Fluorinated olefin copolymers

Abstract

The present invention is a copolymer having a structure represented by general formula (1) [In the formula, R1 represents a fluorine atom, or a C1-10 perfluoroalkyl group or perfluoroalkoxy group which may have-O-between carbon atoms; r2 and R3 are each independently a hydrogen atom, a halogen atom, an optionally substituted aliphatic hydrocarbon group having 1-30 carbon atoms, or an optionally substituted aryl group; r2 and R3 may be bonded to each other to form a ring; the aliphatic hydrocarbon group may contain, between carbon atoms, one or more elements selected from the group consisting of-O-,-Si (CH3) 2-,-CO-, and-NH-; x and y are positive numbers satisfying x + y = 1; and the black spot represents a bonding site]. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a novel copolymer using fluoroolefins and their derivatives as monomers and a method for preparing the copolymer.

[0002] This application claims priority based on Japanese Patent Application No. 2022-129402 filed in Japan on August 15, 2022, and Japanese Patent Application No. 2022-175052 filed in Japan on October 31, 2022, and the contents of which are incorporated herein by reference. Background Art

[0003] The electronegativity of fluorine atoms is high and similarly small as that of hydrogen atoms. Based on this characteristic, fluorine atoms can stably bond with many atoms, and organic compounds into which fluorine is introduced tend to have improved heat resistance, chemical resistance, light resistance, water resistance, etc. compared to before introduction. For example, by adding a monomer containing fluorine to the monomer raw material of the resin, various resistances such as heat resistance, chemical resistance, light resistance, water resistance, etc. can also be imparted to the resin.

[0004] Polytetrafluoroethylene (hereinafter, also referred to as PTFE) is used for various purposes due to its excellent properties. At this time, in order to improve the characteristics of PTFE resin and give new characteristics, it is known that there is a method for modifying PTFE using a monomer that can be copolymerized with tetrafluoroethylene (hereinafter, also referred to as TFE). For example, a modified PTFE micropowder formed by copolymerizing perfluoro (alkyl) ethylene and fluorine (alkyl vinyl ether) with TFE is disclosed in patent documentation 1. In addition, a copolymer obtained by adding a compound having an ethereal oxygen atom introduced between carbon atoms in perfluoro (alkyl) ethylene as a monomer together with perfluoro (alkyl) ethylene in order to improve the molding properties in paste extrusion molding is disclosed in patent documentation 2.

[0005] In the copolymer, the alternation of polymerization is an important index related to the uniformity and density of the functional group introduction, and the physical property of the polymer obtained is greatly affected. As the example of the alternating copolymerization of fluoroolefins and other monomers, for example, the example of the polymerization of simple olefins such as TFE and ethene (non-patent literature 1), TFE and propylene (non-patent literature 2) and vinyl ether (non-patent literature 3) is known. However, TFE hardly produces alternation with other monomers. Fluoroolefins except TFE also have the same trend, and in the alternating copolymerization using fluoroolefins, the selection of copolymerizable monomers has great restrictions.

[0006] It is known that [1.1.1] propellerane (hereinafter, sometimes simply referred to as "propellerane") is a structure with a large deformation potential and reacts with various anionic substances, free radical substances, and cationic substances.

[0007] The method for synthesizing unsubstituted propellerane is described in Non-Patent Document 4. In addition, the method for synthesizing substituted propellerane is described in Non-Patent Document 5, and the method for synthesizing propellerane having a methoxymethyl group as a substituent is described in Non-Patent Document 6.

[0008] According to non-patent document 7, Michl et al. synthesized a homopolymer of propellerane for the first time in 1988, which was a highly crystalline polymer with a thermal decomposition temperature of 290°C and insoluble in solvents. However, since it is insoluble in solvents, it is difficult to perform detailed polymer analysis. Therefore, in non-patent documents 8 to 10, as shown below, examples of improving solubility in solvents by introducing substituents into propellerane and performing polymerization are reported.

[0009]

[0010] Copolymerization of propane was also reported in 1990, and particular attention was paid to alternating copolymerization with electron-deficient monomers. For example, alternating copolymers as shown below were reported in Non-Patent Documents 11 to 13.

[0011]

[0012] Prior art literature

[0013] Patent Literature

[0014] Patent Document 1: Japanese Patent Publication No. 11-509245

[0015] Patent Document 2: International Publication No. 2018 / 221518

[0016] Non-patent literature

[0017] Non-patent literature 1: Naberezhnykh, et al., Bulletin of the Academy of Sciences of the USSR. Division of Chemical Science, 1974, vol. 23 (1), p. 227-228.

[0018] Non-patent document 2: Kostov, et al., Journal of Polymer Science Part A: Polymer Chemistry, 1992, vol. 30 (6), p. 1083-1088.

[0019] Non-patent document 3: Hikita, et al., Journal of Polymer Science Part A-1: ​​Polymer Chemistry Edition, 1972, vol. 10 (10), p. 2941-2949.

[0020] Non-patent document 4: Mondanaro and Dailey, Organic Syntheses, Collective volume, 2004, vol. 10, p. 658.

[0021] Non-patent document 5: Werner et al., Liebigs Annalen, 1996, vol. 11, p, 1705-1715.

[0022] Non-patent document 6: Klopsch and Schlueter, Tetrahedron, 1995, vol. 51 (38), p. 10491-10496.

[0023] Non-patent document 7: Kaszynski and Michl, Journal of the American Chemical Society, 1988, vol. 110 (15), p. 5225-5226.

[0024] Non-patent literature 8: Opitz and Schlueter, Angewandte Chemie International Edition English, 1989, vol. 28 (4), p. 456-458.

[0025] Non-patent literature 9: Freudenberger et al., The Journal of Organic Chemistry, 1993, vol. 58 (23), p. 6497-6498.

[0026] Non-patent document 10: Lassale et al., Acta Polymerica, 1994, vol. 45(5), p. 389-391.

[0027] Non-patent document 11: Gosau and Schlueter, Chemische Berichte, 1990, vol. 123 (12), p. 2449-2451.

[0028] Non-patent document 12: Reddy et al., Macromolecules 1991, vol. 24 (13), p. 3973-3974.

[0029] Non-patent document 13: Gosau, et al., Polymer Bulletin, 1991, vol. 25(3), p. 293-297.

[0030] Non-patent document 14: Fox and Zisman, Journal of Colloid Science. 1950, vol. 5(6), p. 514-531.

[0031] Non-patent literature 15: Matsunaga, et al., Angewandte Chemie International Edition, 2021, vol. 60(5), p. 2578-2582. Summary of the invention

[0032] The object of the present invention is to provide a novel copolymer using fluoroolefins and their derivatives as monomers and a method for preparing the copolymer.

[0033] The present inventors have found that a novel copolymer with high copolymerization alternation can be obtained by using a fluoroolefin as an electron-deficient monomer to be copolymerized with a propane, thereby completing the present invention.

[0034] That is, the present invention is as follows.

[0035] [1] A fluoroolefin copolymer having a structure represented by the following general formula (1):

[0036]

[0037] [Where R 1 is a fluorine atom, a perfluoroalkyl group having 1 to 10 carbon atoms which may have -O- between carbon atoms, or a perfluoroalkoxy group having 1 to 10 carbon atoms which may have -O- between carbon atoms; R 2 and R 3 Each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or an aryl group which may have a substituent; 2 and R 3 can bond to each other to form a ring; the above-mentioned aliphatic hydrocarbon group can contain one or more selected from -O-, -Si(CH3)2-, -CO- and -NH- between carbon atoms; x and y represent the proportion of each monomer (x+y=100(%), x and y are in the range of 10≤x, y≤90 respectively); black dots represent bonding sites].

[0038] [2] The fluoroolefin copolymer according to [1] above, wherein the R 2 and R 3 All are hydrogen atoms.

[0039] [3] The fluoroolefin copolymer according to [1] or [2], wherein R 1 It is a fluorine atom or a perfluoroalkoxy group having 1 to 10 carbon atoms and having -O- between carbon atoms.

[0040] [4] A method for producing a fluoroolefin copolymer, comprising subjecting a compound represented by the following general formula (2) and a compound represented by the following general formula (3) to free radical polymerization to produce a fluoroolefin copolymer having a structure represented by the following general formula (1),

[0041]

[0042] [Where R 1 is a fluorine atom, a perfluoroalkyl group having 1 to 10 carbon atoms which may have -O- between carbon atoms, or a perfluoroalkoxy group having 1 to 10 carbon atoms which may have -O- between carbon atoms]

[0043]

[0044] [Where R 2 and R 3 Each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or an aryl group which may have a substituent; 2 and R 3 can be bonded to each other to form a ring; the above-mentioned aliphatic hydrocarbon group can contain one or more selected from -O-, -Si(CH3)2-, -CO- and -NH- between carbon atoms]

[0045]

[0046] [Where R 1 , R 2 and R 3 Same as above; x and y represent the proportion of each monomer (x+y=100(%), x and y are in the range of 10≤x, y≤90 respectively); black dots represent bonding sites].

[0047] [5] The method for producing a fluoroolefin copolymer according to [4] above, wherein the radical polymerization is carried out at -30°C or lower.

[0048] According to the present invention, a novel copolymer using fluoroolefin and its derivatives as monomers can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 The copolymer 2 obtained in Example 2 is shown in 13 C NMR (100 MHz, CDCL3) spectral data.

[0050] Figure 2 This is a graph showing the results of thermogravimetric measurement of each polymer synthesized in Comparative Example 1, Example 1, Example 2, and Example 3.

[0051] Figure 3 The copolymer 3 synthesized in Example 3 and the polymer 2 synthesized in Comparative Example 2 are shown in FIG. 19 Figure 1 shows the spectral data of F NMR (376 MHz, CDCL3).

[0052] Figure 4 The graph is a graph of the resin film of copolymer 3 in Example 3, with the cosine (cos) value of the contact angle measured for each hydrocarbon solvent as the vertical axis and the literature value of the surface tension (γL) (dyn / cm) of the hydrocarbon solvent as the horizontal axis.

[0053] Figure 5 This is a graph in which the vapor pressure at each concentration of Fomblin 4000 (for calibration) (A) and Copolymer 3 (B) was measured in Example 3, and the measurement data were plotted with each concentration as the horizontal axis and the [vapor pressure] / [concentration] value at each concentration as the vertical axis.

[0054] Figure 6 The graphs show the XPS spectrum of fluorine (A), the XPS spectrum of carbon (B), and the XPS spectrum of oxygen (C) of the thin film of copolymer 3 in Example 3.

[0055] Figure 7 This is a graph showing the results of thermogravimetric measurement of each polymer synthesized in Comparative Example 1, Example 3, and Example 4.

[0056] Figure 8 This is a diagram showing the results of powder X-ray measurement of each polymer synthesized in Comparative Example 1, Example 1, Example 3, and Example 4.

[0057] Fig. 9 This is a graph showing the results of contact angle measurement of copolymer 4 synthesized in Example 4.

[0058] Fig.10 This is a graph showing the results of UV-VIS measurement of the copolymer synthesized in Example 3. DETAILED DESCRIPTION

[0059] In the present invention and the specification of this application, "unit based on monomer" refers to the general term for the atomic group directly formed by the polymerization of one molecule of monomer and the atomic group obtained by chemically converting a part of the atomic group. The unit based on monomer is also referred to as unit. Relative to all the units contained in the polymer, the content (mass %) of each unit is obtained by analyzing the polymer using solid nuclear magnetic resonance spectroscopy (NMR) and can be estimated based on the feed amount of each monomer. Usually, the content of each unit calculated based on the feed amount of each monomer is roughly consistent with the actual content of each unit.

[0060] In the present invention and the specification of this application, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as a lower limit and an upper limit.

[0061] In the present invention and the specification of this application, “C p1－p2 "(p1 and p2 are positive integers satisfying p1<p2) means a group having carbon atoms ranging from p1 to p2.

[0062] In the present invention and the specification of this application, "a group which may have a substituent" includes both a group which has no substituent and a group which has a substituent.

[0063] In the following, "compound (n)" means a compound represented by formula (n).

[0064] In the present invention and the specification of this application, “C 1－30 The term "aliphatic hydrocarbon group" includes a C 1－30 Alkyl, optionally substituted C 2－30 Alkenyl, optionally substituted C 2－30 All of the alkynyl groups. 1－30 The "aliphatic hydrocarbon group" may be a straight chain, a branched chain, or a cyclic group.

[0065] In the present invention and the specification of this application, "C p1－p2 Aliphatic hydrocarbon group is bonded to C p1－p2 A group in which one or more, preferably one to three, hydrogen atoms on carbon atoms of an aliphatic hydrocarbon group are substituted with other functional groups. When there are two or more substituents, the substituents may be of the same type or different types.

[0066] In the present invention and the specification of this application, “C 1－30 "Alkyl" refers to an alkyl group having 1 to 30 carbon atoms, which may be a linear or branched chain, or may include a cyclic structure. 1－30Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0067] In the present invention and the specification of this application, “C 1－10 The term "alkyl" refers to an alkyl group having 1 to 10 carbon atoms, and may be a linear or branched group, or may include a cyclic structure. 2－10 "Alkyl" refers to an alkyl group having 2 to 10 carbon atoms, which may be a straight chain or a branched chain. 1－10 Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

[0068] In the present invention and the specification of this application, “C 1－6 "Alkyl" refers to an alkyl group having 1 to 6 carbon atoms, which may be a straight chain or a branched chain, or may include a cyclic structure. 1－6 Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0069] In the present invention and the specification of this application, "C p1－p2 Alkyl is bonded to C p1－p2 A group in which one or more, preferably one to three, hydrogen atoms on carbon atoms of an alkyl group are substituted with other functional groups. When there are two or more substituents, the substituents may be of the same type or different types.

[0070] As C 2－30 Examples of alkenyl groups include 2－30 A group in which at least one of the groups listed in the alkyl group has a double bond between carbon atoms. 2－30 Examples of the alkenyl group include ethenyl, propenyl, 2-propenyl, butenyl, 1-methylpropenyl, 2-methylpropenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl.

[0071] In the present invention and the specification of this application, "C p1－p2 Alkenyl is bonded to C p1－p2 A group in which one or more, preferably one to three, hydrogen atoms on carbon atoms of the alkenyl group are substituted with other functional groups. When there are two or more substituents, the substituents may be of the same type or different types.

[0072] As C 2－30 Examples of alkynyl groups include 2－30 A group in which at least one of the groups listed in the alkyl group has a triple bond between carbon atoms. 2－30 Examples of the alkynyl group include ethynyl, propynyl, butynyl, pentynyl, heptynyl, octynyl, nonynyl and decynyl.

[0073] In the present invention and the specification of this application, "C p1－p2 Alkynyl is a group bonded to C p1－p2 A group in which one or more, preferably one to three, hydrogen atoms on carbon atoms of the alkynyl group are substituted with other functional groups. When there are two or more substituents, the substituents may be of the same type or different types.

[0074] In the present invention and the present application, the "aryl group" is a cyclic group having aromaticity, and is a group in which the ring consists only of carbon atoms.

[0075] In the present invention and the specification of this application, “C 6－14 "Aryl" is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and is particularly preferably C 6－12 Aryl. As C 6－14 Examples of the aryl group include phenyl, naphthyl, anthracenyl, 9-fluorenyl and the like, and phenyl is particularly preferred.

[0076] In the present invention and the specification of this application, "aryl group having a substituent" means a group in which one or more, preferably one to three, hydrogen atoms bonded to the carbon atoms of the aryl group are substituted with other functional groups. When there are two or more substituents, the substituents may be of the same type or different types. Examples of such substituents include C 1－6 Alkyl, C s－6 Alkenyl, C 1－6 Alkoxy, C 1－6 an alkylthio group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an aldehyde group, a C 1－10 Acyl, optionally substituted C 6－14 Aryl, etc. As "C 6－14Examples of the “aryl group” include phenyl, naphthyl, anthracenyl, 2-methylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2-trifluoromethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 3,5-dimethoxyphenyl, 2-methylthiophenyl, 4-methylthiophenyl, 2,4-dimethylthiophenyl, 3,5-dimethylthiophenyl, 4-chlorophenyl and 4-bromophenyl.

[0077] The fluoroolefin copolymer of the present invention is a copolymer produced using a fluoroolefin compound represented by the following general formula (2) and a propane compound represented by the following general formula (3) as monomers, and has a structure represented by the following general formula (1). In the general formula (1), black dots represent bonding sites.

[0078]

[0079] In the general formulas (1) and (2), R 1 There can be a fluorine atom and a -O- carbon atom between carbon atoms. 1－10 Perfluoroalkyl, or C 1－10 Perfluoroalkoxy. Among these groups, C 1－10 Perfluoroalkyl and C 1－10 The perfluoroalkoxy group may be linear or branched.

[0080] In the general formulas (1) and (2), R 1 There is no -O- between carbon atoms. 1－10 When perfluoroalkyl, as R 1 , preferably C 1－6 Perfluoroalkyl, more preferably C 2－6 Perfluoroalkyl, more preferably C 2－4 The perfluoroalkyl group is more preferably a perfluoroethyl group, a perfluoro-n-propyl group, a perfluoro-isopropyl group, a perfluoro-n-butyl group, a perfluoro-n-butyl group, a perfluoro-isobutyl group, or a perfluoro-tert-butyl group.

[0081] In the general formulas (1) and (2), R 1 There is no -O- between carbon atoms. 1－10 In the case of perfluoroalkoxy, as R 1 , preferably C 1－6 Perfluoroalkoxy, more preferably C 2－6 Perfluoroalkoxy, more preferably C 2－4 The perfluoroalkoxy group is more preferably a perfluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-isopropoxy group, a perfluoro-n-butoxy group, a perfluoro-n-butoxy group, a perfluoro-isobutoxy group, or a perfluoro-tert-butoxy group.

[0082] In the general formulas (1) and (2), R 1C with -O- between carbon atoms 1－10 Perfluoroalkyl or C with -O- between carbon atoms 2－10 In the case of a perfluoroalkoxy group, the group is preferably -(O) e -(C a F 2a )-(O-C b F 2b ) c -C d F 2d+1 (a, b and d are integers greater than 1, c is an integer greater than 0, a+b×c+d≤10 is satisfied, and e is 0 or 1). When c is 0, -(O-C b F 2b ) c - represents a single bond. When e is 0, the group is a perfluoroalkyl group (-(C a F 2a )-(O-C b F 2b ) c -C d F 2d+1 ), when e is 1, the group is a perfluoroalkoxy group (-O-(C a F 2a )-(O-C b F 2b ) c -C d F 2d+1 ).

[0083] In - (O) e -(C a F 2a )-(O-C b F 2b ) c -C d F 2d+1 In, -(C a F 2a )- is a linear perfluoroalkylene group or a branched perfluoroalkylene group. b F 2b - may be a linear perfluoroalkylene group or a branched perfluoroalkylene group. -C d F 2d+1 The perfluoroalkyl group may be a linear perfluoroalkyl group or a branched perfluoroalkyl group.

[0084] As - (O) e -(C a F 2a )-(O-C b F 2b ) c -C d F2d+1 , a is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and further preferably 2 or 3. b is preferably an integer of 1 to 4, more preferably 1 or 2. c is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. d is preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and further preferably an integer of 1 to 3.

[0085] In the general formulas (1) and (2), R 1 , preferably in -(O) e -(C a F 2a )-(O-C b F 2b ) c -C d F 2d+1 wherein c is 0 and the combination of a, d and e (a, d, e) is (2,2,0), (2,3,0), (2,4,0), (2,5,0), (2,6,0), (3,2,0), (3,3,0), (3,4,0), (3,5,0), (3,6,0), (4,2,0), (4,3,0), (4,4,0), (2,2,1), (2,3,1), (2,4,1), (2,5,1), (2,6,1), (3,2,1), (3,3,1), (3,4,1), (3,5,1), (3,6,1), (4,2,1), (4,3,1), or (4,4,1).

[0086] In the general formulas (1) and (2), R 1 , preferably in -(O) e -(C a F 2a )-(O-C b F 2b ) c -C d F 2d+1wherein c is greater than or equal to 1 and the combination of a, b, c, d and e (a, b, c, d, e) is (2,1,1,1,0), (2,1,1,2,0), (2,1,1,3,0), (2,1,1,4,0), (2,1,2,1,0), (2,1,2,2,0), (2,1,2,3,0), (2,1,2,4,0), (2,1,3,1,0), (2,1,3,2,0), (2,1,3,3,0), (2,1,3,4,0), (2,1,4,1,0), (2,1,4,2,0), (2,1,4,3,0), (2,1,4,4,0), (2,2,1,1,0), (2,2,1,2,0), (2, ,0), (2,2,1,4,0), (2,2,2,1,0), (2,2,2,2,0), (2,2,2,3,0), (2,2,2,4,0), (2,2,3,1,0), (2,2,3,2,0), (3,1,1,1,0), (3,1,1,2,0), (3,1,1,3,0), (3,1,1,4,0), (3,1,2,1,0), (3,1,2,2,0), (3,1,2,3,0), (3,1,2,4,0), (3,1,3,1,0), (3,1,3,2,0), (3,1,3,3,0), (3,1,3,4,0), (3,2,1,1,0), ( 3,2,1,2,0), (3,2,1,3,0), (3,2,1,4,0), (3,2,2,1,0), (3,2,2,2,0), (3,2,2,3,0), (3,2,3,1,0), (3,3,1,1,0), (3,3,2,1,0), (2,1,1,1,1), (2,1,1,2,1), (2,1,1,3,1), (2,1,1,4,1), (2,1,2,1,1), (2,1,2,2,1), (2,1,2,3,1), (2,1,2,4,1), (2,1,3,1,1), (2,1,3,2,1), (2,1,3,3,1), (2,1,3,4,1) ,(2,1,4,1,1),(2,1,4,2,1),(2,1,4,3,1),(2,1,4,4,1),(2,2,1,1,1),(2,2,1,2,1),(2,2,1,3,1),(2,2,1,4,1),(2,2,2,1,1),(2,2,2,3,1),(2,2,2,4,1),(2,2,3,1,1),(2,2,3,2,1),(3,1,1,1,1),(3,1,1,2,1),(3,1,1,3,1),(3,1,1,4,1),(3,1,2,1,1),(3,1,2,2,1),(3,1,2,3,1), (3,1,2,4,1), (3,1,3,1,1), (3,1,3,2,1), (3,1,3,3,1), (3,1,3,4,1), (3,2,1,1,1), (3,2,1,2,1), (3,2,1,3,1), (3,2,1,4,1), (3,2,2,1,1), (3,2,2,2,1), (3,2,2,3,1), (3,2,3,1,1), (3,3,1,1,1), or (3,3,2,1,1).

[0087] In the general formulas (1) and (3), R 2 and R 3 are each independently a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), a C 1－30 an aliphatic hydrocarbon group, or an aryl group which may have a substituent. 1－30 The aliphatic hydrocarbon group may be a straight chain, a branched chain, or a cyclic group. 1－30 The aliphatic hydrocarbon group may contain one or more connecting groups selected from -O-, -Si(CH3)2-, -CO- and -NH- between carbon atoms. When two or more of these connecting groups are included, the multiple connecting groups may be adjacent to each other. However, the case where two or more -O- are connected is not included.

[0088] R 2 and R 3 is a C which may have a substituent 1－30 In the case of an aliphatic hydrocarbon group, the C 1－30 Aliphatic hydrocarbon group, which can be C 1－30 Alkyl, can also be C 2－30 Alkenyl, can also be C 2－30 Alkynyl. As R in the general formula (1) and (3) 2 or R 3 , preferably C which may have a substituent 1－10 Alkyl, optionally substituted C 2－10 an alkenyl group, or a C 2－10 Alkynyl, more preferably C 1－10 Alkyl or optionally substituted C 2－10 Alkenyl, preferably C 1－10 Alkyl, more preferably unsubstituted C 1－10 Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), a hydroxyl group, and a phenyl group which may have a substituent.

[0089] The R 2 and R3 The ring is preferably a three- to eight-membered aliphatic cyclic hydrocarbon group, and more preferably a three- to six-membered aliphatic cyclic hydrocarbon group. 2 and R 3 Specific examples of the ring formed by connecting the two groups include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, and cyclooctene.

[0090] R 2 and R 3 In the case of an aryl group which may have a substituent, the aryl group is preferably a phenyl group which may have a substituent, and more preferably a phenyl group which does not have a substituent.

[0091] Examples of the compound represented by the general formula (3) include [1.1.1] propane (CAS No.: 35634-10-7), 2-methyltricyclo[1.1.1.0]pentane (CAS No.: 1398116-41-0), 2-chlorotricyclo[1.1.1.0]pentane (CAS No.: 120158-94-3), 2-fluorotricyclo[1.1.1.0]pentane (CAS No.: 120158-93-2), 2-ethyltricyclo[1.1.1.0]pentane (CAS No.: 185320-63-2), 2-propyltricyclo[1.1.1.0]pentane (CAS No.: 185320-64-3), tricyclo[1.1.1.0]pentanemethanol (CAS No.: 120158-93-2). No.:171856-83-0)、spiro[cyclopropane-1,2'-tricyclo[1.1.1.0]pentane](CAS No.:208392-00-1)、2-(1-methylpropyl)tricyclo[1.1.1.0]pentane(CAS No.:185320-72-3)、2-(2-methylpropyl)tricyclo[1.1.1.0]pentane(CAS No.:185320-65-4)、2-(2,2-difluoro)tricyclo[1.1.1.0]pentane(CAS No.:210572-24-0)、2-(2,2-dichloro)tricyclo[1.1.1.0]pentane(CAS No.:143104-79-4)、2-(2,2-diethyl)tricyclo[1.1.1.0]pentane(CAS No.: 185320-71-2), spiro[cyclobutane-1,2'-tricyclo[1.1.1.0]pentane](CAS No.: 185320-70-1), 2-(1-propenyl)tricyclo[1.1.1.0]pentane(CAS No.: 189825-10-3), spiro[cyclopentane-1,2'-tricyclo[1.1.1.0]pentane](CAS No.: 189825-08-9), spiro[2-cyclopropene-1,2'-tricyclo[1.1.1.0]pentane](CAS No.: 208392-01-2), 2-pentyltricyclo[1.1.1.0]pentane(CAS No.: 119298-85-0), 2-phenyltricyclo[1.1.1.0]pentane(CAS No.:189825-04-5)、2-(2-methylbutyl)tricyclo[1.1.1.0]pentane(CAS No.:185320-66-5)、2-heptyltricyclo[1.1.1.0]pentane(CAS No.:131042-19-8)、spiro[cyclohexane-1,2'-tricyclo[1.1.1.0]pentane(CAS No.:190127-80-1)、2-(2-methylpentyl)tricyclo[1.1.1.0]pentane(CAS No.: 185320-67-6), 2-(2,2-bis(1-methylethyl))tricyclo[1.1.1.0]pentane(CAS No.: 189825-07-8), 2-(3,3-dimethyl-1-butynyl)tricyclo[1.1.1.0]pentane(CAS No.: 189825-13-6), 2-phenylmethyltricyclo[1.1.1.0]pentane(CAS No.: 185320-68-7), 2-(3-methoxypropyl)tricyclo[1.1.1.0]pentane(CAS No.: 137168-28-6), 2-(3-methoxypropyl)tricyclo[1.1.1.0]pentane(CAS No.: 131042-21-2), 2-undecyltricyclo[1.1.1.0]pentane(CAS No.: 131042-20-1), spiro[2-cyclopropene-1,2'-tricyclo[1.1.1.0]pentane(CAS No.: 208392-08-9), 2-(2-methyl-2-phenyl)tricyclo[1.1.1.0]pentane(CAS No.: 189825-06-7), spiro[2-cyclohexene-1,2'-tricyclo[1.1.1.0]pentane](CAS No.: 189825-12-5), 2-(5-methoxypentyl)tricyclo[1.1.1.0]pentane(CAS No.: 131042-22-3), 2-(2-methyl-2-(2-methyl-1-propenyl)tricyclo[1.1.1.0]pentane(CAS No.:189825-11-4)、2-(2-phenylethyl)tricyclo[1.1.1.0]pentane(CAS No.:185320-69-8)、2-[(methoxymethoxy)methyl]tricyclo[1.1.1.0]pentane(CAS No.:171856-79-4)、2-[(methoxymethoxy)ethyl]tricyclo[1.1.1.0]pentane(CAS No.:150622-55-2)、2-(hexamethyl)tricyclo[1.1.1.0]pentane(CAS No.:189825-06-7)、2-(4-methoxyphenyl)tricyclo[1.1.1.0]pentane(CAS No.: 189825-05-6), tricyclo[1.1.1.0]pentane methanol acetate (CAS No.: 171856-81-8), 2-[(4-methoxyphenyl)methyl]tricyclo[1.1.1.0]pentane (CAS No.: 2411144-19-7), 2,2,3,3-tetramethyl-spiro[cyclobutane-1,2'-tricyclo[1.1.1.0]pentane] (CAS No.: 189825-09-0), hexafluoro-tricyclo[1.1.1.0]pentane (CAS No.: 105153-37-5), (1,1-dimethylethyl)dimethyl(tricyclo[1.1.1.0]pentylmethoxy)silane (CAS No.: 171856-80-7), 2,4,5,5-tetrafluoro-tricyclo[1.1.1.0]pentane-2,4-dicarbonyl difluoride (CAS No.: 172897-80-2), carbamic acid (phenylmethyl) tricyclo[1.1.1.0]pentyl methyl ester (CAS No.: 171856-82-9), 2,4,5,5-tetrafluoro-tricyclo[1.1.1.0]pentane-2,4-dicarboxylic acid bis(trifluoromethyl) ester (CAS No.: 172897-78-8), dispiro[2-cyclopropene-1,2'-tricyclo[1.1.1.0]pentane-4',1"-[2]cyclopropene] (CAS No.: 208392-04-5), dispiro[2-cyclopropane-1,2'-tricyclo[1.1.1.0]pentane-4',1"-[2]cyclopropene](CAS No.: 208392-03-4), dispiro[cyclopropane-1,2'-tricyclo[1.1.1.0]pentane-4',1"-cyclopropane](CAS No.: 208392-02-3), tricyclo[1.1.1.0]pentane-2,4-dicarboxylic acid dimethyl ester(CAS No.: 172897-79-9), etc.

[0092] In the general formula (1), x and y represent the ratio of each monomer. x represents the content (mol %) of the polymerized units derived from the fluoroolefin compound represented by the general formula (2) relative to all the units contained in the polymer. y represents the content (mol %) of the polymerized units derived from the propellerane compound represented by the general formula (3) relative to all the units contained in the polymer. x+y=100(%), x and y are in the range of 10≤x, y≤90, respectively. As x, it is preferably 20 or more, more preferably 30 or more, and further preferably 40 to 60.

[0093] The fluoroolefin copolymer of the present invention may contain other polymerized units in addition to the polymerized units derived from the fluoroolefin compound represented by the general formula (2) and the polymerized units derived from the propellerane compound represented by the general formula (3). The fluoroolefin copolymer of the present invention preferably contains 1 mol% or more, more preferably 10 mol% or more, further preferably 25 mol% or more, and further preferably 50 mol% or more of the total content (mol%) of the polymerized units derived from the fluoroolefin compound represented by the general formula (2) and the polymerized units derived from the propellerane compound represented by the general formula (3) relative to all the units contained in the polymer.

[0094] The fluoroolefin copolymer having a structure represented by the general formula (1) is produced by radical polymerization of a fluoroolefin compound represented by the general formula (2) and a propane compound represented by the general formula (3). When the fluoroolefin copolymer contains other polymers, monomers of the other polymer units are added as raw materials.

[0095] The free radical polymerization for synthesizing the fluoroolefin copolymer of the present invention is carried out by adding a photopolymerization initiator as needed to a solvent in which the monomer compound as a raw material is dissolved and irradiating with ultraviolet rays. In addition, the monomer compound itself can be used as a solvent and polymerization (bulk polymerization) can be carried out without using a solvent. The wavelength of the ultraviolet light only needs to be 200 to 400 nm, preferably 300 to 350 nm. The polymerization temperature during the free radical polymerization can be appropriately determined in consideration of the type of monomer used, etc. From the perspective of the stability of the propeller alkane compound represented by the general formula (3) and the better reaction efficiency, it is preferably below 0°C, preferably below -30°C.

[0096] As the solvent used in the free radical polymerization, any solvent that can dissolve the monomer compound used in the raw material and is inactive to the reaction can be appropriately selected from the known solvents used in the chemical reaction. As the solvent, for example, hydrocarbon solvents, ethers, esters, ketones, nitriles, amides, halogenated hydrocarbon compounds, etc. can be cited. As hydrocarbon solvents, for example, pentane, hexane, heptane, benzene, toluene, xylene, etc. can be cited. As ethers, diethyl ether, dibutyl ether, tert-butyl methyl ether (MTBE), cyclopentyl methyl ether (CPME), dimethoxyethane (DME), diethylene glycol dimethyl ether (Diglyme), etc. can be cited. As ketones, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), etc. can be cited. As nitriles, acetonitrile, propionitrile, ethanedinitrile, benzonitrile, etc. can be cited. As amides, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP) and the like can be cited. In addition, fluorinated solvents such as hexafluorobenzene, CFE-419 (ClCF2CFClCF2OCF2CF2Cl), and HFC-365mfc (CAS No.: 406-58-6) can also be used. As solvents, one solvent can be used, or a mixed solvent of two or more solvents can be used. As polymerization solvents, hydrocarbon solvents and ethers are more suitable.

[0097] As the photopolymerization initiator used in the synthesis of the fluoroolefin copolymer of the present invention, it is possible to appropriately select and use it from the known photopolymerization initiators used for free radical polymerization. In the synthesis of the fluoroolefin copolymer of the present invention, for example, an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, etc. can be used, and an alkylphenone-based photopolymerization initiator is preferably used. Among them, an alkylphenone-based photopolymerization initiator having absorption at a wavelength of 230 to 350 nm is particularly preferred. Examples of the alkylphenone-based photopolymerization initiator include 2-hydroxy-2-methyl-1-phenyl-1-propanone (CAS No.: 7473-98-5) (DC (Irgacure) -1173), 2,2-dimethoxy-2-phenylacetophenone (CAS No.: 24650-42-8) (Irgacure -651), 1-hydroxycyclohexyl-phenyl ketone (CAS No.: 947-19-3) (Irgacure -184), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxymethylacetone (CAS No.: 106797-53-9) (Irgacure -2959), 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropane-1-one (CAS No.: 474510-57-1) (Irgacure-127), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one (CAS No.: 71868-10-5) (Irgacure-907), 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (CAS No.: 119313-12-1) (Irgacure-369), 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane-1-one (CAS No.: 119344-86-4) (Irgacure-379EG), etc.

[0098] The fluoroolefin copolymer of the present invention is a fluorine-containing polymer having a cyclic structure alternately with a fluoroolefin monomer in the main chain. Generally, it is known that a fluorine-containing polymer having a cyclic structure is amorphous because the molecular chain is difficult to arrange, and therefore exhibits high transparency while maintaining the characteristic chemical resistance, light resistance, and water resistance of the fluorine-containing polymer. In fact, the fluoroolefin copolymer of the present invention can also be formed into a transparent film, and by being an alternating copolymer of propane and fluoroolefin, the characteristics of the fluorine-containing polymer are maintained, and it is expected to be applied to, for example, optical materials with high chemical resistance, light resistance, and water resistance.

[0099] Example

[0100] Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples.

[0101] In addition, unless otherwise specified, the unit of the yield (%) described in the Examples is mol %.

[0102] <Analysis equipment>

[0103] Among the NMR used in the analysis of the examples, solid state NMR ( 13 For C NMR, “JNM-ECA500 (500 MHz)” manufactured by JEOL Ltd. was used.

[0104] The combustion ion chromatography was performed using an analysis system including a combustion ion chromatograph analyzer (manufactured by Yanaco Kikai Kōkai) consisting of a sample introduction device (THA-24), a combustion furnace (SQ-10), an absorption unit (HSU-35), and an ion chromatograph (ic-2010).

[0105] In the NMR used for analysis in the Examples, etc., 19 F NMR and 1 H NMR was measured using JNM-ECS400 (400 MHz) manufactured by JEOL Ltd. The reference values ​​were set as follows: 1 In H NMR, tetramethylsilane was set to 0 PPM. 19 In F NMR, C6F6 is set to -162 PPM.

[0106] As a thermogravimetric-differential thermal analyzer (TG-DTA), "EXSTAR6000" manufactured by Seiko Instruments was used.

[0107] A high-sensitivity differential scanning calorimeter (DSC) “DSC7020” manufactured by Seiko Instruments was used.

[0108] Gel permeation chromatography (GPC) was measured using "Viscoteck TDA305" manufactured by Malvern.

[0109] The contact angle was measured using a contact angle meter "DMs-401" manufactured by Kyowa Interface Science Co., Ltd.

[0110] [Production Example 1]

[0111] The propellerane used in the following experiments was synthesized according to the method described in Non-Patent Document 4.

[0112]

[0113] The synthesized propellerane was purified by low-temperature vacuum distillation and obtained as a solution in a diethyl ether / pentane mixed solvent. The boiling point of propellerane is 70°C. Hexafluoro-p-xylene was added as an internal standard and the mixture was purified by 1The propellerane solution was quantitatively measured by H NMR to determine the concentration of the propellerane solution. The propellerane solution was used for polymerization in the form of a diethyl ether / pentane mixed solvent.

[0114] [Production Example 2]

[0115] The MOM-propellerane used in the following experiments was synthesized according to the method described in Non-Patent Document 6.

[0116]

[0117] [Comparative Example 1]

[0118] Polymer 1 was synthesized by homopolymerization of propane.

[0119]

[0120] A stirring bar was placed in a Schlenk bottle with a capacity of 30 mL, and the stopper was covered and nitrogen was replaced three times. Then, 5 mL of the diethyl ether / pentane solution (0.17 M) of the propellerane synthesized in Preparation Example 1 and 0.1 equivalent of DC-1173 as a photoinitiator were added by syringe, and the copolymerization was carried out at -70°C for 2 hours by ultraviolet irradiation (xenon lamp 300 W wavelength 250-500 nm). Then, the reaction solution was reprecipitated with methanol, and the supernatant was removed by decantation, and then the polymer 1 (81 mg) insoluble in the solvent was obtained as a white solid by evaporation and vacuum drying.

[0121] solid 13 C NMR (125MHz): δ = 38.2, 48.8ppm

[0122] IR: 3050-2850 (C-H expansion)

[0123] [Example 1]

[0124] Synthesize the copolymer of propane and tetrafluoroethylene (TFE) 1.

[0125]

[0126] A stirring bar was placed in a Schlenk flask with a capacity of 30 mL, and after nitrogen substitution was performed three times with the stopper, a diethyl ether / pentane solution (0.82 M, 1.2 mL) of propane synthesized in Preparation Example 1 and DC-1173 (15.2 μL, 0.1 equivalent) as a photoinitiator were added to the Schlenk flask using a syringe. The reaction system was freeze-degassed with liquid nitrogen, heated to -70°C under a TFE atmosphere at normal pressure, and irradiated with ultraviolet light for 3 hours and 30 minutes to carry out copolymerization. Then, nitrogen was circulated at -70°C to drive TFE out of the system, thereby stopping the reaction. Methanol was added to the reaction solution to precipitate the polymer, and the copolymer was separated by filtration using a Kiriyama funnel. The obtained solid was dried at 40°C for more than 1 hour using a vacuum dryer to obtain a copolymer 1 (79 mg) as a white solid that was poorly soluble in an organic solvent. The content of fluorine atoms was quantified by combustion ion chromatography, and the TFE content was calculated. As a result, the TFE content was 41.9 mol%.

[0127] solid 13 C NMR (125MHz): δ = 19.1, 31.7, 37.2, 38.2, 48.8, 115.2ppm IR: 3050-2850 (C-H stretching), 1250-1000 (C-F stretching) cm -1

[0128] [Example 2]

[0129] The copolymer 2 of MOM-propellerane and tetrafluoroethylene (TFE) was synthesized.

[0130]

[0131] DC-1173 (6.7 μL, 0.1 equivalent) was added to the pentane solution (0.82 M, 0.54 mL) of MOM-propellerane synthesized in Preparation Example 2, and the mixture was cryo-degassed using liquid nitrogen. Then, TFE at normal pressure was blown into the reaction solution, the temperature was raised to -70°C, and ultraviolet rays were irradiated. After 1 hour and 30 minutes, a part of the reaction solution became solid. After another 30 minutes, nitrogen was circulated to drive out TFE, thereby obtaining a yellow solid. After confirming that it was dissolved in CDCL3, a white precipitate was generated when an excess of methanol was added. The white solid was taken out by centrifugation (2000 rpm, 15 minutes) and vacuum dried to obtain copolymer 2 (41.5 mg). The content of fluorine atoms was quantified by combustion ion chromatography, and the TFE content was calculated. As a result, the TFE content was 39.8 mol%. The obtained copolymer 2 is soluble in organic solvents such as chloroform, diethyl ether, and tetrahydrofuran.

[0132] exist Figure 1 The obtained copolymer 2 is shown in 13C NMR (100MHz, CDCL3) spectrum data. In the figure, the upper layer is DEPT135 and the lower layer is 13 C NMR spectral data.

[0133] In addition, the molecular weight of copolymer 2 was measured by GPC using THF as an eluent. As a result, the molecular weight Mn=2.2×10 4 (polystyrene standard), molecular weight distribution Mw / Mn=2.2.

[0134] 19 F NMR (376MHz, CDCL3): -113.5~-114.7ppm(m)

[0135] [Test Example 1]

[0136] Thermogravimetric measurements were performed on the polymers synthesized in Comparative Example 1, Example 1, and Example 2. The measurement results are shown in Figure 2 .

[0137] like Figure 2 As shown, the 5% weight loss temperatures of polymer 1, copolymer 1 and copolymer 2 are 214° C., 396° C. and 344° C., respectively. From these results, it can be seen that the obtained copolymers 1 and 2 have better heat resistance than polymer 1 which is a propane homopolymer.

[0138] [Example 3]

[0139] The copolymer of propellerane and perfluoropropyl vinyl ether (PPVE) was synthesized.

[0140]

[0141] (1) Synthesis of polymer for molecular weight measurement

[0142] A stirring bar was placed in a Schlenk flask with a capacity of 30 mL, and after nitrogen substitution was performed three times by covering the piston, a diethyl ether / pentane solution (4 mL, 0.69 mmol) of propellerane synthesized in Preparation Example 1, PPVE (0.69 mmol) and DC-1173 (0.1 equivalent) as a photoinitiator were added to the Schlenk flask by syringe, and copolymerization was performed by irradiating ultraviolet rays at -70°C for 3 hours. Then, the reaction was post-treated by evaporation and vacuum extraction. Methanol was added thereto for reprecipitation, and after the supernatant was removed by decantation, it was dried by evaporation and vacuum drying to obtain copolymer 3 (152 mg) as a white solid. The obtained copolymer 3 is soluble in organic solvents such as chloroform, diethyl ether, cyclopentyl methyl ether, and hexafluorobenzene.

[0143] The content ratio of the polymerized units derived from each monomer was determined by dissolving the purified polymer in deuterated chloroform and adding hexafluoroparaxylene as an internal standard. 1 H NMR and 19 The integrated ratio of the internal standard substance and the copolymer in F NMR was determined to be m:n=43:57. 1 The peak area ratio of the terminal group to the main chain in HNMR confirmed that the number average molecular weight of the obtained copolymer 3 was 17150. 19 F NMR spectrum data are shown in Figure 3 .

[0144] 1 H NMR (400 MHz, CDCL3 / hexafluorobenzene = 1 / 1 mixed solvent): δ = -1.80 to -2.02 (m, 4H), -2.24 to -2.38 (m, 2H) ppm

[0145] 19 F NMR (376 MHz, CDCL3 / hexafluorobenzene = 1 / 1 mixed solvent): δ = -78.0 to -79.0 (m, 2F), -83.6 (m, 3F), -114.0 to -117.2 (2F), -129.0 to -131.6 (m, 3F) ppm

[0146] IR: 3050-2850 (C-H expansion), 1220 (C-O expansion), 1200-950 (C-F expansion) cm -1

[0147] (2) Synthesis and purification of polymers for thermal analysis and contact angle measurement

[0148] A diethyl ether / pentane solution of propane (11 mL, 3.4 mmol) and PPVE were photopolymerized in the same manner as in Example 3 in terms of "mmol". Methanol was then added to the reaction solution, and the polymer and the solution were separated using a centrifuge. The solvent was distilled off from the gel-like polymer, and vacuum dried. The crude product obtained was dissolved in hexafluorobenzene, reprecipitated again with methanol, and dried by evaporation and vacuum drying. This operation was repeated once more to obtain copolymer 3 (405 mg) as a white solid.

[0149] The obtained copolymer 3 was subjected to thermogravimetric measurement. The results are shown in the table of Experimental Example 1. Figure 2 The 5% weight loss temperature of the copolymer 3 was 255°C. The glass transition point (Tg) of the copolymer 3 measured by DSC was 177.5°C.

[0150] The obtained copolymer 3 was dissolved in hexafluorobenzene at a concentration of 1.8 wt%, and a film was formed on a glass substrate by a drop casting method. The obtained film was a transparent film. The contact angles of water and hydrocarbon solvents were measured on the surface of the film. At the same time, for comparison, the contact angles of water and hydrocarbon solvents were also measured for two 100 μm thick fluororesin films (PFA film (3-5591-04) and ETFE film (3-5590-02), both obtained from ASONE). The contact angles of water were 118° for copolymer 3, 114° for PFA, and 101° for ETFE, and copolymer 3 had the highest water repellency. In addition, the contact angles of various hydrocarbon solvents of copolymer 3, PFA and ETFE are shown in Table 1. For the resin film of copolymer 3, as shown in Figure 4 The cosine (cos) of the measured contact angle values ​​(Table 1) of various solvents was plotted against the surface tension values ​​(γL) of various hydrocarbon solvents described in Non-Patent Document 14 to determine the critical surface tension (γc: γL extrapolated to cosθ=1). Figure 4 In the plot, the γL value of the intersection of the approximate straight line and cosθ=1 is the value of the critical surface tension (γc). The critical surface tension value was obtained by performing the same operation on the resin film of PFA and the resin film of ETFE. As a result, the critical surface tension value was 15.3 dyn / cm for copolymer 3, while that for PFA was 17.1 dyn / cm and that for ETFE was 19.3 dyn / cm, indicating that copolymer 3 had the lowest surface energy. This is lower than the value (18.5 dyn / cm) of polytetrafluoroethylene described in non-patent document 14, indicating that copolymer 3 is a resin with low surface energy even compared to general fluororesins. This low surface energy characteristic is a characteristic that the copolymers of non-patent documents 11 to 13 do not have, and it can be said that it is a characteristic manifested by the introduction of fluoroolefins.

[0151] [Table 1]

[0152]

[0153] (3) Synthesis and purification of polymers for vapor pressure measurement and XPS measurement

[0154] A diethyl ether / pentane solution of propane (9 mL, 3.9 mmol) and PPVE were photopolymerized in the same manner as in Example 3. Methanol was then added to the reaction solution, and the polymer and the solution were separated using a centrifuge. The solvent was distilled off from the gel-like polymer, and vacuum dried. The crude product obtained was dissolved in hexafluorobenzene, reprecipitated again with methanol, and dried by evaporation and vacuum drying. This operation was repeated once more to obtain copolymer 3 (561 mg) as a white solid.

[0155] The obtained copolymer 3 was dissolved in hexafluorobenzene at a concentration of 1.0, 2.0 or 3.0 mass % (10, 20 or 30 g / kg), and the vapor pressure was measured. The vapor pressure measurement was performed using a vapor pressure measuring device (product name "Vapor Pressure Osmometer K-7000", manufactured by KNAUER). As a calibration sample, a perfluoropolyether derivative with a molecular weight of 4090 ("Fomblin (registered trademark) 4000", manufactured by Solvay) was used. For Fomblin 4000 and copolymer 3, the measurement samples adjusted to various concentrations ("mol / kg" in the measurement of Fomblin 4000, "g / kg" in the measurement of copolymer 3) were respectively provided to the vapor pressure measuring device for measurement to obtain the measured value (MV). The measurement data was plotted using each concentration (c) (mol / kg) of Fomblin 4000 as the horizontal axis and the value obtained by dividing the measured value (MV) at each concentration (c) by the concentration (MV / c value) as the vertical axis, and the resulting graph was shown in FIG. Figure 5 (A) The measured data were plotted with the concentrations (c) (g / kg) of copolymer 3 as the horizontal axis and the value obtained by dividing the measured value (MV) at each concentration (c) by the concentration (MV / c value) as the vertical axis. The resulting graph is shown in FIG. Figure 5 (B). Figure 5 As shown in (A) and (B), each plot is a straight line. The intercept of this straight line in Fomblin4000 (K calib ) is 1571( Figure 5 (A)). The intercept of this straight line in copolymer 3 (K meas ) is 0.220( Figure 5 (B)). The molecular weight of copolymer 3 is calculated based on K calib / K meas As a result, it was found that the number average molecular weight of the copolymer 3 was about 7,100.

[0156] The obtained copolymer 3 was dissolved in hexafluorobenzene at 2.0 mass %, and a film was formed on an ETFE film by drop casting. The film of the produced copolymer 3 was measured by XPS (X-ray Photoelectron Spectroscopy). The results are shown in Figure 6 The XPS spectrum of fluorine in the film of copolymer 3 is shown in Figure 6 (A), the XPS spectrum of carbon is shown in Figure 6 (B), the XPS spectrum of oxygen is shown in Figure 6 (C). According to the peak area ratio of each element, the fluorine content on the membrane surface is 51.6 atomic%, the carbon content is 44.1 atomic%, and the oxygen content is 4.3 atomic%. Based on these results, it can be seen that the content ratio of propellerane units and fluoroolefin units on the membrane surface is propellerane:fluoroolefin = 58:42 (mol ratio).

[0157] [Comparative Example 2]

[0158] Polymer 2 was synthesized by homopolymerization of PPVE.

[0159]

[0160] Using PPVE (0.26 mL, 1.5 mmol) and DC-1173 (0.1 equivalent) as a photoinitiator, polymerization and purification were carried out in the same manner as in Example 3 (1) to obtain PPVE homopolymer 2 (164 mg) as a yellow solid. 1 HNMR, 19 The peak area ratio of the terminal group to the main chain in F NMR showed that the number average molecular weight of the obtained polymer 2 was 1686. 19 F NMR spectrum data are shown in Figure 3 .

[0161] 19 F NMR (376MHz, CDCL3): δ=-81.0 (m, 3F), -84.0~-88.0 (m, 2F), -123.0~-130.0 (m, 4F), -143.0~-146.0 (m, 1F)ppm

[0162] IR: 1350-1200 (C-O expansion), 1200-950 (C-F expansion) cm -1

[0163] like Figure 3 As shown, in the copolymer 3 of Example 3 19 In F NMR, the peaks of -84.0 to -88.0 ppm corresponding to OCF2 adjacent to ether oxygen and -143.0 to -146.0 ppm corresponding to OCF of homopolymer 2 of PPVE of Comparative Example 2 were shifted to -78.0 to -79.0 ppm and -127.0 to -129.0 ppm by copolymerization with propane, and no peaks were observed in the regions of -84.0 to -88.0 ppm and -143.0 to -146.0 ppm, suggesting that there were almost no PPVE chains in the polymer chains of copolymer 3. From this result, it can be said that the alternation between propane and PPVE in copolymer 3 is high.

[0164] [Example 4]

[0165] The copolymer 4 of propellerane and 2-(heptafluoropropoxy)hexafluoropropyltrifluorovinyl ether (PHVE) was synthesized.

[0166]

[0167] Using a diethyl ether / pentane solution of propane (5.0 mL, 1.47 mmol), PHVE (1.47 mmol) and DC-1173 (0.1 equivalent) as a photoinitiator, polymerization and purification were carried out in the same manner as in Example 3 (1) to obtain copolymer 4 (441 mg) as a white solid. 1 From the peak area ratio of the terminal group to the main chain in H NMR, it was found that the number average molecular weight of the obtained copolymer 4 was 32,310.

[0168] 1 H NMR (400 MHz, CDCL3 / hexafluorobenzene = 1 / 1 mixed solvent): δ = 2.4-2.2 (m, 2H), 2.0-1.8 (m, 4H) ppm

[0169] 19 F NMR (376 MHz, CDCL3 / hexafluorobenzene = 1 / 1 mixed solvent): δ = -75.0 to -77.0, -79.0 to -81.0 (m, 2F), -80.5 to -83.5 (m, 8F), -114.0 to -117.5 (m, 2F), -130.0 to -131.7 (m, 3F), -144.4 (brd, 1F)

[0170] IR: 3050-2850 (C-H expansion), 1230 (C-O expansion), 1200-900 (C-F expansion) cm -1

[0171] The obtained copolymer 4 was subjected to thermogravimetric measurement. The results were superimposed with the measurement results of copolymer 3 and are shown in Figure 7 The 5% weight reduction temperature of copolymer 4 was 338°C.

[0172] The obtained polymer 1, copolymer 1, copolymer 3 and copolymer 4 were subjected to powder X-ray measurement. The results are shown in Figure 8 In copolymers 3 and 4, the low-angle peaks are broad, which is presumably due to the use of fluoroolefins having long side chains, which reduces the crystallinity.

[0173] The obtained copolymer 4 was subjected to contact angle measurement. It was dissolved in hexafluorobenzene at a concentration of 3.0 mass %, and a film was formed on a glass substrate by drop casting. The contact angles of water and hydrocarbon solvents were measured on the surface of the produced film. The measurement results are shown in Fig. 9 The contact angle of water of the film of copolymer 4 was 116°, and the contact angle of n-hexadecane was 61.6°. The critical surface tension of the film was determined in the same manner as in Example 3 and was found to be 10.9 dyn / cm, showing higher water and oil repellency than that of the film of copolymer 3.

[0174] The obtained copolymer 3 was subjected to UV-VIS measurement. Specifically, the copolymer 3 was dissolved in hexafluorobenzene at a concentration of 3.0% by mass, and films were formed on quartz substrates by drop casting. The results are shown in Fig.10 In the copolymer 3, the transmittance in the wavelength region of 370 nm or longer was 90% or higher, showing very high transparency.

[0175] [Example 5]

[0176] In the copolymer 3 of propane and perfluoropropyl vinyl ether (PPVE), the polymerization conditions were studied in order to obtain a high molecular weight product.

[0177] (1) Research on solvents

[0178] Propellane was synthesized using various solvents in order to examine the most optimal solvent for the synthesis of Copolymer 3. Propellane was synthesized according to the method described in Non-Patent Document 15.

[0179]

[0180] As solvents, diethyl ether, hexane, hexafluorobenzene, CFE-419, and HFC-365mfc were used, and a reduction reaction was carried out using hydrazine to obtain various propellerane solutions. After the propellerane solution was filtered through alumina to remove the hydrazine, the unreacted diiodobiscyclopentane was crystallized by recrystallization, and filtered under nitrogen to purify. When hexafluorobenzene was used as a solvent, the melting point of hexafluorobenzene was 5°C, which was too high to be recrystallized. Therefore, after filtering through alumina, the solution was vacuum transferred to a Schlenk tube for distillation to purify. By adding hexafluoroparaxylene as an internal standard, using 1 The propellerane concentration was determined by H NMR measurement.

[0181] 1 equivalent of PPVE and 0.02 equivalent of DC-1173 were added to each of the obtained propane solutions, and polymerization was carried out in the same manner as in Example 3. Methanol was added after the reaction to stop the polymerization, and then the solvent was evaporated using an evaporator to dry. A small amount of hexafluorobenzene was added to the obtained dry matter to dissolve the solid, and then methanol was used for reprecipitation to purify the polymer. In the system using hexafluorobenzene as the solvent, no polymer was precipitated after the reaction.

[0182] The obtained copolymer 3 was dissolved in hexafluorobenzene at a concentration of 0.8, 1.6 or 2.4 mass % (8, 16 or 24 g / kg), and the vapor pressure was measured in the same manner as in Example 3. As a calibration sample, a perfluoropolyether derivative with a molecular weight of 3850 ("Fomblin (registered trademark) 4000", manufactured by Solvay) was used. Based on the measurement results of the Fomblin 4000 derivative, K calibThe vapor pressure was 1306. Table 2 shows the results of the vapor pressure measurement.

[0183] [Table 2]

[0184] Solvents Km MW Diethyl ether 0.664 2000 Hexane 0.339 3800 CFE-419 0.382 3400 Hexafluorobenzene 0.165 7900

[0185] As shown in Table 2, when hexafluorobenzene is used as the solvent, K mn The smallest, the amount of polymer precipitated after polymerization was small, and the molecular weight of the obtained polymer was also the largest. Based on these results, hexafluorobenzene is considered to be the best solvent, and hexafluorobenzene is used as the solvent for the following polymerization reaction.

[0186] (2) Study on polymerization conditions

[0187] Polymerization was performed by changing the initiator equivalent. The initiator DC-1173 added to the hexafluorobenzene solution of propane was changed to 0.005 equivalent (Entry 2) and 0.08 equivalent (Entry 3), and polymerization and purification were performed in the same manner as in Example 3.

[0188] Next, the concentration of the propellerane solution was studied. The propellerane solution synthesized under the conditions of (1) above had a concentration of 0.3M (Entry 1). The synthesis and purification of propellerane were carried out under the same conditions except that the amount of solvent was halved in the reduction reaction from diiododicyclopentane to propellerane. As a result, a propellerane solution with a concentration of 0.5M was obtained (Entry 4). In addition, after the synthesis and purification of the propellerane solution were carried out under the same conditions, hexafluorobenzene was added to obtain a propellerane solution with a concentration of 0.15M (Entry 5).

[0189] When the polymerization was carried out in hexafluorobenzene solvent, the PPVE content in the copolymer tended to decrease. Therefore, the polymerization was carried out by changing the monomer feed ratio. 4 equivalents (Entry 6) and 9 equivalents (Entry 7) of PPVE were added to the propane solution, and polymerization and purification were carried out in the same manner as in Example 3.

[0190] The copolymer 3 synthesized in this way was dissolved in hexafluorobenzene at a concentration of 0.8, 1.6 or 2.4 mass % (8, 16 or 24 g / kg), and the vapor pressure was measured in the same manner as in Example 3. As a calibration sample, a perfluoropolyether derivative with a molecular weight of 3850 ("Fomblin (registered trademark) 4000", manufactured by Solvay) was used. Based on the measurement results of the Fomblin 4000 derivative, K was calculated. calib The vapor pressure was 1378. Table 3 shows the results of the vapor pressure measurement.

[0191] [Table 3]

[0192] Entry <![CDATA[K mn ]]> MW 2 0.203 6800 3 0.166 8300 4 0.285 4800 5 0.416 3300 6 0.260 5300 7 0.169 8200

[0193] As shown in Table 3, under any polymerization condition, a polymer with a molecular weight significantly larger than the molecular weight of Entry 1 (7900) could not be obtained. That is, even if the initiator equivalent, monomer concentration, and monomer feed ratio were changed, the molecular weight of the obtained polymer did not increase much. Since the melting point of the hexafluorobenzene solution is 5°C, which is relatively high, the reaction temperature was set to 5°C when the polymerization was carried out in the hexafluorobenzene solvent. It is believed that since the polymerization temperature is higher than when the polymerization is carried out in the diethyl ether solvent, the reactivity of the homopolymerizable propellerane is increased, resulting in not only an alternating sequence of propellerane and PPVE, but also a continuous sequence of many propelleranes. By using a mixed solution of hexafluorobenzene and diethyl ether as a solvent, there will be no precipitation after polymerization, and by suppressing the reactivity of the propellerane at a low temperature and performing the polymerization, it can be expected to increase the molecular weight and the PPVE content.

[0194] Example 6]

[0195] Copolymer 3 and Copolymer 4 were evaluated for film forming properties and wettability by spin coating.

[0196] Copolymer 3 and copolymer 4 were respectively formed on silicon wafers using a spin coater. The silicon wafer was cut into 1.5 cm squares in advance, then cleaned by heating with piranha solution at 100°C for 2 hours, and stored in ultrapure water. Before film formation, acetone and hexafluorobenzene were sequentially spin-coated on the silicon wafer to rinse the residual solvent on the substrate. Then, copolymer 3 or copolymer 4 was spin-coated on the silicon wafer to form a film. After film formation, the copolymer 3 film was vacuum dried at 180°C and the copolymer 4 film was vacuum dried at 150°C for more than 12 hours for heat treatment.

[0197] The contact angles of these films were measured. Water and diiodomethane were used as probe liquids. In addition, the measurement was performed more than 7 times, and the average value was calculated from 5 points excluding the maximum and minimum values. In addition, the surface free energy was calculated using the Owens-Wendt equation based on the contact angle values ​​of water and diiodomethane. Their results are shown in Table 4.

[0198] [Table 4]

[0199] film <![CDATA[θ 水 (°)]]> <![CDATA[θ 二碘甲烷 (°)]]> <![CDATA[Surface free energy (mJ / m 2 )]]> Copolymer 3 115 112 6.7 Copolymer 4 117 90 13

[0200] As shown in Table 4, it is found that both copolymer 3 and copolymer 4 have water and oil repellency equivalent to or stronger than that of the existing fluoropolymers.

Claims

1. A fluoroolefin copolymer having a structure represented by the following general formula (1), In formula (1), R 1 is a fluorine atom, a perfluoroalkyl group having 1 to 10 carbon atoms which may have -O- between carbon atoms, or a perfluoroalkoxy group having 1 to 10 carbon atoms which may have -O- between carbon atoms; R 2 and R 3 are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or an aryl group which may have a substituent; 2 and R 3 can be bonded to each other to form a ring; the aliphatic hydrocarbon group can contain one or more selected from -O-, -Si(CH3)2-, -CO- and -NH- between carbon atoms; x and y represent the proportion of each monomer, wherein, x+y=100(%), x and y are in the range of 10≤x, y≤90 respectively; black dots represent bonding sites.

2. The fluoroolefin copolymer according to claim 1, wherein The R 2 and R 3 All are hydrogen atoms.

3. The fluoroolefin copolymer according to claim 1, wherein The R 1 It is a fluorine atom or a perfluoroalkoxy group having 1 to 10 carbon atoms and having -O- between carbon atoms.

4. A method for producing a fluoroolefin copolymer, comprising subjecting a compound represented by the following general formula (2) and a compound represented by the following general formula (3) to free radical polymerization to produce a fluoroolefin copolymer having a structure represented by the following general formula (1), In formula (2), R 1 is a fluorine atom, a perfluoroalkyl group having 1 to 10 carbon atoms which may have -O- between carbon atoms, or a perfluoroalkoxy group having 1 to 10 carbon atoms which may have -O- between carbon atoms, In formula (3), R 2 and R 3 are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or an aryl group which may have a substituent; 2 and R 3 can be bonded to each other to form a ring; the aliphatic hydrocarbon group can contain one or more selected from -O-, -Si(CH3)2-, -CO- and -NH- between carbon atoms, In formula (1), R 1 , R 2 and R 3 Same as above; x and y represent the proportion of each monomer, wherein, x+y=100(%), x and y are in the range of 10≤x, y≤90 respectively; black dots represent bonding sites.

5. The method for producing a fluoroolefin copolymer according to claim 4, wherein The free radical polymerization is carried out at -30°C or below.

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