TW200806698A - Novel polyfluorodiene, method for producing the same, and novel fluorine-containing polymer - Google Patents

Abstract

Disclosed are a novel polyfluorodiene, a production method thereof, and a novel fluorine-containing polymer. Specifically disclosed are a compound represented by the following formula: CF2=CFCH2CHR(CH2)mCX=CH2, a polymer having a repeating unit obtained by polymerization of the compound, and a polymer having a repeating unit represented by the formula (A) below. (In the formulae, R represents an alkyl group having 1-12 carbon atoms or a fluoroalkyl group having 1-12 carbon atoms; m represents 0, 1 or 2; and X represents a hydrogen atom or an alkyl group having 1-12 carbon atoms.)

Description

200806698 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a novel polyfluorinated diene, a process for producing the same, and a novel fluoropolymer. [Prior Art] Patent Document 1 and Patent Document 2 have a polyfluoride selected from the group consisting of CF2 = • CFCF2CF2CH2CH = ch2, cf2 = cfcf(cf3)cf2ch2ch = ch2, and cf2 = cfcf2cf(cf3)ch2ch2 CH2 ( 1,6-Heptadiene) is described by cyclization polymerization to form a polymer having a fluorinated aliphatic ring structure in its main chain. Patent Document 1 and Patent Document 2 also disclose that the polymer has excellent chemical resistance and thermal properties, and can be used in technical fields such as a film, a coating agent, and a molded article by using standard techniques. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Among the carbon atoms, a branched polyfluorinated diene having only one and two carbon atoms bonded to a fluorine atom is unknown. Further, there is no knowledge of the polymer of the polyfluorinated diene and its physical properties. The object of the present invention is to provide a branch-like polyfluorination obtained by bonding a fluorine atom to a carbon atom having no one or two positions on a carbon atom (a carbon atom of a main chain portion) which does not contain a branch. The diene and the fluorinated diene have excellent resistance, heat resistance, transparency, durability and light resistance, water repellency and oil repellency, especially those having excellent water repellency, by polymerization -5 - 200806698 (2) Things. The present invention is an invention having the following features. [1], a compound of the following formula (a), cf2 = cfch2chr (ch2) mcx = ch2 wherein the symbols in the formula have the following meanings (the same applies hereinafter), R: an alkyl group having 1 to 12 carbon atoms Or a fluoroalkyl group having 1 to 12 carbon atoms, m: 0, 1 or 2, X: a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. [2] The compound according to [1], wherein R is an alkyl group having 3 to 6 carbon atoms or a polyfluoroalkyl group having 3 to 6 carbon atoms. [3] The compound according to [1] or [2] wherein R is a polyfluorol group represented by the formula CH2RF (wherein RF is a perfluoroalkyl group having 2 to 5 carbon atoms). [4] A method for producing a compound represented by the following formula (a), which is characterized in that a compound represented by the following formula (f) is reacted with a compound represented by the following formula (6) to obtain the following formula (d): a compound shown by the following formula, wherein the compound is reacted with a compound represented by the following formula (c) to obtain a compound represented by the following formula (b), and secondly, a method of reacting the compound with a dehalogenating agent, CH2=CHR (f) CF2YCFIY (e) CF2YCFYCH2CHIR ( d) -6 - 200806698 (3) CH2 di CX(CH2)mMgZ ( c ) CF2YCFYCH2CHR(CH2)mCX= CH2 ( b ) wherein the symbol in the formula has the following meaning ( The same as the following), * Y, Z: independent chlorine or bromine atoms. '[5], a polymer containing a repeating unit of the following formula (A), [Chemical 1]

.CF2 I XH2 ~CF—〆, / \ /(ch2u ΌΗ IR (A) A method for producing a polymer represented by the formula (a) and containing a repeating unit of the compound. [6], such as [5] The polymer of the item, wherein R is an alkyl group having 3 to 6 carbon atoms or a polyfluoroalkyl group having 3 to 6 carbon atoms. [7] The polymer according to [5] or [6], wherein: The polyfluoroalkyl group of the formula -CH2RF, wherein the RF is a perfluoroalkyl group having a carbon number of 2 to 5, wherein the polymer of any one of [5] to [7], wherein The weight average molecular weight is from 10,000 to 10,000. [9] A precision-worked member which is a polymer using the above item [5], [6], [7] or [8]. The present invention provides a branched polyfluorinated diene in which a carbon atom (having a carbon atom of a main chain moiety) which is not known in the prior art has a fluorine atom bonded to only one carbon atom at the 2-position and the carbon atom. The fluorinated diene of the present invention can obtain excellent chemical resistance, heat resistance, transparency, durability, light resistance, water repellency, and particularly excellent water repellency by polymerization as a result of polymerization of 200,806,698 (4). In the present specification, the compound represented by the formula (a) is referred to as the compound (a), and the repeating unit represented by the formula (A) is referred to as the unit (A). The compound represented by the other structure of the structure and the structural formula thereof The repeating unit shown is also the same as the description of the same. Further, the symbol in the substituent has the same meaning as the above unless otherwise specified. φ The present invention provides the following compound (a): CF2 = CFCH2CHR ( CH2) mCX=CH2 (a) R is preferably an alkyl group having 1 to 6 carbon atoms or a polyfluoroalkyl group having 1 to 6 carbon atoms, and the physical properties of the polymer of the compound (a) (water-repellent property, etc.) The viewpoint is preferably an alkyl group having 3 to 6 carbon atoms or a polyfluoroalkyl group having 3 to 6 carbon atoms, particularly preferably a polyfluoroalkyl group having 3 to 6 carbon atoms. When the carbon number of R is 3 or more, R may be a linear or branched group, and R may be a group having a ring structure. When R is a polyfluoroalkyl group having 1 to 6 carbon atoms, R is a formula for the ease of synthesis. The group represented by -CH2RF is preferred. However, RF is a perfluorocarbon group having a carbon number of 2 to 5. When R is an alkyl group having 1 to 12 carbon atoms, specific examples of R are, for example, -CH2CH3, -(CH2)2CH3, - CH(CH3)2, -(CH2)3CH3 -CH2CH(CH3)2, -ch(ch3)(ch2ch3), -(ch2)4ch3, -(ch2)5ch3, etc. When R is a polyfluoroalkyl group having 1 to 12 carbon atoms, a specific example of R -CH2CF3 , -CH2CF2CF3, -CH2(CF2)2CF3, -CH2CF(CF3)2, - 200806698 (5) CH2(CF2)3CF3, -CF3, -CF2CF3, -(CF2)3CF3, and the like. Further, when R is a polyfluorene group having a carbon number of 1 to 12, the fluorine content of R is preferably 40 to 76% by mass, particularly preferably 45 to 70% by mass. m is preferably 1. 'X is preferably a hydrogen atom or a methyl group, and is particularly preferably a hydrogen atom. - Compound (a) is preferably the following compound (a 1 ) (wherein R1 is an alkyl group having 1 to 6 carbon atoms or a polyfluoroalkyl group having 1 to 6 carbon atoms). CF2-CFCH2CHR1CH2CH-CH2 (al) Specific examples of the compound (a) include the following compounds and the like. CF2 = CFCH2CH(CH2CH3)CH2CH = CH2, CF2 = CFCH2CH((CH2)3CH3)CH2CH = CH2, CF2 = CFCH2CH(CH2CH(CH3)2)CH2CH = CH2, CF2 = CFCH2CH((CH2)5CH3)CH2CH = CH2

CF2 = CFCH2CH(CH2CF3)CH2CH = CH2, CF2 = CFCH2CH(CH2CF2CF3)CH2CH = CH2, CF2 = CFCH2CH(CH2(CF2)2CF3)CH2CH = CH2, CF2 = CFCH2CH(CH2CF(CF3)2)CH2CH = CH2, CF2 = CFCH2CH(CH2(CF2)3CF3)CH2CH = CH2, CF2 = CFCH2CH(CF3)CH2CH = CH2, CF2 = CFCH2CH(CF2CF3)CH2CH = CH2, CF2 = CFCH2CH((CF2)3CF3)CH2CH = CH2. Compound (a), which can be obtained by reacting the following compound (f) with the following compound-9 - 200806698 (6) (e) to give the following compound (d), and secondly, compound (d) and the following compound (c) The reaction gives the following compound (b), and secondly, the compound (b) is reacted with a dehalogenating agent to obtain CH2=CHR(f)CF2YCFIY(e)CF2YCFYCH2CHIR(d)CH2 di CX(CH2)mMgZ (c CF2YCFYCH2CHR(CH2)mCX=CH2(b) CF2=CFCH2CHR(CH2)mCX=CH2 (a) γ and z are preferably chlorine atoms. The reaction conditions in the step of reacting the compound (f) with the compound (e) to obtain the compound (d) are not particularly limited. The temperature in the foregoing step is preferably from 40 ° C to 100 ° C. The pressure in the foregoing step can be carried out under any of the conditions of pressurization, depressurization, and atmospheric pressure. The above steps may be carried out in the presence of a solvent, and may be carried out in the absence of a solvent. In the foregoing step, the compound (e) is preferably used in an amount of from 0.95 to 1.20 moles relative to the compound (f). The foregoing steps are preferably carried out in the presence of a radical initiator. Specific examples of the radical initiator include an azo compound, an organic peroxide, an inorganic peroxide, and the like. More specifically, for example, phenylhydrazine peroxide, diisopropylperoxydicarbonate, di-t-butyl peroxydicarbonate, t-butylperoxyvalerate, perfluorobutyrate peroxidation , perfluorophenylhydrazine peroxide, azoisobutyronitrile, and the like. Specific examples of the compound (f), such as CH2=CHCH2CH3, -10-200806698 (7) CH2=CH(CH2)3CH3, CH2=CHCH2CH(CH3)2, CH2=CH(CH2)5CH3, CH2=CHCH2CF3, CH2 = CHCH2CF2CF3, CH2 = CHCH2(CF2)2CF3, CH2 = CHCH2CF(CF3)2, CH2 = CHCH2(CF2)3CF3, CH2 = CHCF3, CH2 = CHCF2CF3, CH2 = CH(CF2)3CF3, etc. Specific examples of the compound (e) include, for example, CF2C1CFC1I and the like.

Specific examples of the compound (d) are, for example, CF2C1CFC1CH2CHICH2CH3, CF2C1CFC1CH2CHI(CH2)3CH3, CF2C1CFC1CH2CHICH2CH(CH3)2, CF2C1CFC1CH2CHI(CH2)5CH3, CF2C1CFC1CH2CHICH2CF3, CF2C1CFC1CH2CHICH2CF2CF3, CF2C1CFC1CH2CHICH2(CF2)2CF3, CF2C1CFC1CH2CHICH2CF(CF3)2

CF2C1CFC1CH2CHICH2(CF2)3CF3, CF2C1CFC1CH2CHICF3, CF2CICFCICH2CHICF2CF3, CF2C1CFC1CH2CHI(CF2)3CF, etc. The reaction conditions in the step of reacting the compound (d) with the compound (c) to obtain the compound (b) are not particularly limited. The temperature in the foregoing step is preferably -100 ° C to + 25 ° C. In the foregoing steps, the pressure can be carried out under any of an environment of pressurization, depressurization, and atmospheric pressure. The above steps may be carried out in the presence of a solvent, may be carried out in the absence of a solvent, and preferably in the presence of a solvent. The solvent is preferably an aprotic polar solvent. Further, the above steps are preferably carried out in the presence of a radical initiator. 200806698 (8) In the foregoing step, the compound (c) is preferably used in an amount of 1.0 to 2.0 times by mole based on the compound (d). Specific to compound (c) is, for example, CH2=CHCH2MgCl. Specific examples of the compound (b) are, for example, 'CF2C1CFC1CH2CH(CH2CH3)CH2CH=CH2, CF2C1CFC1CH2CH((CH2)3CH3)CH2CH=CH2, CF2C1CFC1CH2CH(CH2CH(CH3)2)CH2CH=CH2, • CF2C1CFC1CH2CH((CH2)5CH3)CH2CH = CH2, CF2C1CFC1CH2CH(CH2CF3)CH2CH = CH2, CF2C1CFC1CH2CH(CH2CF2CF3)CH2CH = CH2, CF2C1CFC1CH2CH(CH2(CF2)2CF3)CH2CH = CH2, CF2C1CFC1CH2CH(CH2CF(CF3)2)CH2CH = CH2, CF2C1CFC1CH2CH(CH2(CF2)3CF3) CH2CH = CH2, CF2C1CFC1CH2CH(CF3)CH2CH = CH2, CF2C1CFC1CH2CH(CF2CF3)CH2CH = CH2, • CF2C1CFC1CH2CH((CF2)3CF3)CH2CH=CH2, etc. The reaction conditions in the step of reacting the compound (b) with the dehalogenating agent to obtain the compound (a) are not particularly limited. When the halogenating agent is removed, in order to dissociate two Y reactants in the compound (b), and two Y are chlorine atoms, the dehalogenation agent is a dechlorinating agent. The dehalogenating agent is preferably zinc, sodium, magnesium, tin, copper or iron, and zinc is most preferred in terms of low-temperature reactivity. The temperature in the foregoing step is preferably from 30 ° C to 100 ° C. In the foregoing step, the pressure can be carried out under any of an environment of pressurization, reduced pressure, and atmospheric pressure. The above steps may be carried out in the presence of a solvent, and may be carried out in the absence of a solvent. -12-200806698 Ο) may be carried out in the presence of a solvent. The solvent is preferably a polar solvent. Specific examples of the polar solvent include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, 1,4-dioxane diethylene glycol dimethyl ether, methanol, and the like. Organic polar solvent, water, and the like. * In the foregoing step, the dehalogenating agent is preferably used in an amount of from 1 * to 20 times by mole, more preferably from 2 to 8 times by mole based on the compound (b). The compound (a) of the present invention is a branch of a carbon atom having no branched chain (a carbon atom of a main chain moiety) which is not shown in the literature, and has only one and two carbon atoms bonded to a fluorine atom. Polyfluorinated diene. Compound (a) can be polymerized by polymerization. The present invention provides a method for producing a polymer comprising a repeating unit of the compound (a) which polymerizes the compound (a). The polymerization of the compound (a) is such that, in the compound (a), four carbon atoms having a carbon-carbon double bond are formed, and two adjacent bonds are bonded to each other to form a ring, and another carbon atom adjacent thereto The formation of a bonding bond is carried out in such a manner as to form a bond with its other monomer molecule. a carbon-carbon double-bonded four carbon atom in the compound (a) represented by the following formula (a'), which is sequentially given to c1, C2, C3, and C4, and a ring formed by bonding C2 and C3. At the same time, ci forms a bonding bond with C4 to generate the following unit C Aa). Similarly, the bond of C2 and C4 forms a ring to form the following unit (Ab), and the bond of C^ and C3 forms a ring to form the following unit (Ac). The bond of C1 and C4 forms a ring to form the following Unit (Ad) 〇-13- 200806698 (10)

C1F2= C2FCH2CHR ( CH2) mc3x II C4H

The repeating unit of the compound (a) is composed of one or more repeating units selected from the group consisting of units (Aa), units (Ab), and units (A〇 and units (Ad). Compound (a) The repeating unit is a part of which repeating unit, which can be obtained by changing the kind of R and X of the compound (a), polymerization conditions, etc. Usually, the unit (Aa) is the most stable, followed by The unit (Ab ) and the unit (Ac ) are stable, and the unit (Ad) is unstable. Therefore, the repeating unit of the compound (a) contains almost no unit (Ad ), and the compound (a) has fewer repeating units. The unit (Ab ) and the unit (Ac ) are contained. Therefore, the repeating unit of the compound (a) is usually composed of the unit (Aa). The polymerization of the compound (a) is carried out in the presence of a radical initiator A free radical initiator such as an azo compound, an organic peroxide, an inorganic peroxide, etc. Specifically, for example, azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) Hydrochloride, 4,4'-azobis(4--14-200806698 (11) cyanovalerate), 2,2 '-Azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(1-cyclohexanecarbonitrile), diisopropylperoxydicarbonate , perfluorophenylhydrazine peroxide, perfluorophenylhydrazine total oxide, perfluoroantimony peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, K2S2O8, (ΝΗ4)2 §2〇8, etc. The polymerization method of the compound (a) is not particularly limited, and any one of a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be used. The pressure is not particularly limited. The polymerization temperature is preferably from 0 ° C to 200 ° C, preferably from 30 ° C to 1 ° C. The polymerization pressure can be under reduced pressure and under pressure. The polymerization of the compound (a) may be carried out only by the compound (a), or the compound (a) may be copolymerized with the compound (a) and then with other polymerizable compounds (hereinafter also referred to as Other compounds may be copolymerized. In the polymerization of the compound (a), one type of the compound (a) may be used, or two or more kinds of the compound (a) may be used. The other polymerizable compound is not particularly limited, and is preferably, for example, a (meth) acrylate, a non-fluoro olefin, an acyclic fluoromonoolefin, a cyclic fluoromonoolefin or a fluorodiene. Acrylate is a general term for acrylate and methacrylate. Specific examples of (meth) acrylate are methyl (meth) acrylate, ethyl (meth) acrylate, butyl butyl (meth) acrylate, (a) 2-ethylhexyl acrylate, octyl (meth) acrylate, decyl (meth) acrylate, decyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (methyl) ) 2-hydroxyethyl acrylate, (meth) propylene-15- 200806698 (12) 1-adamantyl acid, 3-hydroxy-1-adamantyl (meth) acrylate, 2-methyl (meth) acrylate Alkyl-adamantyl ester, 2-oxo-tetrahydrofuran-3-yl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, and the like. Examples of the non-fluorine-based olefin other than the (meth) acrylate, such as an olefin having no fluorine atom, and the like, for example, acrylic acid, methacrylic acid, decylamine acrylate, ethylene, ethylene chloride, vinylidene chloride, propylene, chlorine Butadiene, butadiene, alkyl vinyl ether (methyl vinyl ether, etc.), alkyl vinyl ester (ethyl acetate, etc.), and the like. Specific examples of the acyclic fluoromonoolefin include, for example, fluorinated ethylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and polyfluorovinyl ether (perfluoropropyl ethene ether, etc.) Specific examples of the cyclic fluoromonoolefin are, for example, any of the following compounds. 〔化3〕

I CF2 CF2-CF (CF3)

The CF fluorodiene is preferably, for example, the following compound (g 1 ) or (g2 ). CF2==CF-Q1-CW1 = CF2 ( gl ), CF2-CF.Q2-CW2 = CF2 ( g2 ). Among them, the symbols in the formula have the following meanings. Q1: a perfluoroalkylene group or a perfluoro(oxoalkylene) group having a carbon number of 1 to 4. W1: a hydrogen atom or a fluorine atom. -16- 200806698 (13) Q2: a hydroxyl group, a carboxyl group, an alkoxycarbonyl group, or an alkylene group having a carbon atom number of 3 to 20 which may have a fluorine atom. W2: a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Q2 is ·2(:(εΡ3)(ΟΗ)(:Η2-, -ch2ch(c(cf3)2(oh)ch2-, -ch2ch(ch2c(cf3)2(oh))ch2·, -ch2ch( Cooh)ch2-, -cf2c(cf3)(ococ(ch3)3)ch2-, -CH2CH(C(CF3)2(OCOC(CH3)3)CH2-, -CH2CH(CH2C(CF3)2(OCOC(CH3) 3) CH2-, or -CH2CH(COOCH3)CH2- is preferred. w2 is preferably a hydrogen atom. Specific compounds (gl) such as CF2 = CFOCF2CF = CF2, CF2 = CFOCF2CF2CF = CF2, CF2 = CFOCF2CF(CF3)CF = CF2, CF2 = CFOCF(CF3)CF2CF = CF2, etc. Specifics of compound (g2)

CF2 = CFCF2C(CF3)(OH)CF2CH = CH2, CF2CFCH2CH(C(CF3)2(OH))CH2CH = CH2, CF2 = CFCH2CH(CH2C(CF3)2(OH))CH2CH = CH2, CF2 = CFCH2CH(COOH CH2CH = CH2, CF2 = CFCF2C(CF3)(OCOC(CH3)3)CH2CH = CH2, cf2 = cfch2ch(c(cf3)2(ococ(ch3)3)ch2ch=ch2, CF2 = CFCH2CH(CH2C(CF3) 2 (OCOC(CH3)3)CH2CH = CH2, cf2 = cfch2ch(cooch3)ch2ch = ch2, etc. The present invention provides a polymer containing the following unit (A). [Chemical 4] -17- 200806698 (14) Unit ([5] units ([6]; cf2; cf2 〆; CF2 〆; cf2 this hair, or by

, CF2, i/CH2 CF-C/\JCH2)m ΌΗI R (A) : A) is preferably in the following unit (Al), CF2 /CH2 \CF-CH , CH^

CH

Specific examples of CHI R 2 (At) : A), for example, repeating units shown in the following formula, ch2

Vt-OH / \ C02 /CH2

CH ch2ch3 J , CF—CH / \ CH2 ^ch2 , CH CH2CF3 , CF—CH / \ ch2 ch2 , CF2 /CH; , CF-CH / \ CH2 /CH2

rCF2 /GH2 ^CF-CH

Cl

H2 yCH2 CH XCH IL (ch2)3ch3" CH2CH(CH3)2 : cf2 /CH2 Ί 〆\CF-CH ~ / \ , cf2 ^ch2 \CF-CH , ch2 ^οη2 XCH J / \ CH2 χ〇Η2 , CH _ CH2CF2CF3 - CH2(CF2)2〇F3 , ch9 /CF2 /CH2 〆, CF-CH, / \ ch2 ch2 ^CH | CH2(CF2)3CF3 I ch2cf(cf3>2 /CH2, CF-CH / \ /CH2 Ί \CF—CH , / \ , 〆/CH: ^CF-CH % /CH2 CH2 /CH2 XCH / \ CH2 xch2 'CH cf3 J cf2cf3 _ (CF2)3CF3 polymer, can be only by unit (A) The formed polymer oxygen site (A) and the repeating unit formed by the polymerization of other compounds -18-200806698 (15) (hereinafter also referred to as "other units") may also be obtained as a copolymer. In the case of the polymer of the present invention, the unit (A) is preferably contained in an amount of 0.1 to 99.9 mol% relative to the total repeat unit, and the other unit contains ~99.9 mols, % relative to the total repeat unit. Further, the unit (A) may be composed of only one type of unit (a) or 'or two or more types of units (A). Also, in the copolymer, the unit ( A) The arrangement of other units may be either φ-free or block-like. Other repeating units 'for example, (meth) acrylate, non-fluoro olefin, acyclic fluorinated monoene, The repeating unit formed by polymerization of the cyclic fluorinated monoene or fluorodiene is preferred. The weight average molecular weight of the polymer of the present invention is not particularly limited, and is generally preferably from 1,000 to 1,000,000. The product is a polymer with excellent resistance, heat resistance, transparency, durability and light resistance, water repellency, especially dynamic water repellency Φ. The polymer of the invention is very suitable as an optical fiber material and light. Waveguide material, pellicle material, lens material, encapsulating material (for LED, etc.), interlayer insulating film material (for semiconductor elements, liquid crystal display, multilayer wiring board, etc.), antireflection film material for display, oil sealant (for a ventilating fabric, a bearing portion in a motor fluid bearing device, etc.), etc. The polymer of the present invention is usually dissolved in an organic solvent to form a polymer solution. Type used. For example, the group into the polymer solution was applied to a surface of a substrate and then dried via, the membrane (16) of the present invention is a polymer • 19- 200806698 formed on the surface of the substrate. As the coating method, for example, a roll coating method, a smear method, a dipping method, a spin coating method, a water coating method, a mold coating method, a Langmuir Blodgett method, or the like can be used. The amount of the polymer contained in the polymer solution composition can be appropriately adjusted depending on the use, and it is usually 0.01 to 20% by mass based on the organic solvent. The organic solvent may be a fluorine-based organic solvent or a non-fluorine-based solvent. From the viewpoint of having a high solubility of the polymer of the present invention to a non-fluorine-based solvent, it is preferred to use a fluorine-based organic solvent. The organic solvent may be one organic solvent or two or more organic solvents. Specific examples of the non-fluorine-based solvent include alcohols such as methyl alcohol, ethyl alcohol, and diacetone alcohol; acetone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and N-methylpyrrolidone. Ketones such as r-butyrolactone; propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, carbitol acetate, 3-methoxypropionic acid Methyl ester, ethyl 3-ethoxypropionate, methyl yS-methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, citric acid 2 ethoxy Ethyl ester, isoamyl acetate, methyl lactate, ester, ethyl lactate and other esters; aromatic hydrocarbons such as toluene and xylene; propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether, Glycol ethers such as ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether; N,N-dimethylformamide, N,N-dimethylacetamide and the like. Specific examples of the fluorine-based organic solvent include polyfluoro aromatic compounds such as perfluorobenzene, pentafluorobenzene, I3, bis(trifluoromethyl)benzene; perfluoro(tributyl-20-200806698 (17) amine), Polyfluoroalkylamines such as perfluoro(tripropylamine); polyfluoroalkanes such as 2H, 3H-perfluoropentane, 1H-perfluorohexane, perfluorodecalin, perfluorocyclohexane; methyl (perfluoroisopropyl)ether, methyl (perfluorobutyl)ether, methyl (perfluorohexylmethyl) ether, methyl (perfluorooctyl) ether, ethyl (perfluorobutyl) ether, A polyfluoroether such as perfluoro(2-butyltetrahydrofuran). [Embodiment] The present invention will be specifically described by way of examples, but the invention is not construed as being limited thereto. In the examples, the number average molecular weight is called Μη, the weight average molecular weight is called Mw, the benzoquinone peroxide is called ΒΡΟ, the azobisisobutyl group is called ΑΙΒΝ, the tetrahydrofuran is called THF, the dichloropentafluoropropane is called R225, the diisopropyl group. The base peroxydicarbonate is referred to as IPP. Pressure is the absolute pressure unless otherwise stated. The Μη and Mw of the polymer were measured by gel permeation chromatography (internal standard: polystyrene, developing solvent: THF). [Example 1] Production example of CF2 = CFCH2CH((CH2)3CH3)CH2CH = CH2

In a reactor (300 mL internal volume, made of glass), CF2C1CFC1I (192g) and hydrazine (5.8g) were added, and CH2 = CH(CH2)3CH3 (55g) was slowly dropped at 70 °C in the reactor, and dripped. After completion, the mixture was stirred for 3 hours in the reactor. The solution in the reactor was distilled under reduced pressure to obtain a fraction of 80 to 85 ° C / 10 hPa (absolute pressure) of -21 - 200806698 (18) CF2C1CFC1CH2CHI ((CH2)3CH3) (188 g). Add CF2C1CFC1CH2CHI((CH2)3CH3) (188g) and THF (490g) to the reactor (internal volume 2L, made of glass), containing CH2=CHCH2MgCl 2mol/* L at the reactor internal temperature -70 °C The THF solution (3 4 5 g) was added dropwise over 1 hour. After the completion of the dropwise addition, the internal temperature of the reactor was allowed to stand at 0 ° C, and the mixture was further stirred in the reactor for 1 hour. In the reactor, after adding a saturated aqueous solution of ammonium chloride (1 L), the solution in the reactor was separated to recover a solution of the organic layer. After the solution was concentrated, it was distilled under reduced pressure to give a residue of <RTIgt;</RTI>></RTI>> C2C1CFC1CH2CH ((CH2)3CH3) CH2CH=CH2 (96 g). In a reactor (internal volume 500 mL, made of glass), zinc (32 g) and N-methyl-2-pyrrolidone (244 g) were added at a reactor temperature of 75 〇C to make CF2C1CFC1CH2CH((CH2)3CH3)CH2CH Two ch2 (96g) were dripped in 1 hour. After the completion of the dropwise addition, the mixture was stirred in a reactor at a temperature of 75 ° C for 6 hours. The solution in the reactor is distilled under reduced pressure to obtain a fraction of 62 to 63 ° C / 15 hPa of CF 2 = CFCH 2 CH ((CH 2 ) 3 CH 3 ) CH 2 CH = CH 2 ( 34 g ) (hereinafter, also referred to as compound (a-1 ) ). The NMR spectrum of the compound (a-Ι) is shown below. W-NMR (3 99·8 ΜΗζ, solvent: heavy acetone, standard · tetramethyl decane) 5 (ppm): 0·90 (m, 3H), 1·33 (m, 7H), 2.20 (m, 4H) ), 5.05 (m, 2H), 5·80 (m, 1H). 19F-NMR (376.2ΜΗζ, solvent··································· 6 ( m, 1 F). [Example 2] CF2 = CFCH2CH (CH2CF(CF3)2) CH2CH = CH2 Production Example' In a reactor (internal volume 500 mL, made of glass), CH2 di-CH2CH2OCOCH3 (158 g) and AIBN (4 · 7 7 g) were added. (CF3) 2CFI (43 0 g) was gradually dropped at a reactor internal temperature of 65 ° C, and after completion of dropwise addition I, the mixture was stirred in the reactor for 4 hours. The solution in the reactor was recovered, and a reactor (1 L of internal volume, made of glass) containing zinc (105 g) and methanol (446 g) was added, and the recovered solution in the above reactor was slowly dropped at 25 °C. After the completion of the dropwise addition, the mixture was stirred in a reactor at an internal temperature of 25 ° C for 13 hours. The solution in the reactor was distilled under reduced pressure to obtain CH2=CHCH2CF(CF3)2 (199 g) of a fraction of 50 to 55 °C / atmosphere. In the reactor (internal volume 500 mL, made of glass), add φ CF2C1CFC1I (312g) and AIBN (3 · 0 g ), and at the internal temperature of the reactor at 70 ° C, CH2=CHCH2CF(CF3)2 (199g) The mixture was slowly dropped, and after the completion of the dropwise addition, the mixture was stirred in the reactor for 6 hours. The solution in the reactor was distilled under reduced pressure to obtain a fraction of 77 to 80 ° C / 1 lhPa (absolute pressure) of CF2C1CFC1CH2CHI(CH2CF(CF3)2) (43 0g) 〇

In a reactor (internal volume 2L, made of glass), CF2C1CFC1CH2CHI (CH2CF(CF3)2) (43 0g) and THF (935g) were added, and CH2= was added at a reactor temperature of -70 ° C for 1 hour. CHCH2MgCl 2mol/L in THF (482g). Dropping the knot -23- 200806698 (20) After the bundle, the reactor was stirred at the internal temperature of the reactor at 25 ° C for 12 hours. The concentrated liquid obtained by concentrating the filtrate obtained by filtering the solution in the reactor is washed with a 1 m ο 1 /L aqueous hydrochloric acid solution and a saturated saline solution to carry out liquid separation, and distilled under reduced pressure to obtain a distillation at 45 to 48 ° C / 3 hPa. Part of CF2C1CFC1CH2CH (CH2CF(CF3)2) CH2CH = CH2 (1 75 g). In a reactor (internal volume 500 mL, made of glass), zinc (55 g) and N-methyl-2-pyrrolidone (310 g) were added, and CF2C1CFC1CH2CH (CH2CF(CF3)2) was added at a reactor internal temperature of 75 °C. CH2CH-ch2 (1 75 g) was added dropwise over 1 hour, and after completion of the dropwise addition, the mixture was stirred in a reactor at an internal temperature of 75 ° C for 17 hours. The concentrate obtained by concentrating the filtrate obtained by filtering the solution in the reactor is washed with a 1 m ο 1 /L aqueous hydrochloric acid solution and a saturated saline solution, and separated by distillation under reduced pressure at a temperature of 42 to 45 ° C / 20 hPa. Part of 〇? 2 = CFCH2CH(CH2CF(CF3)2)CH2CH = CH2 (92g) (hereinafter, also referred to as compound (a-2)). The NMR spectrum of the compound (a-2) is shown below. !H-NMR (3 99.8MHz, solvent: heavy acetone, standard: tetramethyl cleavage) δ (ppm ) : 2 · 4 2 ( m,7Η ) , 5 · 14 ( m,2 Η ), 5.80 (m 5 1H). 19F-NMR (376.2ΜΗζ, solvent: heavy acetone, standard · CFCls) δ (ppm): -185.1 (m » IF), -172.3 (m, IF), -123.7 (m, IF), -104.9 ( m, IF), -76.5 (m, 6F) ° -24- 200806698 (21) [Example 3] Polymerization example of compound (al) In a pressure-resistant reactor (internal volume 30 mL, made of glass), a compound (a) was added. -1) (2.5g) with ethyl acetate (9.7g), then add 50

A mass % polymerization initiator of IPP in R225 (0.63 g). After degassing under reduced pressure in a pressure-resistant reactor, polymerization was carried out at a reactor temperature of 40 ° C for 18 hours. Next, the solid component formed after the solution in the reactor was dropped into methanol was recovered, and the solid component was vacuum dried at 70 ° C for 24 hours, and then a white powder was obtained at 25 ° C (1.72 g). (hereinafter, also referred to as polymer (A-1)). The polymer (A-1) is a polymer formed by a repeating unit represented by the following formula (A-1).

"CF2 /CH2

^CF-CH (A-1) /CH2 (CH2)3CH3 / \cr " The Mn of the polymer (Α·1) is 5400 and the Mw is 1 03 00. Further, the contact angle of the polymer (A-1) with respect to water was 95°, the rolling angle was 1 Γ, and the receding contact angle was 84°. [Example 4] Polymerization Example of Compound (a-2) (Part 1) In a pressure-resistant reactor (internal volume 3 OmL, made of glass), Compound (a-2) (2.5 g) and ethyl acetate (4.5) were added. g), a solution of R225 (0.21 g) containing IPP of 50% by mass of a polymerization initiator was further added. After degassing under reduced pressure in a pressure-resistant reactor, polymerization was carried out at a reactor temperature of 40 ° C for 18 hours. Next, the solid component formed by the solution in the reactor after dropping into the methanol -25-200806698 (22) is recovered, and the solid component is vacuum-dried at 90 ° C for 24 hours, and then obtained as a white powder at 25 ° C. Polymer (2.17 g) (hereinafter, also referred to as polymer (A-2)). The polymer (A-2) is a polymer formed by a repeating unit (hereinafter, also referred to as unit (A-2)) represented by the following formula (A-2). , [Chemical 8] /CF2 /〇η2 \CF—CH / \ /CH2 XCH I ch2cf (cf (A-2) The polymer (A-2) has a Μη of 7300 and a Mw of 15900. The glass transition temperature of the polymer (A-2) measured by the analytical method was 82 ° C. Further, the contact angle of the polymer (A-2 ) with respect to water was 107 °, the roll angle was 4 °, and the receding contact angle was It is 109°. The polymer (A-2) is soluble relative to acetone, THF, ethyl acetate, R225, and xylene hexafluoride. [Example 5] Polymerization of Compound (a-2) (Part 2) In a pressure-resistant reactor (internal volume 3 OmL, made of glass), compound (a-2) (2.5 g) and ethyl acetate (4.8 g) and isopropanol (〇.9 g) were added, and then placed in a pressure-resistant container. An R225 solution (0.25 g) containing IPP of 50% by mass of a polymerization initiator was added, and after degassing under reduced pressure in a pressure-resistant reactor, polymerization was carried out at a reactor internal temperature of 4 (TC for 18 hours. Second, recovery) The solid component formed after the solution in the reactor is dropped into methanol, and the solid component is vacuum dried at 90 ° C for 24 hours, and then obtained as a white powdery polymer at 25 -26 - 200806698 (23) ° C ( 0.77g ) ( Next, it is also called polymer (A-3). The polymer (a_3) is a polymer formed by the unit (A-2). The polymer (A-3) has a Μη of 4,800 and a Mw of 6,100. The glass transition temperature of the polymer (A-3) determined by the scanning analysis method is 74 ° C. Further, the polymer (A-3 ) is relative to acetone, THF, ethyl acetate, R225 and Xylene hexafluoride is soluble. ^ The present invention can provide a polymer having excellent chemical resistance, heat resistance, transparency, durability, light resistance, water repellency, and particularly excellent water repellency. It is very suitable as an optical fiber material, an optical waveguide material, a pellicle material, a lens material, a packaging material (for LEDs, etc.), an interlayer insulating film material (for semiconductor elements, liquid crystal display, multilayer wiring boards, etc.) And the anti-reflection film material for the display, the oil sealant, etc. Further, the applicant has filed the application of the Japanese Patent φ Application No. 2006-158866, the patent application scope, the abstract, and the like. All cited in this specification and belong to this issue DISCLOSURE The disclosed. -27-

Claims (1)

200806698 (1) X. Patent application scope 1 _ A compound of the following formula (a), CF2-CFCH2CHR(CH2)mCX=CH2 (a) wherein the symbol in the formula has the following meaning, 'R: carbon An alkyl group of 1 to 12 or a fluoroalkyl group having 1 to 12 carbon atoms, ' m : 0, 1 or 2, X: a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Φ 2- is the compound of claim 1, wherein R is a hospital base having 3 to 6 carbon atoms or a gas radical having 3 to 6 carbon atoms. A compound according to claim 1 or 2, wherein R is a polyfluoroalkyl group represented by the formula -CH2RF (wherein RF is a perfluoroalkyl group having 2 to 5 carbon atoms). 4. A method for producing a compound represented by the following formula (a), which comprises reacting a compound represented by the following formula (f) with a compound represented by the following formula (e) to obtain the following formula (d): The compound shown below, and the compound φ is reacted with a compound represented by the following formula (e) to obtain a compound represented by the following formula (b), and secondly, a method of reacting the compound with a dehalogenating agent, CH2 = CHR ( f) CF2YCFIY ( e ) CF2YCFYCH2CHIR ( d) cn2 = CX(CH2)mMgZ ( c) CF2YCFYCH2CHR(CH2)mCX two ch2 ( b) CF2 = CFCH2CHR(CH2)mCX = ch2 ( a ) where the symbol has the lower Meaning, -28- 200806698 (2) R: alkyl group having 1 to 12 carbon atoms or fluoroalkyl group having 1 to 12 carbon atoms, Y, Z: each independently chlorine atom or bromine atom, m: 0, 1 Or 2, X: a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. 5. A polymer containing a repeating unit represented by the following formula (A), [Chemical Formula 1]: CF, K CF-C (A) CH2 (CH2)n, CH IR wherein the symbol in the formula has the following meaning, R: alkyl group having 1 to 12 carbon atoms or fluoroalkyl group having 1 to 12 carbon atoms, m: 0, 1 or 2, X : a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. 6. The polymer of claim 5, wherein R is an alkyl group having 3 to 6 carbon atoms or a polyfluoroalkyl group having 3 to 6 carbon atoms. 7. The polymer of claim 5 or 6, wherein R is a polyfluoroalkyl group of the formula -CH2RF (wherein RF is a perfluoroalkyl group having 2 to 5 carbon atoms). 8. The polymer according to any one of claims 5 to 7, wherein the weight average molecular weight is from 1,000 to 1,000,000. 9. A precision machined component which is a polymer using the fifth, sixth, seventh or eighth aspect of the patent application. -29- 200806698 VII. Designated representative map: (1) The designated representative figure of this case is: None (2), the symbol of the representative figure is simple: no 8. If there is a huayu type in this tea, please reveal the chemical formula that best shows the characteristics of the invention: GHz (CH2)m R -4-