JP2006016571A - Fluorine-containing compound, fluorine-containing cyclic polymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a fluorine-containing polymer that has high concentration of a functional group and sufficient properties of the functional group and causes no lowering in Tg. <P>SOLUTION: The fluorine-containing polymer has a monomer unit obtained by subjecting a fluorine-containing diene represented by formula (1): CF<SB>2</SB>=CFCH<SB>2</SB>-CHQ-R<SP>2</SP>(Q is a (CH<SB>2</SB>)<SB>n</SB>(CF<SB>3</SB>)<SB>2</SB>OR<SP>1</SP>(n is 0 or 1; R<SP>1</SP>is hydrogen, a ≤20C alkyl group, a ≤15C alkoxycarbonyl group or a CH<SB>2</SB>R<SP>3</SP>(R<SP>3</SP>is a ≤15C alkoxycarbonyl group)); R<SP>2</SP>is a cyclic unsaturated hydrocarbon group or an alkyl group in which at least one hydrogen atom is substituted with a cyclic unsaturated hydrocarbon; in R<SP>2</SP>, a part of carbon atoms in the cyclic unsaturated hydrocarbon group may be substituted with a hetero atom or a carbonyl group, a part of hydrogen atoms in the cyclic unsaturated hydrocarbon group may be substituted with a fluorine atom, an alkyl group or a fluoroalkyl group) to cyclic polymerization. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel fluorine-containing compound, an improved fluorine-containing cyclized polymer having a functional group, and a method for producing the same.

  As the fluorine-containing polymer having a functional group, functional group-containing fluorine-containing polymers used for fluorine-based ion exchange membranes and curable fluorine resin coatings are known, but these are all linear polymers having a basic skeleton. And obtained by copolymerization of a fluoroolefin typified by tetrafluoroethylene and a monomer having a functional group.

  Polymers containing a functional group and having a fluorinated alicyclic structure in the main chain are also known. As a method for introducing a functional group into a polymer having a fluorinated alicyclic structure in the main chain, polymerization may be used. A method using terminal groups of the obtained polymer, a method in which a polymer is treated at a high temperature to oxidatively decompose the side chain or terminal of the polymer to form a functional group, a monomer having a functional group is copolymerized, and if necessary In other words, a method of introducing by adding a treatment such as hydrolysis is known (see Patent Documents 1 to 3).

  As a method for introducing a functional group into a polymer having a fluorinated aliphatic ring structure in the main chain, there is the method described above, but in the method of introducing a functional group by treating the terminal group of the polymer, the functional group concentration is low, There is a disadvantage that sufficient functional group characteristics cannot be obtained. Further, in the method of introducing a monomer having a functional group by copolymerization, if the functional group concentration is increased, problems such as a decrease in mechanical properties due to a decrease in glass transition temperature (Tg) occur.

Japanese Patent Laid-Open No. 4-189880 JP-A-4-226177 JP-A-6-220232

  The problem to be solved by the present invention is to provide a fluorine-containing compound, a fluorine-containing polymer, and a method for producing the same, which can obtain a sufficient functional group property with a high functional group concentration and do not cause a decrease in Tg. That is.

In order to solve the above-mentioned problems, the present invention provides the following inventions relating to a fluorine-containing polymer having a functional group or a functional group-containing side chain group directly bonded to a fluorine-containing aliphatic ring.
The present invention provides a fluorinated diene represented by the following formula (1).
_{CF 2 = CFCH 2 -CHQ-R} 2 ··· (1)
However, in formula (1), Q is (CH ₂ ) _n C (CF ₃ ) ₂ OR ¹ (n is 0 or 1, R ¹ is hydrogen, an alkyl group having 20 or less carbon atoms, or an alkoxy group having 15 or less carbon atoms. A carbonyl group or CH ₂ R ³ (R ³ is an alkoxycarbonyl group having 15 or less carbon atoms), and an alkyl group, an alkoxycarbonyl group and R ³ constituting R ¹ are fluorine atoms, part or all of the hydrogen atoms of which are R ² represents a cyclic unsaturated hydrocarbon group or an alkyl group in which at least one hydrogen atom is substituted with a cyclic unsaturated hydrocarbon, and may have an etheric oxygen atom. ² , some of the carbon atoms in the cyclic unsaturated hydrocarbon group may be substituted with hetero atoms or carbonyl groups, and some of the hydrogen atoms in the cyclic unsaturated hydrocarbon group may be fluorine atoms or alkyl groups. , Fluo It may be substituted by an alkyl group.

  The present invention also provides a fluorine-containing polymer having a monomer unit formed by cyclopolymerization of the fluorine-containing diene represented by the above formula (1).

  The present invention also provides a method for producing a fluorine-containing polymer, which comprises cyclopolymerizing the fluorine-containing diene represented by the above formula (1).

  According to the present invention, a fluoropolymer having an aliphatic ring structure in the main chain and a functional group in the side chain can be produced. The fluorine-containing polymer obtained by the present invention has a ring structure in the main chain, and has high chemical stability and heat resistance. In addition, since a functional group is introduced into the ring side chain, sufficient functional group characteristics can be expressed without lowering Tg, which has been difficult to achieve with conventional fluoropolymers. The fluorine-containing polymer of the present invention includes, for example, ion exchange resins, ion exchange membranes, fuel cells, various battery materials, photoresists, optical fibers, electronic members, transparent film materials, thick film films, adhesives, fiber materials, and weather resistance. It can be used for paints.

The present invention makes it possible to produce a fluorinated cyclized polymer having a functional group in the ring side chain.
That is, according to the present invention, a fluorine-containing polymer having a monomer unit obtained by cyclopolymerization of a fluorine-containing diene represented by the following formula (1) (hereinafter sometimes simply referred to as the fluorine-containing diene of the present invention) is obtained. be able to.

_{CF 2 = CFCH 2 -CHQ-R} 2 ··· (1)
However, in formula (1), Q is (CH ₂ ) _n C (CF ₃ ) ₂ OR ¹ (n is 0 or 1, R ¹ is hydrogen, an alkyl group having 20 or less carbon atoms, or an alkoxy group having 15 or less carbon atoms. A carbonyl group or CH ₂ R ³ (R ³ is an alkoxycarbonyl group having 15 or less carbon atoms), and an alkyl group, an alkoxycarbonyl group and R ³ constituting R ¹ are fluorine atoms, part or all of the hydrogen atoms of which are R ² represents a cyclic unsaturated hydrocarbon group or an alkyl group in which at least one hydrogen atom is substituted with a cyclic unsaturated hydrocarbon, and may have an etheric oxygen atom. ² , some of the carbon atoms in the cyclic unsaturated hydrocarbon group may be substituted with hetero atoms or carbonyl groups, and some of the hydrogen atoms in the cyclic unsaturated hydrocarbon group may be fluorine atoms or alkyl groups. , Fluo It may be substituted by an alkyl group.

  In the formula (1), the cyclic unsaturated hydrocarbon group is a hydrocarbon group in which at least one of adjacent carbon-carbon bonds among the carbon atoms constituting the ring is an unsaturated bond, and is a monocyclic unsaturated carbon group. Examples thereof include hydrogen, a polycyclic unsaturated hydrocarbon, a condensed polycyclic hydrocarbon partially hydrogenated, a bridged cyclic hydrocarbon having an unsaturated bond, and a spiro hydrocarbon having an unsaturated bond. The number of carbon atoms constituting the ring is preferably 4 to 6, and a part of the carbon atoms may be substituted with a hetero atom or a carbonyl group. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom, and among them, an oxygen atom is preferable. The number of unsaturated bonds is preferably one or two, and cyclic unsaturated hydrocarbons having one unsaturated bond are particularly preferable. A part of hydrogen atoms in the cyclic unsaturated hydrocarbon may be substituted with a fluorine atom, an alkyl group, or a fluoroalkyl group. As the alkyl group, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is particularly preferable. The fluoroalkyl group also preferably has 1 to 3 carbon atoms, and particularly preferably a trifluoromethyl group. Specifically, a monocyclic group such as a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group as shown below, a multicyclic group such as a 4-cyclohexylcyclohexenyl group, a condensed ring group such as a hydronaphthenyl group, and a norbornenyl group Spiro ring groups such as a polycyclic group and a spiro [3.4] octenyl group are included. Moreover, a methylcyclopentenyl group, a trifluoromethylcyclopentenyl group, a methylcyclohexenyl group, a trifluoromethylhexenyl group, a dihydrofuryl group, a dihydropyranyl group, a cyclohexenonyl group, a cyclopentenonyl group, and the like can be given. Preferably, it is a cyclopentenyl group, a cyclohexenyl group, or a dihydrofuryl group.

As the alkyl group constituting the alkyl group in which at least one hydrogen atom is substituted with a cyclic unsaturated hydrocarbon, it is preferable that only one hydrogen atom is substituted with a cyclic unsaturated hydrocarbon group. Moreover, as this alkyl group, a C1-C4 alkyl group is preferable and a methyl group is especially preferable. Most preferred is a methyl group in which one of the hydrogen atoms is substituted with a cyclic unsaturated hydrocarbon group. Specifically, the cyclic unsaturated hydrocarbon group in the above specific examples such as cyclopentenylmethyl group and cyclohexenylmethyl group is substituted. A methyl group is mentioned. When the alkyl group having 1 to 4 carbon atoms is not a methyl group, an alkyl group having 2 to 4 carbon atoms in which one of the hydrogen atoms at the 1-position of the alkyl group is substituted with a cyclic unsaturated hydrocarbon is preferable.
When R ² is a cyclic unsaturated hydrocarbon group, the carbon atom adjacent to the carbon atom forming the unsaturated bond is bonded to the remaining part of formula (1) as shown in formula (2). Is preferred. When R ² is an alkyl group in which at least one hydrogen atom is substituted with a cyclic unsaturated hydrocarbon group, the alkyl group is a methyl group and forms an unsaturated bond as shown in formula (3). The carbon atom to be bonded is preferably bonded to the carbon atom of the methyl group.

Specific examples of the fluorine-containing diene of the present invention include those represented by the following formula, but are not limited thereto.

In the above formula, R ¹ is a hydrogen atom, an alkyl group having 20 or less carbon atoms, an alkoxycarbonyl group having 15 or less carbon atoms, or CH ₂ R ³ (R ³ is an alkoxycarbonyl group having 15 or less carbon atoms), and the alkyl The group preferably has 15 or less carbon atoms, and the alkoxycarbonyl group preferably has 12 or less carbon atoms. The alkyl group, alkoxycarbonyl group, and R ³ constituting R ¹ may have some or all of the hydrogen atoms substituted with fluorine atoms, or may have an etheric oxygen atom. Specific examples methyl group, a trifluoromethyl _{group, - (t-C 4 H} 9), - CH 2 OCH 3, -CH 2 O-C 2 H 5, -CH 2 OCH 2 CF 3, -C (O _{) O (t-C 4 H} 9), - CH 2 C (O) O (t-C 4 H 9), 2- tetrahydropyranyl group, -C (O) O (adM ), - CH 2 C ( O) O (AdM) and those shown below. (However, AdM represents a 2-methyladamantyl-2-yl group, and is represented in the form of -OR ¹ in order to clarify the bonding position.)

上記式（４）または（５）において、Ｑは式（１）について上記した通りである。 The fluorine-containing diene of the present invention is preferably represented by the following formula (4) or (5) because it is easily available and gives a polymer having a high Tg and excellent mechanical properties.

In the above formula (4) or (5), Q is as described above for the formula (1).

The fluorine-containing polymer of the present invention has monomer units formed by cyclopolymerizing the above-described fluorine-containing diene of the present invention.
The structure of this monomer unit is such that when R ² is a cyclic unsaturated hydrocarbon group and has the structure represented by formula (2), and R ² is substituted with at least one hydrogen atom by a cyclic unsaturated hydrocarbon group A case where the alkyl group is a group having a structure represented by the formula (3) will be described as an example. In the case of the former (formula (2)), from the result of spectroscopic analysis, etc., the fluoropolymer of the present invention has at least one of the following monomer units (a), (b) or (c) as a repeating unit. It is thought that it has the structure. The main chain of the cyclized polymer refers to a carbon chain composed of four carbon atoms that form a polymerizable unsaturated bond.

In the latter case (formula (3)), from the result of spectroscopic analysis, etc., the fluorine-containing polymer of the present invention contains at least one of the following monomer units (d), (e) or (f). It is considered that the structure has a repeating unit. The main chain of this cyclized polymer refers to a carbon chain composed of four carbon atoms that constitute a polymerizable unsaturated bond.

  In the monomer units (a) to (f), Q is as described above for the formula (1).

In the fluorine-containing polymer of the present invention, when OR ¹ is an acidic group, such as when R ¹ is a hydroxyl group, the acidic group reacts with a blocking agent such as alcohols, carboxylic acids, or active derivatives thereof. And may be blocked. Here, examples of the active derivative include alkyl halides, acid chlorides, acid anhydrides, chlorocarbonates, dialkyl dicarbonates (such as di-tert-butyl dicarbonate), and 3,4-dihydro-2H-pyran. .

Specific examples of R ¹ as the blocked acidic group include a methoxymethyl group, an ethoxymethyl group, a 2-methoxyethoxymethyl group, COO (t-C ₄ H ₉ ), CH (CH ₃ ) OC ₂ H ₅ , 2 In addition to the tetrahydropyranyl group, the following groups are exemplified.

Moreover, the following huge blocked acidic groups having 20 or more carbon atoms can be introduced.

  Specific examples of reagents useful as blocking agents are described in A. J. Pearson and W. R. Roush, edited by Handbook of Reagents for Organic Sybthesis: Activating Agents and Protecting Groups, John Wiley & Sons (1999).

In the fluorine-containing polymer of the present invention, (the ratio of OR ¹ which is blocked to the total number of acidic groups OR ¹⁾ block Karitsu of OR ¹ is an acidic group is preferably 10 to 100 mol%, in particular 10 to 50 mol% Is preferred.

  The fluorine-containing polymer of the present invention must contain at least one repeating unit among monomer units formed by cyclopolymerization of the fluorine-containing diene represented by the above formula (1). A monomer unit derived from a radically polymerizable monomer other than those may be included as long as it is not impaired. In this case, the proportion of other monomer units is preferably 50 mol% or less, particularly preferably 30 mol% or less.

Examples of other monomers that can be exemplified include α-olefins such as ethylene, propylene, and isobutylene, fluorine-containing olefins such as tetrafluoroethylene and hexafluoropropylene, and perfluoro (2,2-dimethyl-1,3-dioxole). Fluorinated cyclic monomers, perfluorodienes and hydrofluorodienes that can undergo cyclopolymerization such as perfluoro (butenyl vinyl ether), acrylic esters such as methyl acrylate and ethyl methacrylate, vinyl acetate, vinyl benzoate, Monomers derived from vinyl esters such as vinyl adamantylate, vinyl ethers such as ethyl vinyl ether and cyclohexyl vinyl ether, cyclic olefins such as cyclohexene, norbornene and norbornadiene, maleic anhydride, vinyl chloride, etc. Unit, and the like.
In addition, a monomer having a blocked acidic group can also be used. (Meth) acrylic acid esters such as tetrahydropyranyl acrylate, vinyl ethers such as tert-butyl vinyl ether, CH ₂ ═CHCH ₂ C (CF ₃ ) ₂ OCO ₂ —tC ₄ H ₉ , CH ₂ ═CHCH _{2 C (CF 3) 2 OCH (} CH 3) OC 2 H 5 and the like.

Of these, the following hydrofluorodienes, acrylic esters and methacrylic esters are preferred.
_{CF 2 = CFCF 2 -C (CF} 3) (OH) -CH 2 CH = CH 2
_{CF 2 = CFCF 2 -C (CF} 3) (OCH 2 OCH 3) -CH 2 CH = CH 2
_{CF 2 = CFCH 2 -CH (CH} 2 C (CF 3) 2 OH) -CH 2 CH = CH 2
_{CF 2 = CFCH 2 -CH (CH} 2 C (CF 3) 2 OCH 2 OCH 3) -CH 2 CH = CH 2
_{CF 2 = CFCH 2 -CH (C} (CF 3) 2 OH) -CH 2 CH = CH 2
_{CF 2 = CFCH 2 -CH (C} (CF 3) 2 OCH 2 OCH 3) -CH 2 CH = CH 2
CH ₂ = CHC (O) OR
CH ₂ = C (CH ₃ ) C (O) OR
CH ₂ = CFC (O) OR
CH ₂ = C (CF ₃ ) C (O) OR

In the above formula, specific examples of the OR group include the following groups.
OC (CH ₃ ) ₃ , OCH (CF ₃ ) ₂

  The molecular weight of the fluoropolymer of the present invention is appropriately selected according to the application. For example, when used as a photoresist material, since it is necessary to be able to be uniformly dissolved in an organic solvent and to be uniformly applied to a substrate, the number average molecular weight in terms of polystyrene is usually 1,000 to 100,000. Appropriate, preferably 2,000 to 20,000. If the number average molecular weight is less than 1,000, the resulting resist pattern tends to be defective, the remaining film ratio after development is lowered, and the shape stability during pattern heat treatment is liable to occur. On the other hand, if the number average molecular weight exceeds 100,000, the coating property of the composition may be poor or the developability may be deteriorated.

  The fluorine-containing polymer of the present invention can be obtained by cyclopolymerizing the fluorine-containing diene of the present invention under a polymerization initiation source. In this specification, when it says cyclopolymerization, in addition to cyclopolymerizing one kind of fluorine-containing diene of the present invention to obtain a homopolymer, two or more fluorine-containing dienes are cyclopolymerized, In addition, a copolymer is obtained by copolymerization, and a copolymer having another monomer unit as a repeating unit is obtained by copolymerization with the above-mentioned other monomer while cyclopolymerizing the fluorinated diene of the present invention. Including that.

The polymerization initiation source is not particularly limited as long as the polymerization reaction proceeds radically, and examples thereof include a radical generator, light, and ionizing radiation. In particular, radical generators are preferable, and peroxides, azo compounds, persulfates and the like are exemplified. Of these, the following peroxides are preferred.
_{C 6 H 5 -C (O)} O-OC (O) -C 6 H 5
_{C 6 F 5 -C (O)} O-OC (O) -C 6 F 5
_{C 3 F 7 -C (O)} O-OC (O) -C 3 F 7
(CH ₃ ) ₃ C—C (O) O—OC (O) —C (CH ₃ ) _{3
(CH 3) 2 CH-C} (O) O-OC (O) -CH (CH 3) 2
_{(CH 3) 3 C-C} 6 H 10 -C (O) O-OC (O) -C 6 H 10 -C (CH 3) 3
(CH ₃ ) ₃ C—O—C (O) O—OC (O) —O—C (CH ₃ ) ₃
(CH ₃ ) ₂ CH—O—C (O) O—OC (O) —O—CH (CH ₃ ) ₂
(CH ₃ ) ₃ C—C ₆ H ₁₀ —O—C (O) O—OC (O) —O—C ₆ H ₁₀ —C (CH ₃ ) ₃
However, -C ₆ H ₅ represents a phenyl group, -C ₆ F ₅ is heptafluoro phenyl group, -C ₆ H ₁₀ is cyclohexylene.

  The polymerization method is not particularly limited, so-called bulk polymerization in which the monomer is directly subjected to polymerization, fluorinated hydrocarbon, chlorinated hydrocarbon, fluorinated chlorinated hydrocarbon, alcohol, hydrocarbon, and other organic materials that dissolve the monomer. Examples include solution polymerization performed in a solvent, suspension polymerization performed in the presence or absence of a suitable organic solvent in an aqueous medium, and emulsion polymerization performed by adding an emulsifier to an aqueous medium.

  The organic solvent used as a solvent in the polymerization is not limited to one type, and may be a mixed solvent of a plurality of types of organic solvents. Specifically, aliphatic hydrocarbons such as pentane, hexane, and heptane, hydrocarbon alcohols such as methanol, ethanol, n-propanol, isopropanol, and t-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like. Hydrocarbon ketones, hydrocarbon ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, methyl t-butyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and cyclic aliphatic hydrocarbons such as tetrahydrofuran and 1,4-dioxane Ethers, nitriles such as acetonitrile, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, t-butyl acetate, methyl propionate, propionic acid Hydrocarbon esters such as chill, aromatic hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, R-113, R-113a, R-141b, R-225ca , Fluorochlorinated hydrocarbons such as R-225cb, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, 1,1,1, Fluorinated hydrocarbons such as 2,2,3,3,4,4-nonafluorohexane, fluorinated hydrocarbon ethers such as methyl 2,2,3,3-tetrafluoroethyl ether, 2,2, 2-trifluoroethanol, 1,1,1,3,3,3-hexafluoroisopropanol, 2,2,3,3-tetrafluoropropanol, 2,2,3,3,4,4,5,5- Fluorohydrocarbons such as octafluoropentanol Alcohols such including but not limited to.

  The temperature and pressure at which the polymerization is carried out are not particularly limited, but are preferably set appropriately in consideration of various factors such as the boiling point of the monomer, the required heating source and the removal of the polymerization heat. For example, a suitable temperature can be set between 0 ° C. and 200 ° C., and a practically suitable temperature can be set if it is about room temperature to 100 ° C. The polymerization pressure may be reduced or increased. Practically, suitable polymerization can be carried out at atmospheric pressure to about 100 atm, and even at atmospheric pressure to about 10 atm.

As described above, in the fluorine-containing polymer of the present invention, the OR ¹ group that is an acidic group may be blocked. In order to obtain a fluorine-containing polymer in which the OR ¹ group which is an acidic group is blocked, a fluorine-containing diene in which the OR ¹ group is not blocked is cyclopolymerized to produce a fluorine-containing polymer. The OR ¹ group in the fluorine-containing polymer may be blocked with a blocking agent, or the fluorine-containing diene in which the OR ¹ group is blocked with a blocking agent in advance is subjected to cyclopolymerization so that the OR ¹ group is A blocked fluorine-containing polymer may be obtained.

Next, although the Example of this invention is described concretely, this invention is not limited to these. Abbreviations used in the following examples are as follows.
THF; tetrahydrofuran, BPO; benzoyl peroxide, PFBPO; perfluorobenzoyl peroxide, PFB; perfluorobutyryl peroxide, PSt; polystyrene, R225; dichloropentafluoropropane (solvent).

１Ｌのガラス反応器にＣＦ₂ＣｌＣＦＣｌＩの５００ｇ、ＣＨ₂=ＣＨＣ(ＣＦ₃) ₂ＯＨの３４４gとＢＰＯの３２．６gを入れ、９５℃で７１時間加熱した。反応粗液を減圧蒸留して、５４４ｇのＣＦ₂ＣｌＣＦＣｌＣＨ₂ＣＨＩ(Ｃ(ＣＦ₃)₂ＯＨ) (５５−５８℃／０．２ｋＰａ）を得た。
５Ｌのガラス反応器に上記で合成したＣＦ₂ＣｌＣＦＣｌＣＨ₂ＣＨＩ(Ｃ(ＣＦ₃) ₂ＯＨ)の３４４ｇと脱水ＴＨＦの１．７Ｌを入れ、−７０℃に冷却した。そこに１−ブロモ−２−シクロペンテンとマグネシウムから調製した２-シクロペンテニルマグネシウムブロミドの２Ｍ ＴＨＦ溶液１．８Ｌを窒素雰囲気下で約５．５時間かけて滴下した。
０℃まで昇温し、１６時間攪拌した後、飽和塩化アンモニウム水溶液１．６Ｌを添加して室温まで昇温した。反応液を分液し、有機層をエバポレーターで濃縮し、次いで減圧蒸留して２４０ｇの化合物Ｘ（１，２−ジクロロ−１，１，２，６，６，６−ヘキサフルオロ−４−（２−シクロペンテニル−１−イル）−５−トリフルオロメチル−５−ヒドロキシヘキサン）を得た。

１Ｌのガラス反応器に亜鉛７６ｇと水３００ｇを入れ、９０℃に加熱した。そこに上記で合成した化合物Ｘの２４０ｇを滴下し、２４時間攪拌した。反応液に塩酸７０ｍＬを滴下して２時間攪拌した後、ろ過して分液し、減圧蒸留して１４９ｇの含フッ素ジエン化合物（６）を得た。 (Example 1)
Synthesis of 1,1,2,6,6,6, -hexafluoro-4- (2-cyclopentenyl-1-yl) -5-trifluoromethyl-5-hydroxyhexene (6)

CF ₂ ClCFClI of 500g glass reactor 1L, put _{CH 2 = CHC (CF 3)} 2 OH of 344g and BPO of 32.6 g, was heated for 71 hours at 95 ° C.. The reaction crude liquid was distilled under reduced pressure to obtain 544 g of CF ₂ ClCFClCH ₂ CHI (C (CF ₃ ) ₂ OH) (55-58 ° C./0.2 kPa).
In a 5 L glass reactor, 344 g of CF ₂ ClCFClCH ₂ CHI (C (CF ₃ ) ₂ OH) synthesized above and 1.7 L of dehydrated THF were placed and cooled to −70 ° C. Thereto, 1.8 L of a 2M THF solution of 2-cyclopentenylmagnesium bromide prepared from 1-bromo-2-cyclopentene and magnesium was added dropwise over about 5.5 hours under a nitrogen atmosphere.
After heating up to 0 degreeC and stirring for 16 hours, 1.6 L of saturated ammonium chloride aqueous solution was added and it heated up to room temperature. The reaction solution was separated, the organic layer was concentrated with an evaporator, and then distilled under reduced pressure to give 240 g of compound X (1,2-dichloro-1,1,2,6,6,6-hexafluoro-4- (2 -Cyclopentenyl-1-yl) -5-trifluoromethyl-5-hydroxyhexane).

A 1 L glass reactor was charged with 76 g of zinc and 300 g of water and heated to 90 ° C. 240 g of the compound X synthesized above was dropped therein and stirred for 24 hours. To the reaction solution, 70 mL of hydrochloric acid was added dropwise and stirred for 2 hours, followed by filtration, liquid separation, and distillation under reduced pressure to obtain 149 g of a fluorinated diene compound (6).

NMR spectrum
¹⁹ F-NMR (376.2 MHz, solvent: CDCl ₃ , standard: CFCl ₃ )
δ (ppm):
-73.6 (m, 6F), -104.1 (m, 1F), -123.1 (m, 1F), -175.4 (m, 1F).

実施例１において、１−ブロモ−２−シクロペンテンとマグネシウムから調製した２−シクロペンテニルマグネシウムブロミドの替わりに、１−ブロモ−２−シクロヘキセンとマグネシウムから調製した１−シクロヘキセニルマグネシウムブロミドを用いることによって、含フッ素ジエン化合物（７）を得ることができる。 (Example 2)
Synthesis of 1,1,2,6,6,6-hexafluoro-4- (2-cyclohexenyl-1-yl) -5-trifluoromethyl-5-hydroxyhexene (7)

In Example 1, instead of 2-cyclopentenylmagnesium bromide prepared from 1-bromo-2-cyclopentene and magnesium, 1-cyclohexenylmagnesium bromide prepared from 1-bromo-2-cyclohexene and magnesium was used. A fluorine-containing diene compound (7) can be obtained.

実施例１において、１−ブロモ−２−シクロペンテンとマグネシウムから調製した２−シクロペンテニルマグネシウムブロミドの替わりに、１−ブロモメチル−１−シクロペンテンとマグネシウムから調製した１−シクロペンテニルメチルマグネシウムブロミドを用いることによって、含フッ素ジエン化合物（８）を得ることができる。 (Example 3)
1,1,2,6,6,6, -hexafluoro-4- (1-cyclopentenylmethyl) -5-trifluoromethyl-5-hydroxyhexene (8)

In Example 1, instead of 2-cyclopentenylmagnesium bromide prepared from 1-bromo-2-cyclopentene and magnesium, 1-cyclopentenylmethylmagnesium bromide prepared from 1-bromomethyl-1-cyclopentene and magnesium was used. A fluorine-containing diene compound (8) can be obtained.

実施例１において、１−ブロモ−２−シクロペンテンとマグネシウムから調製した２−シクロペンテニルマグネシウムブロミドの替わりに、４−ブロモ−２，３−ジヒドロフランとマグネシウムから調製したグリニャール反応剤を用いることによって、含フッ素ジエン化合物（９）を得ることができる。 (Example 4)
1,1,2,6,6,6, -hexafluoro-4- (2-cyclopentenyl-4-oxo-1-yl) -5-trifluoromethyl-5-hydroxyhexene (9)

In Example 1, instead of 2-cyclopentenylmagnesium bromide prepared from 1-bromo-2-cyclopentene and magnesium, by using a Grignard reagent prepared from 4-bromo-2,3-dihydrofuran and magnesium, A fluorine-containing diene compound (9) can be obtained.

実施例１において、１−ブロモ−２−シクロペンテンとマグネシウムから調製した２−シクロペンテニルマグネシウムブロミドの替わりに、１−ブロモ−４−トリフルオロメチル−２−シクロペンテンとマグネシムから調製したグリニャール反応剤を用いることによって、含フッ素ジエン化合物（１０）を得ることができる。 (Example 5)
1,1,2,6,6,6, -hexafluoro-4- (2-cyclopentenyl-4-trifluoromethyl-1-yl) -5-trifluoromethyl-5-hydroxyhexene (10)

In Example 1, instead of 2-cyclopentenylmagnesium bromide prepared from 1-bromo-2-cyclopentene and magnesium, a Grignard reagent prepared from 1-bromo-4-trifluoromethyl-2-cyclopentene and magnesium is used. As a result, the fluorinated diene compound (10) can be obtained.

(Example 6)
4 g of the fluorine-containing diene compound (6) obtained in Example 1 and 2.2 g of ethyl acetate were charged into a glass pressure-resistant reactor having an internal volume of 30 mL. Next, 6.23 g of a 3 wt% R225 solution of PFB was added as a polymerization initiator. After the system was frozen and degassed, it was sealed and polymerized in a constant temperature shaking tank (20 ° C.) for 41 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, followed by vacuum drying at 90 ° C. for 21 hours. As a result, 1.33 g of an amorphous polymer having a fluorine-containing ring structure in the main chain represented by the following formula was obtained. The PSt equivalent molecular weight measured by GPC using THF as a solvent is a number average molecular weight (Mn) 10600, a weight average molecular weight (Mw) 21300, and Mw / Mn = 2.01. It was. The obtained polymer was soluble in acetone, THF, methanol, and R225.

Claims (3)

A fluorine-containing diene represented by the formula (1).
_{CF 2 = CFCH 2 -CHQ-R} 2 ··· (1)
(In the formula (1), Q is (CH ₂ ) _n C (CF ₃ ) ₂ OR ¹ (n is 0 or 1, R ¹ is hydrogen, an alkyl group having 20 or less carbon atoms, or 15 or less carbon atoms) An alkoxycarbonyl group or CH ₂ R ³ (R ³ is an alkoxycarbonyl group having 15 or less carbon atoms), and an alkyl group, an alkoxycarbonyl group, and R ³ constituting R ¹ are fluorine atoms in which some or all of the hydrogen atoms are fluorine. R ² represents a cyclic unsaturated hydrocarbon group or an alkyl group in which at least one hydrogen atom is substituted with a cyclic unsaturated hydrocarbon. In R ² , some of the carbon atoms in the cyclic unsaturated hydrocarbon group may be substituted with hetero atoms or carbonyl groups, and some of the hydrogen atoms in the cyclic unsaturated hydrocarbon group may be fluorine atoms, alkyls Group, full Roarukiru may be substituted in the group.)   A fluorine-containing polymer having a monomer unit obtained by cyclopolymerizing the fluorine-containing diene according to claim 1.   A method for producing a fluorine-containing polymer, comprising cyclopolymerizing the fluorine-containing diene according to claim 1.