JPH10251351A - Fluoroalkyl group-bearing compound, its production and polyelectrolyte - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject novel compound that is prepared by introduction of fluoroalkyl groups directly via the carbon-carbon bond and is useful in cosmetics and surfactants. SOLUTION: This novel compound is represented by the formula: RF-(CH2 CR<1> L)m1 -(CH2 CR<1> R<4> )m2 -RF R<1> is H, methly; L is C(=O)O(CH2 CH2 O)p R<1> , C(=O)O(CH2 CHMeO)p R<1> , C(=O)O(CH2 CH2 O)p -(CH2 CHMeO)q R<1> , C(=O)O(CH2 CH2 O)p -(CH2 CH2 CH2 CH2 O)q R<1> ; p, q are each 1-100; R<4> is -C(=O)R<6> ; R<6> is a 1-20C alkylamino, pyrrolidino; m1 and m2 are each 0-5,000; RF is-(CF2 )n1 X, -CF(CF3 )[OCF2 CF (CF3 )]n2 -OC3 F7 ; X is H, Cl, F; n1 is 1-10; n2 is 0-8} and has a molecular weight of 300-1,000,000, for example, the compound of the formula: C3 H7 OCF(CF3 )-[CH2 CHCOO(CH2 CH2 O)4-5 CH3 ]-[CH2 CHCOOH]-C3 F7 OCF(CF3 ). The compound of the formula: RF-(CH2 CR<1> L)m1 -(CH2 CR<1> R<4> )m2 -RF is prepared by reaction of a peroxyfluoroalkanoyl of the formula: RFC(=O)OO(=O)CR4 with a compound of the formula: CH2 =CR<1> L and a compound of the formula: CH2 =CR<1> R<4> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel fluoroalkyl group-containing compound, a method for producing the same, and a solid polymer electrolyte.

[0002]

2. Description of the Related Art In recent years, compounds containing a fluoroalkyl group in an organic compound have attracted attention as useful compounds such as light resistance, water and oil repellency, and physiological activity.
In particular, a fluoroalkyl group-containing polymer having a fluoroalkyl group introduced into an organic compound has a low surface tension, a low refractive index, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, mold release, In various fields because of having excellent properties such as chemical properties, for example, a surface for imparting water and oil repellency and stain resistance to surfaces of optical lenses, eyeglass lenses, glassware, paints, etc. It is considered to be useful in the fields of processing agents, cosmetics, biomaterials, raw materials for medicines and agricultural chemicals, and materials for imparting releasability. In particular, compounds having a hydroxyl group or a carboxyl group, and further having a fluoroalkyl group introduced at the polymerization end, have been widely developed in various material fields as materials exhibiting excellent aggregation functions caused by fluorine. It is an expected useful compound. However, there is no report on the synthesis of these compounds. Furthermore, since the conventional fluoroalkyl group-containing compound is easily introduced through an ester bond or an amino bond, [for example, a fluorine-containing epoxy compound in which a fluoroalkyl group is introduced through an amino bond; J . Fluorine
Chem., 55, 1 (1991)], and generally have disadvantages such as low weather resistance. Therefore, development of a fluoroalkyl group-containing polymer in which a fluoroalkyl group is directly introduced through a carbon-carbon bond is an important study item.

On the other hand, as a polymer solid electrolyte of a lithium battery, a solution in which an inorganic alkali salt is dissolved in an aprotic solvent (electrolyte solution) is used, but the electrolyte solution flows out during battery assembly. Easy to seal the can body,
Further, there is a problem that a leak liquid is easily generated even after the battery is assembled. In order to solve the drawbacks of the electrolytic solution, the development of an organic or inorganic solid electrolyte is strongly desired. In order to solve such a problem, in particular, a fluorine in which the effect of fluorine is efficiently exhibited. In fact, there is a strong demand for the development of alkyl group-containing solid electrolytes.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a low surface tension, low refractive index, heat resistance, cold resistance, oil resistance, electrical insulation, antifogging property, antifouling property, release property, optical lens. It has excellent properties such as water / oil repellency, stain resistance and chemical resistance on the surface of eyeglass lenses, glassware, paints, etc., and fluoroalkyl groups useful as cosmetics and even surfactants are directly carbon-based. An object of the present invention is to provide a compound containing a fluoroalkyl group introduced by a carbon bond. Further objects of the present invention are:
An object of the present invention is to provide a method for producing a fluoroalkyl group-containing compound in which a fluoroalkyl group is introduced by a carbon-carbon bond easily and in a high yield without using a reaction catalyst and a special device. Another object of the present invention is to provide a fluoroalkyl group-containing ion conductor in which the effect of fluorine is sufficiently exhibited.

[0005]

According to the present invention, the following general formula (I): R _F- (CH ₂ CR ¹ L) _m1- (CH ₂ CR ¹ R ⁴ ) _m2 -R _F (I) [wherein, R ¹ represents a hydrogen atom or a methyl group, and L represents C (= O) O
(CH ₂ CH ₂ O) _p R ¹ , C (= O) O (CH ₂ CHMeO) _p R ¹ , C (= O) O (CH ₂ CH
₂ O) _p- (CH ₂ CHMeO) _q R ¹ , C (= O) O (CH ₂ CH ₂ O) _p- (CH ₂ CH ₂ CH ₂ CH ₂
O) _q R ¹ or Si (CH ₃ ) ₂ (OCH ₂ CH ₂ ) _m OR ² (m represents an arbitrary integer of 1 to 20, R ² represents an alkyl group having 1 to 4 carbon atoms,
When L is Si (CH ₃ ) ₂ (OCH ₂ CH ₂ ) _m OC ₂ H ₅ , _{m 2} may be 0), R ⁴ is —C (= O) R ⁶ , and R _F is — (CF ₂ ) _n1 X, -CF
_{(CF 3) [OCF 2 CF} (CF 3)] indicates _n2 -OC ₃ F _7, and m1 and m @ 2 0 to 5
An integer of 000 (provided that p and q each represent an integer of 1 to 100, m1 represents an integer of 1 or more, and R ⁶ represents
20 represents an alkylamino group, a dialkylamino group, a pyrrolidino group, a piperidino group, or a morpholino group;
X represents a fluorine atom, a chlorine atom or a hydrogen atom, and n2 represents an integer of 0 to 8)]], and a fluoroalkyl group-containing compound having a molecular weight of 300 to 1,000,000 is provided.

Further, in the present invention, the following general formula (I)
_{I) R F C (= O} ) OO (O =) CR F (II) [ wherein, R _F is as above. And a fluoroalkanoyl peroxide represented by the following general formula (III) CH ₂ = CR ¹ L (III) and the following general formula (IV) CH ₂ = CR ¹ R ⁴ (IV) wherein L and R ¹ , R ⁴ is as defined above. And a method for producing the fluoroalkyl group-containing compound.

Furthermore, in the present invention, at least the following general formula _{(I) R F - (CH} 2 CR 1 L) m1 - (CH 2 CR 1 R 4) m2 -R F (I) [ In the formula, R ¹ , L, R ^4, R _F is as above. However, R ⁴ is a halogen atom, a cyano group, Si (R ⁵ ) ₃ or -C (= O) OR ⁹
R ⁵ represents an alkyl group having 1 to 4 carbon atoms, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, CH ₂ CH ₂ CH ₂ Si (R ¹⁰ ) ₃ and R ¹⁰ represents an alkyl group or an alkoxy group having 1 to 4 carbon atoms. And a polymer electrolyte comprising the above-mentioned fluoroalkyl group-containing compound having a molecular weight of 300 to 1,000,000 and at least one electrolyte.

Further, in the present invention, at least one of the electrolytes is an alkali metal salt, a quaternary ammonium salt,
There is provided a polyelectrolyte that is a secondary phosphonium salt, a transition metal salt or a protic acid. You. Further, the present invention provides a polymer electrolyte to which a plasticizer is added.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in more detail. The fluoroalkyl group-containing compound of the present invention has the following general formula (I): R _F- (CH ₂ CR ¹ L) _m1- (CH ₂ CR ¹ R ⁴ ) _m2 -R _F (I) wherein R ¹ is Represents a hydrogen atom or a methyl group, L is C (= O) O
(CH ₂ CH ₂ O) _p R ¹ , C (= O) O (CH ₂ CHMeO) _p R ¹ , C (= O) O (CH ₂ CH
₂ O) _p- (CH ₂ CHMeO) _q R ¹ , C (= O) O (CH ₂ CH ₂ O) _p- (CH ₂ CH ₂ CH ₂ CH ₂
O) _q R ¹ or Si (CH ₃ ) ₂ (OCH ₂ CH ₂ ) _m OR ² (m represents an arbitrary integer of 1 to 20, R ² represents an alkyl group having 1 to 4 carbon atoms,
When L is Si (CH ₃ ) ₂ (OCH ₂ CH ₂ ) _m OC ₂ H ₅ , m1 may be 0), and R ⁴ is a halogen atom, a cyano group, Si (R ⁵ )
₃ , -C (= O) OR ⁹ , -C (= O) R ⁶ , R _{F is-} (CF ₂ ) _n1 X, -CF (CF ₃ )
_{[OCF 2 CF (CF 3)} ] indicates _n2 -OC ₃ F _7, m1 and m2 represents an integer of 0 to 5000 (where, p, q represents any integer 1 to 100, m1 is 1 or more R ⁹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, CH ₂ CH ₂ CH ₂ Si (R ¹⁰ ) ₃ , and R ⁶ represents a carbon atom 1-2
0 represents an alkylamino group, a dialkylamino group, a pyrrolidino group, a piperidino group, or a morpholino group; R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms; an alkoxy group;
X is a fluorine atom, a chlorine atom, or a hydrogen atom, and n2 is an integer of 0 to 8)]], which is a fluoroalkyl group-containing compound having a molecular weight of 300 to 1,000,000.

In the above, L is Si (CH ₃ ) ₂ (OCH ₂ CH ₂ ) _n OR ²
Are preferred. m is preferably 1 to 15, particularly preferably 1 to 10, and m1 and m2 are preferably 1 to 1
000, particularly preferably 1 to 500, but L is Si (C
_{H 3) 2 (OCH 2 CH} 2) m2 in the case of _n OR ² is preferably 1 to 100
0, particularly preferably 0 to 500. p and q are preferably 3 to 50, particularly preferably 5 to 10. R ² is preferably a methyl group or an ethyl group. n1 is preferably 1 to
8, n2 is preferably 0-3. The molecular weight is preferably 500-20,000, particularly preferably 500-1000.
0.

In the fluoroalkyl group-containing compound represented by the general formula (I), applicable fluoroalkyl group (R _F ), ie,-(CF ₂ ) _n1 X, -CF (CF ₃ )-(OCF ₂ CF
(CF ₃ )) _n2- OC ₃ F ₇ is, specifically, CF ₃ , F (CF ₂ ) ₂ , F (C
_{F 2) 3, F (CF} 2) 4, F (CF 2) 5, F (CF 2) 6, F (CF 2) 7, F (C
F ₂ ) ₈ , F (CF ₂ ) ₉ , F (CF ₂ ) ₁₀ , HCF ₂ , H (CF ₂ ) ₂ , H (CF ₂ ) ₃
, H (CF ₂ ) ₄ , H (CF ₂ ) ₅ , H (CF ₂ ) ₆ , H (CF ₂ ) ₇ , H (CF ₂ ) ₈
, H (CF ₂ ) ₉ , H (CF ₂ ) ₁₀ , ClCF ₂ , Cl (CF ₂ ) ₂ , Cl (C
F ₂ ) ₃ , Cl (CF ₂ ) ₄ , Cl (CF ₂ ) ₅ , Cl (CF ₂ ) ₆ , Cl (CF ₂ ) ₇ , Cl (C
_{F 2) 8, Cl (CF} 2) 9, Cl (CF 2) 10, CF (CF 3) OC 3 F 7, CF (CF 3)
(OCF ₂ CF (CF ₃ )) ₁ -OC ₃ F ₇ , CF (CF ₃ ) (OCF ₂ CF (CF ₃ )) ₂ -OC ₃ F ₇
, CF (CF ₃ ) (OCF ₂ CF (CF ₃ )) ₃ -OC ₃ F ₇ , CF (CF ₃ ) (OCF ₂ CF (CF
₃ )) ₄ -OC ₃ F ₇ , CF (CF ₃ ) (OCF (CF ₃ ) ₂ CF) ₅ -OC ₃ F ₇ , CF (CF ₃ )
(OCF ₂ CF (CF ₃ )) ₆ -OC ₃ F ₇ , CF (CF ₃ ) (OCF ₂ CF (CF ₃ )) ₇ -OC ₃ F ₇
, CF (CF ₃ ) (OCF ₂ CF (CF ₃ )) ₈ -OC ₃ F ₇ . In this case, undesirable when the carbon number i.e. of n1 and n2 of R _F is more than 10 and 8, since the solubility is decreased with respect to the solvent.

The fluoroalkyl group-containing compound represented by the general formula (I) in the present invention may contain a compound in which a fluoroalkyl group (R _F ) is introduced into only one terminal of the compound at an arbitrary ratio. .

The fluoroalkyl group-containing compound R _F- (CH ₂ CR ¹ L) _m1- (CH ₂ CR ¹ R ⁴ ) _m2 -R _F (I) represented by the general formula (I) (III) As specific examples of monomers represented by CH ₂ = CR ¹ L (III) and the following general formula (IV) CH ₂ = CR ¹ R ⁴ (IV), for example, CH ₂ =
CHC (= O) O (CH 2 CH 2 O) p H, CH 2 = CHC (= O) O (CH 2 CHMeO) p H, CH
₂ = CHC (= O) O (CH ₂ CH ₂ O) _p- (CH ₂ CHMeO) _q H, CH ₂ = CHC (= O) O (C
H ₂ CH ₂ O) _p- (CH ₂ CH ₂ CH ₂ CH ₂ O) _q H, CH ₂ = CMeC (= O) O (CH ₂ CH ₂ O)
_{p H, CH 2 = CMeC (} = O) O (CH 2 CHMeO) p H, CH 2 = CMeC (= O) O (CH 2 C
H ₂ O) _p- (CH ₂ CHMeO) _q H, CH ₂ = CMeC (= O) O (CH ₂ CH ₂ O) _p- (CH ₂ CH
₂ CH ₂ CH ₂ O) _q H, CH ₂ = CHC (= O) O (CH ₂ CH ₂ O) _p Me, CH ₂ = CHC (=
O) O (CH ₂ CHMeO) _p Me, CH ₂ = CHC (= O) O (CH ₂ CH ₂ O) _p- (CH ₂ CHMe
O) _q Me, CH ₂ = CHC (= O) O (CH ₂ CH ₂ O) _p- (CH ₂ CH ₂ CH ₂ CH ₂ O) _q Me
_{, CH 2 = CMeC (= O} ) O (CH 2 CH 2 O) p H, CH 2 = CMeC (= O) O (CH 2 CHMe
O) _p Me, CH ₂ = CMeC (= O) O (CH ₂ CH ₂ O) _p- (CH ₂ CHMeO) _q Me, CH ₂
= CMeC (= O) O (CH ₂ CH ₂ O) _p- (CH ₂ CH ₂ CH ₂ CH ₂ O) _q Me, acryloylmorpholine, methacryloylmorpholine, dimethylacrylamide, isopropylacrylamide, octadecylacrylamide, dodecylacrylamide, acryloylpiperidine And acryloylpyrazine. Where p and q are 1
It may represent any integer of from 100 to 100, and may represent an integer containing these values in an arbitrary ratio. In the formula, Me represents a methyl group.

In the fluoroalkyl group-containing compound represented by formula (I), m1 and m2 are from 0 to 5000
Indicates an integer. Here, m1 represents an integer of 1 or more. M1
Or, when m2 exceeds 5000, production is difficult. Further, the average molecular weight of the fluoroalkyl group-containing compound represented by the general formula (I) is 300 to 1,000,000
In order to more remarkably exhibit the characteristics of the fluoroalkyl group, the content is preferably set to 500 to 20,000. When the average molecular weight is less than 300, production is difficult, and when it exceeds 1,000,000, production is difficult.

The process for producing a fluoroalkyl group-containing compound according to the present invention is characterized in that a specific fluoroalkanoyl peroxide is reacted with a specific starting monomer, and water is added to the reaction system in order to make the reaction proceed smoothly. It can also be added.

The fluoroalkanoyl peroxide used in the present invention is represented by the general formula (II). The general formula (I
In the fluoroalkanoyl peroxide represented by I), when n1 is 11 or more or n2 is 9 or more, it cannot be used because the solubility of the fluoroalkanoyl peroxide is reduced when reacting in the presence of a solvent. . The R _F in peroxide -fluoroalkanoyl represented by the general formula (II) is the same as R _F listed in polymer represented by formula (I), wherein the peroxide -fluoroalkanoyl is specifically Specifically, for example, diperfluoro-2-methyl-3-hexanoyl peroxide, perfluoro-2,5-dimethyl-3,6-dioxanonanol peroxide, diperfluoro-2,5,8-trimethyl-peroxide Preferred are 3,6,9-trioxadodecanoyl, diperfluorobutyryl peroxide, diperfluoroheptanoyl peroxide and the like.

In the present invention, when the fluoroalkanoyl peroxide is reacted with the monomers represented by the general formula (II) or the general formulas (II) and (III), the compound represented by the general formula (II) The mixing molar ratio of the monomer represented by the formula (III) and the monomer represented by the formula (III) can be any ratio, but is preferably from 1: 0.01 to 10:
0, and the charged molar ratio when reacting the fluoroalkanoyl peroxide with the monomer represented by the general formula (II) or the general formula (II) and the general formula (III) is 1: 1. It is preferably in the range of 1 to 5000, particularly preferably in the range of 1: 0.5 to 1000. When the charged molar ratio of the raw material monomer is 0.1.
When the amount is less than the above, a large amount of a product resulting from the self-decomposition of the peroxide is generated, and when the amount exceeds 5,000, the yield of the desired fluoroalkyl group-containing compound is undesirably reduced. The molecular weight of the obtained polymer can be adjusted by adjusting the charged molar ratio of the fluoroalkanoyl peroxide. That is, a polymer having a low molecular weight can be obtained by increasing the molar ratio of the fluoroalkanoyl peroxide to the monomers, and a polymer having a high molecular weight can be obtained by decreasing the molar ratio. Further, the reaction can be carried out at normal pressure, and the reaction temperature is usually in the range of -20 to 150 ° C, preferably 0 to 100 ° C. If the reaction temperature is lower than −20 ° C., the reaction time tends to be longer. Conversely, if it exceeds 150 ° C., the pressure during the reaction increases, and the reaction operation is difficult, which is not preferable. Further, the reaction time can be usually in the range of 30 minutes to 20 hours, but practically 1 to 10 hours.
It is desirable to set conditions so that time is reached.

In the production method of the present invention, the desired fluoroalkyl group-containing compound can be directly obtained by a one-step reaction by reacting the fluoroalkanoyl peroxide with the monomers under the various reaction conditions. However, in the reaction of the fluoroalkanoyl peroxide, it is preferable that water is added to the monomers represented by the general formula (II) in an amount of 1 to 90% by weight to dissolve the monomers and use the resultant in the reaction. At the time of the reaction, a known additive such as a dispersant may be used in an appropriate ratio for the reaction. If water is not used in this reaction, it tends to be generally difficult to obtain the desired polymer in good yield. Further, it is preferable to use an organic solvent in order to carry out the reaction more smoothly. As the organic solvent, a halogenated aliphatic solvent and a halogenated aromatic solvent are particularly preferable, and specifically, for example, methylene chloride, chloroform, 2-chloro-1,2-dibromo-
1,1,2-trifluoroethane, 1,2-dibromohexafluoropropane, 1,2-dibromotetrafluoroethane, 1,1-difluorotetrachloroethane,
1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,3,3-trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,1-trichloropentafluoropropane, 1 , 1,2-trichlorotrifluoroethane,
1,1,1,2,2-pentafluoro-3,, 3-dichloropropane, 1,1,2,2,3-pentafluoro-
1,3-dichloropropane, benzotrifluoride, hexafluoroxylene, pentafluorobenzene and the like can be used. Particularly, industrially, 1,1,1,2,2
-Pentafluoro-3,3-dichloropropane, 1,
Solvents such as 1,2,2,3-pentafluoro-1,3-dichloropropane, benzotrifluoride and the like or a mixed solvent in which these solvents are mixed at an arbitrary ratio can be preferably exemplified. When the solvent is used, the concentration of the fluoroalkanoyl peroxide in the solvent is usually 0.1 to 3%.
It is desirably about 0% by weight.

The polymer represented by the general formula (I) obtained by the production method of the present invention can be purified by a known method such as reprecipitation method, column chromatography, dialysis and the like.

In the present invention, a monomer constituting the general formula (V) R _F- (CH ₂ CR ¹ L) _m1- (CH ₂ CR ¹ R ⁴ ) _m2 -R _F (V): CH ₂ = CR ¹ L specific examples _{include, CH 2 = CHC (= O} ) O (CH 2 CH 2 O) p H, CH 2 = CHC (= O) O (CH 2 CHMe
O) _p H, CH ₂ = CHC (= O) O (CH ₂ CH ₂ O) p- (CH ₂ CHMeO) _q H, CH ₂ = CH
C (= O) O (CH ₂ CH ₂ O) p- (CH ₂ CH ₂ CH ₂ CH ₂ O) _q H, CH ₂ = CMeC (= O) O
(CH ₂ CH ₂ O) pH, CH ₂ = CMeC (= O) O (CH ₂ CHMeO) pH, CH ₂ = CMeC
(= O) O (CH ₂ CH ₂ O) _p- (CH ₂ CHMeO) _q H, CH ₂ = CMeC (= O) O (CH ₂ CH ₂
O) _p- (CH ₂ CH ₂ CH ₂ CH ₂ O) _q H, CH ₂ = CHC (= O) O (CH ₂ CH ₂ O) _p Me,
CH ₂ = CHC (= O) O (CH ₂ CHMeO) _p Me, CH ₂ = CHC (= O) O (CH ₂ CH ₂ O) p
-(CH ₂ CHMeO) _q Me, CH ₂ = CHC (= O) O (CH ₂ CH ₂ O) _p- (CH ₂ CH ₂ CH ₂ C
H ₂ O) _q Me, CH ₂ = CMeC (= O) O (CH ₂ CHMeO) _p Me, CH ₂ = CMeC (= O)
O (CH ₂ CH ₂ O) _p- (CH ₂ CHMeO) _q Me, CH ₂ = CMeC (= O) O (CH ₂ CH ₂ O)
_p- (CH ₂ CH ₂ CH ₂ CH ₂ O) _q Me (where p and q are 1
Represents an integer of from 100 to 100, and these values may represent an integer in an arbitrary ratio, and Me represents a methyl group). CH ₂ CRCR ¹ R ⁴ Specific examples of the monomer include, for example, acryloylmorpholine, methacryloylmorpholine, dimethylacrylamide, isopropylacrylamide, octadecylacrylamide, dodecylacrylamide, acryloylpiperidine, acryloylpyrazine, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, acrylonitrile, Vinyl acetate, vinyl propionate, vinyl butyrate, (meth) acrylic acid, methyl (meth) acrylate,
T-butyl (meth) acrylate, propyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate, 2-
Hydroxypropyl (meth) acrylate, trimethoxyvinylsilane, triethoxyvinylsilane, diacetyloxymethylvinylsilane, diethoxymethylvinylsilane, triacetyloxyvinylsilane, triisopropoxyvinylsilane, trimethylvinylsilane, trimethylvinylsilane
-t-butoxyvinylsilane, ethoxydiethylvinylsilane, diethylmethylvinylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldiacetyloxymethylsilane, 3-methacryloxypropyldiethoxymethyl Silane, 3-methacryloxypropyltriacetyloxysilane, 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropyltrimethylsilane, 3-methacryloxypropyltri-t-butoxysilane, 3-methacryloxypropylethoxydiethylsilane 3,3-methacryloxypropyldiethylmethylsilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloyl Xypropyldiacetyloxymethylsilane, 3-acryloxypropyldiethoxymethylsilane, 3-acryloxypropyltriacetyloxysilane, 3-acryloxypropyltriisopropoxysilane, 3-acryloxypropyltrimethylsilane, 3-acryloxypropyl Tri-t-butoxysilane, 3-acryloxypropylethoxydiethylsilane, 3-acryloxypropyldiethylmethylsilane and the like can be preferably exemplified.

The fluoroalkyl group-containing compound represented by the general formula (V) in the present invention is synthesized by reacting the corresponding monomer with the fluoroalkanoyl peroxide represented by the general formula (II) shown above. be able to.

In the present invention, the polymer electrolyte comprising a complex containing the fluoroalkyl group-containing compound represented by the general formula (V) and at least one electrolyte is an organic compound which is generally used as a so-called plasticizer. (Expressed as a plasticizer in the present invention) is preferable because the ionic conductivity of the solid electrolyte is further improved. As a plasticizer that can be used, a compound having a large dielectric constant, a boiling point of 100 ° C. or higher, and a wide electrochemical stability range is suitable. Examples of such a plasticizer include oligoethers such as triethylene glycol methyl ether and tetraethylene glycol dimethyl ether, carbonates such as ethylene carbonate, propylene carbonate, diethyl carbonate and vinylene carbonate, benzonitrile and aromatic nitriles such as tolunitrile. And sulfur compounds such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and sulfolane, and phosphoric acid esters. Of these, oligoethers and carbonates are preferred, and carbonates are particularly preferred. The ionic conductivity of the polymer solid electrolyte increases as the amount of the plasticizer added increases, but when the amount is too large, the mechanical strength of the polymer solid electrolyte decreases. Preferably, the addition amount is 5 times or less the weight of the fluoroalkyl group-containing compound represented by the general formula (V) in the present invention.

As the electrolyte used for the composite, an electrolyte containing ions to be used as a carrier in a battery or the like may be used. The electrolyte having a large dissociation constant in a solid electrolyte is desirable, and an alkali metal salt [eg, LiN (CF ₃ SO ₂ ) ₂ , LiCF ₃ SO ₃ , LiPF
_{6, LiClO 4, LiI, LiBF} 4, LiSCN, LiAsF 6, NaCF 3 S
_{O 3, NaPF 6, NaClO 4} , NaI, NaBF 4, NaAsF 6, KCF 3 SO
₃ , KPF ₆ , KI, etc.], quaternary ammonium salts [for example, (C
H ₃ ) ₄ NBF ₄ , (CH ₃ CH ₂ ) ₄ ClO ₄ etc.], quaternary phosphonium salts [eg, (CH ₃ ) ₄ PBF ₄ etc.], transition metal salts [eg,
AgClO ₄ etc.] or a protic acid [hydrochloric acid, perchloric acid, borofluoric acid etc.] is recommended. Among them, alkali metal salts, quaternary ammonium salts, and quaternary phosphonium salts are particularly preferable because of their large dissociation constant. The composite ratio of the polymer in the solid polymer electrolyte of the present invention and the electrolyte used for the composite is preferably a ratio of one electrolyte molecule to one to 100 carbonate groups of the plasticizer. When the electrolyte used in the composite is present in a ratio of one or more carbonate groups, the movement of ions is greatly inhibited. On the other hand, in a ratio of 1/100 or less, the absolute amount of ions becomes insufficient and the ion conductivity decreases. Not preferred.

Interestingly, the fluoroalkyl group-containing compound represented by the general formula (I) of the present invention can be used in an aqueous solution or an organic solvent system by increasing the concentration.
The gel can be easily formed by the aggregation action of the fluoroalkyl group and the intermolecular hydrogen bond between the hydrophilic groups, and the dissolved metal ion can be captured when the metal ion is present in the solution. Also, once the fluoroalkyl group-containing compound solution that has captured the metal ion is added again to an aqueous solution or an organic solvent that does not contain the metal ion, the captured metal ion is released. Examples of the metal ions that can be captured or released include ions of all metal elements. The form of the metal ion may be complex or the charge may be cationic or anionic. For example, group I (alkali metal and copper group), group II (alkaline earth metal and zinc) Group, except boron, group III except carbon and silicon, group VIII (iron group and platinum group), V,
An ion composed of an element belonging to each subgroup a of the groups VI and VII can be mentioned.

[0025]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. Example 1 As a fluoroalkanoyl peroxide, 4 mmol of perfluoro-2-methyl-3-oxahexanoyl peroxide was used.
l, as monomer A, 3 mmol of Bremma-PME-400 (manufactured by NOF Corporation) and, as monomer B, 14 mmol of acrylic acid, 50 g each of AK-22
5 (1,1-dichloro-2,2,3,3,3-pentafluoropropane: 1,3-dichloro-1,2,2,3,
3-pentafluoropropane = 1: 1.35 manufactured by Asahi Glass Co., Ltd.) and reacted at 45 ° C. for 5 hours under a nitrogen stream. After the reaction, the obtained product was filtered and then sufficiently washed with methanol to remove residual monomers. Further, the oligomers were filtered and dried at 50 ° C. under vacuum to obtain a fluoro compound shown below. An alkyl group-containing triol homo-oligomer (oligomer-1) was obtained (yield: 33).
%). Rf- [CH ₂ CHCOO (CH ₂ CH ₂ O) _4-5 CH ₃ ]-[CH ₂ CHCOOH] -Rf

Examples 2 to 12 Fluoroalkyl group-containing triol homo-oligomers shown in Table 1 were synthesized in the same manner as in Example 1 except that the fluoroalkanoyl peroxide, the monomer A and the monomer B were changed. 12).

Examples 13 to 28 0.2 g of each of the oligomers 1 to 12 synthesized in Examples 1 to 12 was dissolved in 5 mL of a solvent, and 30 mg of an electrolyte was added and mixed well. This solution was applied on a glass plate under an argon atmosphere to form a cast film having a thickness of about 50 μm and dried under reduced pressure. The ionic conductivity of the polymer electrolyte comprising the composite containing the electrolyte was measured by the impedance method. The oligomers, electrolytes, solvents, types of plasticizers, measurement temperatures and ionic conductivity used are summarized in Table 2.

Example 29 After the oligomer synthesized in Example 1 (0.05 g) was equilibrated and swollen in 3.33 ml of water, 5 ml of an aqueous solution of chromium nitrate was added, and the mixture was allowed to stand for 24 hours to capture metal ions. The amount of capture is the absorption spectrum of the supernatant (580 nm for Cr ³⁺ )
Was determined from the measurement. After trapping the metal ions, the gel portion was separated by suction filtration, a constant amount of water was added, and the amount of chromium ions released was determined from the absorption spectrum of the supernatant. The oligomers captured 45% of the metal ions from the absorption spectrum, and on the one hand, the captured metal ions were found to release 15% of the captured metal ions.

Example 30 The measurement was carried out according to Example 29 except that cobalt chloride was used instead of chromium nitrate. As a result, it was found that 60% of the cobalt ions were captured and 20% of the captured cobalt ions were released.

[0030]

[Table 1]

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

Industrial Applicability The fluoroalkyl group-containing compound of the present invention is a novel compound. Since the fluoroalkyl group is directly bonded not by an ester bond but by a carbon-carbon bond, the property derived from the fluoroalkyl group can be maintained for a long time. It is a compound that can be maintained for a long time and has high weather resistance. Therefore, as a novel fluoropolymer surfactant,
As a compound having properties such as low surface tension, low refraction, heat resistance, cold resistance, oil resistance, electrical insulation, anti-fogging, anti-fouling, and chemical resistance, especially flip-flop.
Surface treatment agents with hydrophilic properties and oil repellency and anti-staining properties, as well as materials for the surface of paints, optical lenses, eyeglass lenses, glassware, etc., and raw materials for cosmetics, etc. Can be used. Further, according to the production method of the present invention, a fluoroalkyl group-containing compound can be produced by a one-step reaction easily in a short time with good yield and without using a reaction catalyst and a special apparatus.

The polymer electrolyte comprising the composite containing the electrolyte according to the present invention can form a film having high flexibility, and has a high electrical conductivity. -Also useful as a solid polymer electrolyte for electronic devices such as sensors and electrochromic devices. In particular, the solid polymer electrolyte of the present invention, as shown in the above examples, can effectively exhibit the effect of fluorine, so that it can prevent liquid leakage and the like, and furthermore has weather resistance and chemical resistance It is a rich material.

Claims (6)

[Claims] 1. The following general formula (I): R _F- (CH ₂ CR ¹ L) _m1- (CH ₂ CR ¹ R ⁴ ) _m2 -R _F (I) wherein R ¹ is a hydrogen atom or a methyl group Where L is C (= O) O
(CH ₂ CH ₂ O) _p R ¹ , C (= O) O (CH ₂ CHMeO) _p R ¹ , C (= O) O (CH ₂ CH
₂ O) _p- (CH ₂ CHMeO) _q R ¹ , C (= O) O (CH ₂ CH ₂ O) _p- (CH ₂ CH ₂ CH ₂ CH ₂
O) _q R ¹ or Si (CH ₃ ) ₂ (OCH ₂ CH ₂ ) _m OR ² (m represents an arbitrary integer of 1 to 20, R ² represents an alkyl group having 1 to 4 carbon atoms,
When L is Si (CH ₃ ) ₂ (OCH ₂ CH ₂ ) _m OC ₂ H ₅ , _{m 2} may be 0), R ⁴ is —C (= O) R ⁶ , and R _F is — (CF ₂ ) _n1 X, -CF
_{(CF 3) [OCF 2 CF} (CF 3)] indicates _n2 -OC ₃ F _7, and m1 and m @ 2 0 to 5
Represents an integer of 000 (provided that p and q each represent an integer of 1 to 100, m1 represents an integer of 1 or more, and R ⁶ has 1 to 1 carbon atoms)
20 represents an alkylamino group, a dialkylamino group, a pyrrolidino group, a piperidino group, or a morpholino group;
X represents a fluorine atom, a chlorine atom, or a hydrogen atom, and n2 represents an integer of 0 to 8)]], a fluoroalkyl group-containing compound having a molecular weight of 300 to 1,000,000. 2. The following general formula (II): R _F C (= O) OO (O =) CR _F (II) wherein R _F is as defined above. And a fluoroalkanoyl peroxide represented by the following general formula (III) CH ₂ = CR ¹ L (III) and the following general formula (IV) CH ₂ = CR ¹ R ⁴ (IV) wherein L and R ¹ , R ⁴ is as defined above. The method for producing a fluoroalkyl group-containing compound according to claim 1, wherein 3. At least the following general formula (I): R _F- (CH ₂ CR ¹ L) _m1- (CH ₂ CR ¹ R ⁴ ) _m2 -R _F (I) wherein R ¹ , L and R ⁴ , _RF are as described above. However, R ⁴ is a halogen atom, a cyano group, Si (R ⁵ ) ₃ or -C (= O) OR ⁹
R ⁵ represents an alkyl group having 1 to 4 carbon atoms, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, CH ₂ CH ₂ CH ₂ Si (R ¹⁰ ) ₃ and R ¹⁰ represents an alkyl group or an alkoxy group having 1 to 4 carbon atoms. ] A polymer electrolyte comprising a complex containing the above-mentioned fluoroalkyl group-containing compound having a molecular weight of 300 to 1,000,000 and at least one electrolyte. 4. The electrolyte according to claim 3, wherein at least one of the electrolytes is an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, a transition metal salt or a protonic acid.
3. The polymer electrolyte according to item 1. 5. The polymer electrolyte according to claim 3, wherein a plasticizer is added. 6. A metal ion trapping agent and a releasing agent having the structure of the fluoroalkyl group-containing compound according to claim 1.