoms. In other words, the term "fluorine-containing cyclic olefin (co)polymer" means to include fluorine-containing cyclic olefin polymers and fluorine-containing cyclic olefin copolymers. Hereinafter, each structural unit of the fluorine-containing cyclic olefin (co)polymer of this embodiment will be described.

[0022] [Structural unit represented by general formula (1)] As described above, the structural unit represented by the general formula (1) is a structural unit derived from fluorinated norbornene. In the present embodiment, the content of the structural unit represented by the general formula (1) is more than 40 mol%, so that the cyclic olefin (co)polymer is rich in fluorine.

[0023] In general formula (1), R 1 ~R 8 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. 1 ~R 8 may be the same or different.

[0024] R 1 ~R 8 Specific examples of the alkyl group include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; and an alkyl group having 1 to 20 carbon atoms. These may be different from each other, may be partially different, or may be the same as each other.

[0025] R 9 ~R 12 each independently represents a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, an alkyl group having a fluorine atom, an alkoxy group having a fluorine atom, an ether bond-containing alkyl group having a fluorine atom, or -COOR 13 Or -OCOR 13 R represents a substituent represented by the formula: 9 ~R 12 At least one fluorine atom is contained therein, and R 9 or R 10 And, R 11 or R 12 may form a ring together. R 13 is a substituted or unsubstituted alkyl group, or an alkyl group having a fluorine atom.

[0026] R in general formula (1) 9 ~R 12 The substituted or unsubstituted alkyl group represented by the formula (I) preferably has a carbon atom number of 1 to 30, and more preferably has a carbon atom number of 1 to 20. Examples of the alkyl group include a methyl group, an ethyl group, and an n-propyl group. Examples of the substituted alkyl group include an aralkyl group, a hydroxyalkyl group (eg, a hydroxyethyl group), and an alkoxyalkyl group (eg, a methoxyethyl group). The aralkyl group preferably has a carbon atom number of 7 to 30, and more preferably has a carbon atom number of 7 to 20. Examples of the aralkyl group include a benzyl group and a phenethyl group. Other substituents of the substituted alkyl group include, for example, halogen atoms (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy groups (eg, methoxy group, ethoxy group), and the like. Above R 9 ~R 12 Examples of the fluorine-containing alkyl group represented by the formula (I) include fluorine-containing alkyl groups having 1 to 30 carbon atoms, preferably perfluoroalkyl groups having 1 to 10 carbon atoms, and more preferably perfluoroalkyl groups having 1 to 4 carbon atoms. Above R 9 ~R 12 Examples of the alkoxy group containing a fluorine atom represented by the formula (I) include an alkoxy group containing a fluorine atom having 1 to 30 carbon atoms, and a perfluoroalkoxy group having 1 to 10 carbon atoms is preferred. Above R 9 ~R 12 The ether bond-containing alkyl group containing a fluorine atom represented by the formula (I) can be, for example, an alkoxy group containing a fluorine atom having 1 to 30 carbon atoms, and a perfluoroalkoxy group having 1 to 10 carbon atoms is preferred. Above R 9 ~R 12 In -COOR 13 Or -OCOR 13 Also preferred is R 13 is a substituted or unsubstituted alkyl group or an alkyl group containing a fluorine atom, and is more preferably an alkyl group containing a fluorine atom. 13 and -OCOR 13 Of these, -COOR 13 is preferred, where R 13 Examples of the substituted or unsubstituted alkyl group and the alkyl group containing a fluorine atom in the above R 9 ~R 12 Examples similar to those given in the above can be mentioned.

[0027] Above R 9 ~R 12is preferably a fluorine atom, an alkyl group containing a fluorine atom, or an alkoxy group containing a fluorine atom, and more preferably a fluorine atom or an alkyl group containing a fluorine atom. Above R 9 ~R 12 At least two of R may be bonded to each other to form a ring structure. The ring structure may be a monocyclic or polycyclic ring. For example, R 9 ~R 12 can be exemplified by the case where two of the above are bonded to each other to form an alkylene group, and further, R 9 and R 10 Either of these and R 11 and R 12 and any one of the following may be bonded to each other to form an alkylene group. R 9 and R 10 , or R 11 and R 12 Specific examples of the divalent hydrocarbon group formed by combining with each other include alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group.

[0028] R 9 or R 10 And, R 11 or R 12 When these rings form a ring, the ring formed may be a monocyclic ring or a polycyclic ring, a polycyclic ring having a bridge, a ring having a double bond, or a ring consisting of a combination of these rings. These rings may have a substituent such as a methyl group. Above R 9 ~R 12 At least one fluorine atom is contained therein, and 9 ~R 12 It is preferable that R contains three or more fluorine atoms. 9 ~R 12 At least one trifluoromethyl group (-CF 3 It is further preferred that the aryl group contains a aryl group.

[0029] In the general formula (1), m represents 0 or 1, and is preferably 1. In addition, in the general formula (1), m is 1 and R 9 ~R 12 It is more preferable that at least three of the R 9 ~R 12 Three of the R 9 ~R 12 One of the groups is a trifluoromethyl group (-CF 3 It is particularly preferred that the aryl group is a aryl group.

[0030] Specific examples of monomers from which the structural unit represented by general formula (1) is derived are shown below. However, the following examples are compounds before fluorine substitution, and in reality, R in general formula (1) 9 ~R 12and at least one of the corresponding atoms or atomic groups is replaced by a fluorine atom or a substituent having a fluorine atom. 5-Methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-hexyl-bicyclo[2.2.1]hept-2-ene cycloolefins such as 5-octyl-bicyclo[2.2.1]hept-2-ene, 5-octadecyl-bicyclo[2.2.1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, and 5-propenyl-bicyclo[2.2.1]hept-2-ene; .0.12,5]deca-3,7-diene (trivial name: dicyclopentadiene), tricyclo[4.3.0.12,5]deca-3-ene; tricyclo[4.4.0.12,5]undeca-3,7-diene or tricyclo[4.4.0.12,5]undeca-3,8-diene or their partially hydrogenated products (or adducts of cyclopentadiene and cyclohexene), tricyclo[4.4.0.12,5]undec-3-ene; three-ring cyclic olefins such as 5-cyclopentyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexenyl-bicyclo[2.2.1]hept-2-ene, 5-phenyl-bicyclo[2.2.1]hept-2-ene; tetracyclo[4.4.0.12,5.17,10]dodec-3-ene (also simply called tetracyclododecene), 8-methyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-methylidenetetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-vinyltetracyclo[4,4.0.12,5.17,10]dodec-3-ene, 8-propenyl-tetracyclo[4.4.0.12,5.17,10]dodec-3-ene, and other cyclic olefins; 8-Cyclopentyl-tetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo[4.4.0.12,5.17,10]dodec-3-ene; tetracyclo[7.4.13,6.01,9.02,7]tetradec-4,9,11,13-tetraene (also called 1,4-methano-1,4,4a,9a-tetrahydrofluorene), tetracyclo[8.4.14,7.01,10.03,8]pentadeca-5,10,12,14- Tetraene (also called 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene); pentacyclo[6.6.1.13,6.02,7.09,14]-4-hexadecene, pentacyclo[6.5.1.13,6.02,7.09,13]-4-pentadecene, pentacyclo[7.4.0.02,7.13,6.110 ,13]-4-pentadecene; heptacyclo[8.7.0.12,9.14,7.111,17.03,8.012,16]-5-eicosene, heptacyclo[8.7.0.12,9.03,8.14,7.012,17.113,16]-14-eicosene; and polycyclic olefins such as cyclopentadiene tetramers.

[0031] Among these, alkyl-substituted norbornenes (e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups) and alkylidene-substituted norbornenes (e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkylidene groups) are preferred, and 5-ethylidene-bicyclo[2.2.1]hept-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidenenorbornene) is particularly preferred.

[0032] Two specific examples of monomers from which the structural unit represented by general formula (1) is derived are given below. However, the fluorine-containing cyclic olefin (co)polymer of the present embodiment is not limited to the following two examples.

[0033] [ka]

[0034] The content of the structural unit represented by the general formula (1) is more than 40 mol%, preferably 60 mol% or more, and more preferably 80 mol% or more. If the structural unit is less than 40 mol%, it becomes difficult to obtain the properties of the fluororesin, such as water repellency and low dielectric constant.

[0035] [Structural units derived from α-olefins having 2 to 10 carbon atoms] The α-olefin having 2 to 10 carbon atoms derived from a structural unit derived from an α-olefin having 2 to 10 carbon atoms is not particularly limited, and examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 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, and 1-dodecene. Among these, ethylene, 1-hexene, 1-octene, and 1-decene are preferred.

[0036] The content of the structural unit derived from an α-olefin having 2 to 10 carbon atoms is 0 mol% or more and less than 60 mol%. As described above, when the structural unit is 0 mol%, it is a homopolymer of only the structural unit represented by general formula (1), and when it exceeds 0 mol%, it is a copolymer of the structural unit and the structural unit represented by general formula (1). In the case of a copolymer, the content of the structural unit derived from an α-olefin having 2 to 10 carbon atoms is preferably 5 to 59 mol%, more preferably 10 to 50 mol%, and even more preferably 20 to 40 mol%.

[0037] As described above, the fluorine-containing cyclic olefin (co)polymer of the present embodiment has the same property as the cyclic olefin (co)polymer, that is, the cyclic olefin copolymer is easier to mold than the cyclic olefin homopolymer.

[0038] The fluorine-containing cyclic olefin (co)polymer of this embodiment is preferably amorphous. Being amorphous makes it transparent, and it can be applied to molded products that require transparency. In other words, the fluorine-containing cyclic olefin (co)polymer of this embodiment is preferably such that the DSC curve obtained by measuring with a differential scanning calorimeter under a nitrogen atmosphere at a temperature rise rate of 20°C / min according to the method described in JIS K7121 does not have a melting point peak within the range of 25 to 350°C. That is, the fact that such a DSC curve does not have a melting point peak within the range of 25 to 350°C means that the fluorine-containing cyclic olefin (co)polymer is transparent.

[0039] As described above, the fluorine-containing cyclic olefin (co)polymer of the present embodiment has the properties of fluororesins to a certain extent, and therefore can be used in release films for fuel cells by taking advantage of its releasability and low dielectric properties, and in high-frequency antenna substrates, antennas, printed circuit boards, thin films and coatings for fuel cell membranes, catalyst coatings, sensors, heat-resistant industrial films, etc. by taking advantage of its low dielectric properties.

[0040] The above-mentioned fluorine-containing cyclic olefin (co)polymer of this embodiment can be produced by the production method of the fluorine-containing cyclic olefin (co)polymer of this embodiment shown below.

[0041] <Method of producing fluorine-containing cyclic olefin (co)polymer> The method for producing a fluorine-containing cyclic olefin (co)polymer of the present embodiment includes a charging step of charging at least a monomer containing a monomer represented by the following general formula (2) and an α-olefin having 2 to 10 carbon atoms, a catalyst, and a solvent into a polymerization vessel, and a polymerization step of polymerizing the monomer in the polymerization vessel in the presence of the catalyst. The charging step is characterized in that the amount of the monomer represented by general formula (2) charged is more than 40 mol%, the amount of the α-olefin having 2 to 10 carbon atoms charged is 0 mol% or more and less than 60 mol%, and the monomer represented by general formula (2) is also used as a solvent, and the amount of the monomer represented by general formula (2) charged in the solvent is more than 50 mass%.

[0042] [ka] [In general formula (2), R 1 ~R 12 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted or unsubstituted alkyl group, an alkyl group having a fluorine atom, an alkoxy group having a fluorine atom, an ether bond-containing alkyl group having a fluorine atom, or 13 Or -OCOR 13 R represents a substituent represented by the formula: 1 ~R 12 At least one fluorine atom is contained therein, and R 9 or R 10 And, R 11 or R 12 may form a ring together. R 13 is a substituted or unsubstituted alkyl group, or an alkyl group having a fluorine atom. In addition, m represents 0 or a positive integer, and when m is 2 or more, R 5 ~R 8may be the same or different in each repeating unit. When m=0, R 1 ~R 4 and R 9 ~R 12 At least one of the is not a hydrogen atom.

[0043] In the method for producing a fluorine-containing cyclic olefin (co)polymer of this embodiment, in the charging step, the monomer represented by general formula (2) is charged not only as a monomer but also as a solvent. That is, in the polymerization step, polymerization is performed by bulk polymerization. Therefore, the reaction rate of the monomer represented by general formula (2) is higher than when other solvents are used, and the content of the structural unit derived from the monomer represented by general formula (2) in the fluorine-containing cyclic olefin (co)polymer can be increased. As a result, the polymer becomes fluorine-rich and the properties of the fluororesin can be enjoyed to a certain extent.

[0044] The monomer represented by the general formula (2) is a monomer from which the constitutional unit represented by the general formula (1) is derived. 1 ~R 8 Explanation of R 9 ~R 12 The explanation of the structural unit represented by the above general formula (1) is the same as that of the structural unit represented by the above general formula (1), and the specific examples and preferred aspects or examples are also the same. Therefore, the explanation of the monomer represented by the general formula (2) is omitted. Similarly, a monomer containing an α-olefin having 2 to 10 carbon atoms is a monomer from which a structural unit derived from an α-olefin having 2 to 10 carbon atoms is derived. Therefore, the explanation of the structural unit derived from an α-olefin having 2 to 10 carbon atoms applies to the α-olefin having 2 to 10 carbon atoms as described above, and the same applies to specific examples and preferred aspects or examples. Therefore, the explanation of the α-olefin having 2 to 10 carbon atoms is omitted. Each step will be described below.

[0045] [Preparation process] In the charging step, at least the monomer represented by the general formula (2) and a monomer containing an α-olefin having 2 to 10 carbon atoms, a catalyst, and a solvent are charged into a polymerization vessel. In the charging step, the amount of the monomer represented by the general formula (2) charged is more than 40 mol%, and the amount of the α-olefin having 2 to 10 carbon atoms charged is 0 mol% or more and less than 60 mol%. In addition, the monomer represented by the general formula (2) is also used as a solvent, and the amount of the monomer represented by the general formula (2) charged in the solvent is more than 50 mass%.

[0046] The amount of the monomer represented by the general formula (2) is more than 40 mol%, and the amount of the α-olefin having 2 to 10 carbon atoms is 0 mol% or more and less than 60 mol%. As described above, in the case of a homopolymer, the amount of the α-olefin having 2 to 10 carbon atoms is 0 mol%. In that case, the amount of the monomer represented by the general formula (2) is naturally 100 mol%. By feeding the monomer represented by the general formula (2) in an amount of more than 40 mol%, the content of fluorinated norbornene in the resulting fluorine-containing cyclic olefin copolymer increases, making the copolymer fluorine-rich, and thus the properties of the fluororesin can be enjoyed as described above.

[0047] (catalyst) As the catalyst, a catalyst containing a metal element of Group 10 of the periodic table, a catalyst containing a metal element of Group 4 of the periodic table, etc. can be used. By using a catalyst containing a metal element of Group 10 of the periodic table and / or a catalyst containing a metal element of Group 4 of the periodic table, the reaction rate of the monomer represented by General Formula (2) can be further increased in combination with using the monomer represented by General Formula (2) not only as a monomer but also as a solvent. Examples of metal elements of Group 10 of the periodic table include nickel (Ni), palladium (Pd), and platinum (Pt), with palladium being particularly preferred. Examples of metal elements of Group 4 of the periodic table include titanium (Ti), zirconium (Zr), and hafnium (Hf), with Ti being particularly preferred. Examples of catalysts containing a metal element of Group 10 of the periodic table include sulfates, nitrates, chlorides, complexes, alkyl forms, etc. of the metal element. Examples of catalysts containing a metal element of Group 4 of the periodic table include chlorides, complexes, alkyl forms, etc. of the metal element. A catalyst containing a metal element of Group 10 of the periodic table and a catalyst containing a metal element of Group 4 of the periodic table have been described above, but in terms of catalytic activity, the former is more preferable than the latter.

[0048] The amount of the catalyst used is preferably 0.000001 to 0.001 mol, and more preferably 0.00001 to 0.0001 mol, per 1 mol of the monomer represented by the general formula (1).

[0049] On the other hand, when using a catalyst containing a metal element of Group 10 of the periodic table as described above, it is generally not necessary to use an aluminoxane or an organoboron compound. That is, in the present embodiment, the catalyst may be an embodiment that does not contain an aluminoxane or an organoboron compound. The aluminoxane is an aluminoxane that has been used as a cocatalyst in the polymerization of various olefins, and is typically an organic aluminoxane. Examples of the organic aluminoxane include methylaluminoxane and modified methylaluminoxane in which a part of the methyl group of methylaluminoxane is replaced with another alkyl group. Similarly, the organic boron compounds are various organic boron compounds that have been conventionally used as co-catalysts or the like in the polymerization of various olefins, and examples thereof include tetrakis(pentafluorophenyl)trityl borate, dimethylphenylammonium tetrakis(pentafluorophenyl)borate, and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.

[0050] (solvent) In this embodiment, the monomer represented by the general formula (2) is also used as a solvent. That is, the monomer represented by the general formula (2) also serves as a solvent. However, the solvent is not limited to being entirely the monomer represented by the general formula (2), and other solvents may be used as necessary, such as to dissolve other catalysts. Therefore, the amount of the monomer represented by the general formula (2) in the solvent is set to more than 50 mass%. The content of the monomer represented by formula (2) as the solvent is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, in the total solvent. If it is not necessary to use another solvent, the content of the monomer represented by formula (2) as the solvent is preferably 100% by mass.

[0051] Examples of the solvent other than the monomer represented by general formula (2) include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), benzene, toluene, and xylene, and halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloromethane, dichloroethane, and chlorobenzene.

[0052] (Other ingredients) In the charging step, other components may be charged, such as a chain transfer agent (hydrogen or an organometallic compound) for adjusting the molecular weight of the cyclic olefin (co)polymer.

[0053] [Polymerization process] In the polymerization step, the monomers in a polymerization vessel are polymerized in the presence of a catalyst. The temperature during polymerization is not particularly limited and can be, for example, 0 to 200° C. In view of a good yield of the cyclic olefin (co)polymer, the temperature during polymerization is preferably 20° C. or higher, more preferably 30° C. or higher, even more preferably 50° C. or higher, even more preferably 60° C. or higher, and particularly preferably 70° C. or higher. The temperature during polymerization may be 80° C. or higher, and can also be 85° C. or higher. The upper limit of the temperature during polymerization is not particularly limited, and the upper limit of the temperature during polymerization may be, for example, 190° C. or less, 180° C. or less, or 160° C. or less.

[0054] The polymerization time is not particularly limited, and the polymerization is carried out until a desired yield is reached or the molecular weight of the polymer increases to a desired level. The polymerization time varies depending on the temperature, the catalyst composition, and the monomer composition, but is typically 0.01 to 120 hours, preferably 0.1 to 80 hours, and more preferably 0.2 to 10 hours. The polymerization conditions are not particularly limited as long as a cyclic olefin (co)polymer having desired physical properties can be obtained, and known conditions can be used.

[0055] The cyclic olefin (co)polymer produced by the production method of the present embodiment corresponds to the cyclic olefin (co)polymer of the present embodiment described above. As described above, the cyclic olefin (co)polymer can be applied to various fields as a new material having both the properties of the cyclic olefin (co)polymer and the properties of the fluororesin. EXAMPLES

[0056] The present embodiment will be described in more detail below with reference to examples, but the present embodiment is not limited to the following examples.

[0057] Synthesis of Monomer (1) (Fluorinated Norbornene) First, monomers A and B having the structures shown below were synthesized as monomer (1) (fluorinated norbornene) used in the examples and comparative examples. (Synthesis of Monomer A) Monomer A was obtained by mixing 3,3,3-trifluoropentene and cyclopentadiene in a 1:1 ratio and stirring the mixture in an autoclave for 84 hours while heating at 135°C. (Synthesis of Monomer B) Cyclopentadiene and hexafluoropropene were mixed in a 1:1 ratio and stirred in an autoclave for 72 hours while heating at 220° C. to obtain Monomer B.

[0058] [ka]

[0059] [Examples 1 to 5, Comparative Examples 1 to 3] In each of the Examples and Comparative Examples, 2.2 mL of fluorinated norbornene was added as monomer (1) shown in Table 1 to a 30 mL glass eggplant flask that had been fully replaced with nitrogen under a nitrogen atmosphere. Then, ethylene was passed through the eggplant flask as monomer (2) to saturate it (however, in Example 5, this operation was not performed, and the next operation was performed successively). Then, the eggplant flask was heated to 90°C, and after it was confirmed that the temperature in the eggplant flask was sufficiently stabilized, catalyst (1) and catalyst (2) shown in Table 1 were added in the amounts shown in Table 1. After reacting for 60 minutes, 2-propanol was added to the eggplant flask to terminate the polymerization. In this manner, a cyclic olefin (co)polymer was obtained. Only Example 5 was a cyclic olefin homopolymer, and the others were cyclic olefin copolymers. In Examples 1 to 5, no solvent was added separately, and monomer (1) was used as the solvent. In Comparative Examples 1 to 3, toluene was used as the solvent.

[0060] Among the catalysts (1) used, the structures of the Ti catalyst and Ni catalyst are as follows: 2 (dba) 3 indicates tris(dibenzylideneacetone)dipalladium. Furthermore, MMAO-3A as catalyst (2) was prepared by dissolving 6.5 mass % (as the content of Al atoms) MMAO-3A in toluene ([(CH 3 ) 0.7 (iso-C 4 H 9 ) 0.3 AlO] n (manufactured by Tosoh Finechem Corporation, containing 6 mol % trimethylaluminum based on the total aluminum) [ka] [In the structural formula of the Ti catalyst, R 1 represents a tert-Bu group, R 2 indicates hydrogen.]

[0061] [Table 1]

[0062] Meanwhile, the yield relative to the amount of catalyst, the cyclic olefin content, and the glass transition temperature Tg of the cyclic olefin (co)polymers obtained in each of the Examples and Comparative Examples are shown in Table 2. The cyclic olefin content is the proportion of structural units derived from monomer A and / or monomer B, and the higher the content, the higher the proportion of fluorine.

[0063] [Table 2]

[0064] From Table 2, it can be seen that in Examples 1 to 5, the cyclic olefin content exceeded 40 mol% in all cases, and a fluorine-rich cyclic olefin (co)polymer was obtained. In contrast, in Comparative Examples 1 to 3, in which toluene was used as the solvent, the cyclic olefin content was 40 mol% or less in all cases, and a fluorine-rich cyclic olefin (co)polymer was not obtained. That is, it is presumed that the fluorinated norbornene content could be increased by using fluorinated norbornene (monomer represented by general formula (2)) as a solvent as well.

Claims

1. It contains a structural unit represented by the following general formula (1) and a structural unit derived from an α-olefin having 2 to 10 carbon atoms, A fluorine-containing cyclic olefin copolymer, wherein the content of the structural unit represented by the general formula (1) exceeds 40 mol % and the content of the structural unit derived from the α-olefin having 2 to 10 carbon atoms is in the range of 5 to 59 mol %. 【Chemistry 1】 [In general formula (1), R １ ~R ８ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group; R ９ ~R １２ each independently represents a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, an alkyl group having a fluorine atom, an alkoxy group having a fluorine atom, an ether bond-containing alkyl group having a fluorine atom, or —COOR １３ Or -OCOR １３ R represents a substituent represented by ９ ~R １２ containing at least one fluorine atom therein, and R ９ or R １０ And, R １１ or R １２ may form a ring together. R １３ is a substituted or unsubstituted alkyl group, or an alkyl group having a fluorine atom. Furthermore, m represents 0 or a positive integer, and when m is 2 or more, R ５ ~R ８ may be the same or different in each repeating unit. When m=0, R １ ~R ４ and R ９ ~R １２ At least one of is not a hydrogen atom.

2. The fluorine-containing cyclic olefin copolymer according to claim 1, which is amorphous.

3. 3. The fluorine-containing cyclic olefin copolymer according to claim 1, wherein a DSC curve obtained by measurement with a differential scanning calorimeter in a nitrogen atmosphere at a heating rate of 20°C / min according to the method described in JIS K7121 does not have a melting point peak in the range of 25 to 350°C.

4. A composition comprising the fluorine-containing cyclic olefin copolymer according to claim 1 or 2 and a monomer represented by the following general formula (2): 【Chemistry 2】 [In general formula (2), R 1 to R 12 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted or unsubstituted alkyl group, an alkyl group having a fluorine atom, an alkoxy group having a fluorine atom, an ether bond-containing alkyl group having a fluorine atom, or a substituent represented by —COOR 13 or —OCOR 13 , wherein R 1 to R 12 contain at least one fluorine atom, and R 9 or R 10 and R 11 or R 12 may be joined together to form a ring.] R 13 is a substituted or unsubstituted alkyl group, or an alkyl group having a fluorine atom. Furthermore, m represents 0 or a positive integer, and when m is 2 or greater, R 5 to R 8 may be the same or different in each repeating unit. When m=0, at least one of R 1 to R 4 and R 9 to R 12 is not a hydrogen atom.]

5. A film or coating comprising the fluorine-containing cyclic olefin copolymer of claim 1 or 2.

6. a charging step of charging at least a monomer represented by the following general formula (2) and a monomer containing an α-olefin having 2 to 10 carbon atoms, a catalyst, and a solvent into a polymerization vessel; a polymerization step of polymerizing the monomer in the polymerization vessel in the presence of the catalyst, In the charging step, the amount of the monomer represented by the general formula (2) charged is more than 40 mol %, the amount of the α-olefin having 2 to 10 carbon atoms charged is 0 mol % or more and less than 60 mol %, and the monomer represented by the general formula (2) is also used as a solvent, and the amount of the monomer represented by the general formula (2) charged in the solvent is more than 50 mass %. 【Transformation 3】 [In general formula (2), R １ ~R １２ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted or unsubstituted alkyl group, an alkyl group having a fluorine atom, an alkoxy group having a fluorine atom, an ether bond-containing alkyl group having a fluorine atom, or —COOR １３ Or -OCOR １３ R represents a substituent represented by １ ~R １２ containing at least one fluorine atom therein, and R ９ or R １０ And, R １１ or R １２ may form a ring together. R １３ is a substituted or unsubstituted alkyl group, or an alkyl group having a fluorine atom. Furthermore, m represents 0 or a positive integer, and when m is 2 or more, R ５ ~R ８ may be the same or different in each repeating unit. When m=0, R １ ~R ４ and R ９ ~R １２ At least one of is not a hydrogen atom.

7. 7. The method for producing a fluorine-containing cyclic olefin (co)polymer according to claim 6, wherein at least one of the catalysts is a catalyst containing a metal element of Group 10 of the periodic table or a catalyst containing a metal element of Group 4 of the periodic table.

8. 8. The method for producing a fluorine-containing cyclic olefin (co)polymer according to claim 7, wherein when at least one of the catalysts contains a metal element of Group 10 of the periodic table, the catalyst does not contain an aluminoxane.

9. 8. The method for producing a fluorine-containing cyclic olefin (co)polymer according to claim 7, wherein when at least one of the catalysts contains a metal element of Group 10 of the periodic table, the catalyst does not contain an organoboron compound.

Images