JP2001253916A - Fluoroalkyl group-containing phosphonic acid oligomers, method of producing the same and their use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new fluoroalkyl group-containing phosphonic acid oligomer having an excellent ionic conductance, useful as a nonaqueous surfactant. SOLUTION: This fluoroalkyl group-containing phosphonic acid oligomer is represented by general formula (1) (R1 and R2 are each a (CF2)m1Y or a CF (CF3)-[OCF2CF(CF3)]m2-OC3F7; Y is hydrogen atom, fluorine atom or chlorine atom; m1 is an integer of 1-10; m2 is an integer of 0-10; R3 is hydrogen atom or methyl group; B is an alkylene group; n is an integer of 1-1,000).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel fluoroalkyl group-containing phosphonic acid oligomer and a method for producing the same, a non-aqueous surfactant, and a polymer solid electrolyte having excellent ionic conductivity.

[0002]

2. Description of the Related Art Fluoroalkyl group-containing compounds have attracted attention as compounds exhibiting useful properties such as light resistance, water / oil repellency, and physiological activity. Conventionally, fluoroalkyl group-containing carboxylic acids such as perfluorooctanoic acid show high interface properties in an aqueous solution,
It is widely known and used as a fluorine-based surfactant.

[0003] However, since the known fluorine-based surfactant is a compound composed of only a hydrophilic group and a water-repellent group, it has excellent properties such as water repellency and oil repellency due to fluorine atoms and hydrophilicity. Was difficult to express alternately in various environments.

In the field of surfactants, surfactants into which fluorine, especially a long-chain fluoroalkyl group has been introduced,
It is noted that it has superior performance due to fluorine as compared with conventional hydrocarbon-based surfactants, and there are numerous reports on low-molecular-weight surfactants. However, there is almost no knowledge of a high molecular weight surfactant into which a fluoroalkyl group has been introduced.

[0005] In recent years, polymer materials having high ionic conductivity have attracted attention.
It is called a polymer solid electrolyte, and is particularly attracting attention as an electrolyte for next-generation lithium ion secondary batteries.

[0006] As a high-performance battery, a polymer battery using a polymer instead of an electrolyte solution as an electrolyte has attracted attention. (Katsuji Ashida “Electronic Materials” No. 11, 109
For example, in a polymer battery, the ionic conduction of a polymer solid electrolyte typified by polyethylene oxide is a cation ion such as a lithium ion, as shown by ion transfer in a polymer solid electrolyte in the following chemical formula. Conduction takes place using the lone pair of ether oxygen as a medium. (Katsumichi Ono “The Journal of the Rubber Association of Japan” 9 , 61
P. 1993)

[0007]

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Since such a polymer battery has a high energy density, it is possible to make the battery small and thin. (Toshihiro Ichino "Polymer" 45 , p. 868, 1996
As shown in the structure of a polymer gel electrolyte in the following structural formula, the development of a polymer gel electrolyte has been actively developed recently for the purpose of higher ion conductivity than a solid polymer electrolyte. (Noboru Koyama, Osamu Hadozaki "Modern Chemistry" N
o. 10, p. 34, 1996) However, drawbacks such as liquid leakage, low chemical resistance and low weather resistance have been pointed out, and it is urgently necessary to solve these problems. Therefore, to solve these problems, it is an important research item to develop a new polymer gel electrolyte having a fluorine function.

[0009]

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[0010]

SUMMARY OF THE INVENTION The present inventors have previously proposed various new functional materials while taking advantage of the advantages of fluoroalkyl groups. For example, fluoroalkyl group-containing phosphonium salt oligomers having antibacterial properties (JP-A-11-246577, JP-A-11-246578)
JP-A-11-246579), fluoroalkyl group-containing phosphonate oligomers useful as surfactants (JP-A-11-246573 and JP-A-11-246574), and fluoroalkyl group-containing phosphinic acid oligomers (Japanese Patent Application No. 11-45901)
No., Japanese Patent Application No. 11-45915).

The present inventors have been actively conducting research on the synthesis and properties of oligomers having a fluoroalkyl group introduced at both ends. (H. Sawa
da (Hideo Sawada), "Chem. Rev.", vol.
96, ppl779, 1996) In particular, cast films in the presence of lithium ions of poly (oxyethylene) unit-containing co-oligomers having fluoroalkyl groups introduced at both ends synthesized by the following reaction are particularly suitable for ion conduction. Reported that (HS
awada (Hideo Sawada) et al. , "J. Jp
n. Oil Chem. Soc. 47, p.
p685, 1998)

[0012]

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In addition, by introducing a betaine segment or a triol segment into an oligomer having a fluoroalkyl group introduced at both ends by the reaction shown below, ionic interaction between betaine segments can be achieved in addition to the aggregation effect of the fluoroalkyl group. It was reported that the action or the hydrogen bond between the triol segments acted synergistically to form a gel in water or even a polar organic solvent in spite of the system without using a crosslinking agent. (H. Sawa
da (Hideo Sawada) et al. , “Polyme
r ", vol. 38, pp 743, 1998),
(H. Sawada (Hideo Sawada) et al., "B.
ull. Chem. Soc. Jpn. ", Vol.
0, pp2839, 1997)

[0014]

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Accordingly, the present invention provides a poly (oxyethylene) having a betaine segment or a triol segment having a fluoroalkyl group introduced at both ends in order to develop a novel polymer gel electrolyte provided with an excellent function of fluorine. Synthesis and properties of unit-containing cooligomers,
In particular, the gelling ability of these oligomers was examined. Furthermore, application to polymer gel electrolyte was also studied.

Further, the present inventors have conducted intensive studies on a novel functional material having a fluoroalkyl group. As a result, by introducing a phosphonic acid segment into an oligomer having a fluoroalkyl group, a non-aqueous interface was obtained. The inventors have found that they are useful as an activator, and furthermore, are oligomers having high ionic conductivity and also useful as a solid polymer electrolyte, and have completed the present invention.

That is, the present invention provides a novel fluoroalkyl group-containing phosphonic acid oligomer having excellent ionic conductivity, a process for producing the same, and a non-aqueous surfactant and a solid polymer electrolyte as uses thereof. With the goal.

[0018]

DISCLOSURE OF THE INVENTION The present invention provides a fluoroalkyl group-containing phosphonic acid oligomer comprising:
The following general formula (1)

[0019]

Embedded image

(Wherein, R ¹ and R ² are — (CF ₂ ) _m1 Y or —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] _{m 2} —
Shows OC ₃ F ₇ . ｛Wherein, Y represents a hydrogen atom, a fluorine atom or a chlorine atom. m1 is an integer of 1 to 10, m2 is 0
And an integer of 10 to 10. ｝ R ³ represents a hydrogen atom or a methyl group. B represents an alkylene group. n shows the integer of 1-1000. ) Is a structural feature.

The fluoroalkyl group-containing phosphonic acid oligomers to be provided by the present invention are represented by the following general formula (2):

[0022]

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(Wherein R ¹ and R ² represent — (CF ₂ ) _m1 Y or —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] _{m 2} —
Shows OC ₃ F ₇ . ｛Wherein, Y represents a hydrogen atom, a fluorine atom or a chlorine atom. m1 is an integer of 1 to 10, m2 is 0
And an integer of 10 to 10. ｝ R ³ and R ⁴ represent a hydrogen atom or a methyl group. B represents an alkylene group.

A is the following general formula (3)

[0025]

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Wherein X ¹ is a hydrogen atom or a methyl group;
² represents an alkyl group having 1 to 6 carbon atoms, and t represents 2 to 30.
Indicates an integer of 0. An alkylene oxide group having an ester bond represented by｝, or the following general formula (4)

[0027]

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In the formula, Z represents an alkylene group.ス ル ホ ン represents a sulfonic acid group. n shows the integer of 1-1000. The moles of a: b are from 1:99 to 99: 1. ) Is a structural feature.

Further, the process for producing the fluoroalkyl group-containing phosphonic acid oligomer represented by the above general formula (1) to be provided by the present invention is described by the following general formula (5)

[0030]

Embedded image (Wherein R ¹ and R ² are as defined above), and a fluoroalkanoyl peroxide represented by the following general formula (6)

[0031]

Embedded image (Wherein, R ³ and B are as defined above).
It is characterized by reacting with a phosphonic acid compound having an acrylic group.

Further, the process for producing the fluoroalkyl group-containing phosphonic acid oligomer represented by the above general formula (2) to be provided by the present invention is described by the following general formula (5)

[0033]

Embedded image (Wherein R ¹ and R ² are as defined above), and a fluoroalkanoyl peroxide represented by the following general formula (6)

[0034]

Embedded image (Wherein, R ³ and B are as defined above).
A phosphonic acid compound having an acrylic group, and the following general formula (7)

[0035]

Embedded image (Wherein, R ⁴ and A are as defined above).
It is characterized by reacting with a compound having an acrylic group.

The surfactant provided by the present invention comprises, as an active ingredient, a fluoroalkyl group-containing phosphonic acid oligomer represented by the above general formula (1) or (2). It is a feature.

The solid polymer electrolyte to be provided by the present invention is characterized by containing a fluoroalkyl group-containing phosphonic acid oligomer represented by the above general formula (1) or (2). It is assumed that.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The fluoroalkyl group-containing phosphonic acid oligomer according to the present invention has the following general formula (1)

[0039]

Embedded image And the following general formula (2)

[0040]

Embedded image And a fluoroalkyl group-containing phosphonic acid oligomer represented by the formula:

In the formulas of the fluoroalkyl group-containing phosphonic acid oligomers represented by the above general formulas (1) and (2),
R ¹ and R ² are represented by the following general formula (8)

[0042]

Embedded image (Wherein, Y represents a hydrogen atom, a fluorine atom, or a chlorine atom. M1 represents an integer of 1 to 10), or a fluoroalkyl group represented by the following general formula (9)

[0043]

Embedded image (Wherein, m2 represents an integer of 0 to 10). R ¹ and R ² may be the same or different groups.

R in the formula (1) or (2)
³ , R ⁴ is a hydrogen atom or a methyl group. B is a linear or branched alkylene group, specifically, a linear or branched alkylene group having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group. Pentamethylene group, ethylethylene group, propylene group, butylene group, hexylene group, decylene group and the like. n is an integer of 1 to 1000, preferably 1 to 50, particularly preferably 1 to 20.

In the above formula (2), A represents the following formula (3)

[0046]

Embedded image Or an alkylene oxide group having an ester bond represented by the following general formula (4):

[0047]

Embedded image Is a sulfonic acid group represented by

In the formula of the alkylene oxide group having an ester bond represented by the general formula (3), X ¹ represents a hydrogen atom or a methyl group. X ² represents lower alkyl having 1 to 6 carbon atoms. Specific examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. t shows the integer of 2-300.

In the formula of the sulfonic acid group represented by the general formula (4), Z is specifically a linear or branched alkylene group having 1 to 10 carbon atoms. Examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, a decylene group, a 2-methylpropylene group, a 2-methylbutylene group, and a 3-methylbutylene group.

In addition, in the oligomers represented by the general formulas (1) and (2), an oligomer in which a fluoroalkyl group represented by R ¹ and R ² is introduced into only one terminal of the oligomer may be used. It may be contained in a ratio.

<Production Method> Next, a method for producing the fluoroalkyl group-containing phosphonic acid oligomers represented by the general formulas (1) and (2) according to the present invention will be described.

In the method for producing the fluoroalkyl group-containing phosphonic acid oligomer represented by the general formula (1), the following general formula (5)

[0053]

Embedded image (Wherein R ¹ and R ² are as defined above), and a fluoroalkanoyl peroxide represented by the following general formula (6)

[0054]

Embedded image (Wherein, R ³ and B are as defined above).
It is characterized by reacting with a phosphonic acid compound having an acrylic group.

Further, the method for producing the fluoroalkyl group-containing phosphonic acid oligomer represented by the general formula (2) is characterized in that the fluoroalkanoyl peroxide represented by the general formula (5) is used as a reaction raw material, A phosphonic acid compound having a (meth) acrylic group represented by the formula (6) and the following general formula (7)

[0056]

Embedded image (Wherein, R ⁴ and A are as defined above).
It is characterized by reacting with a compound having an acrylic group.

<Fluoroalkanoyl peroxide> Specific examples of the fluoroalkanoyl peroxide represented by the above general formula (5) as a reaction raw material include diperfluoro-2-methyl-3-oxadioxide. Hexanoyl, diperfluoro-2,5-dimethyl-3,6-dioxano nanoyl peroxide, diperfluoro-2,5,8-peroxide
Examples include trimethyl-3,6,9-trioxadodecanoyl, diperfluorobutyryl peroxide, diperfluoroheptanoyl peroxide, diperfluorooctanoyl peroxide, and the like.

As a method for producing such fluoroalkanoyl peroxides, widely known methods can be used.
As an example, a fluoroalkyl group-containing acyl halide may be added to a sodium hydroxide, potassium hydroxide, potassium hydrogen carbonate, sodium carbonate or carbonate in the presence of a fluorinated aromatic solvent or a fluorinated aliphatic solvent such as freon. The desired fluoroalkanoyl peroxide can be easily obtained by a method of reacting hydrogen peroxide in the presence of an alkali such as potassium.

<Phosphonic acid compound having a (meth) acrylic group> In the phosphonic acid compound having a (meth) acrylic group represented by the general formula (6) as a reaction raw material, B represents a linear or A branched alkylene group,
Specifically, a linear or branched alkylene group having 1 to 10 carbon atoms is preferable, for example, a methylene group, an ethylene group,
Examples include a trimethylene group, a tetramethylene group, a pentamethylene group, an ethylethylene group, a propylene group, a butylene group, a hexylene group, and a decylene group.

Specific examples of the compound include acroyloxymethylphosphonic acid, methacryloyloxymethylphosphonic acid, 2-acroyloxyethylphosphonic acid,
-Methacryloyloxyethylphosphonic acid, 3-acryloyloxypropylphosphonic acid, 3-methacryloyloxypropylphosphonic acid, 4-acryloyloxybutylphosphonic acid, 4-methacryloyloxybutylphosphonic acid, 5-acryloyloxypentylphosphonic acid, 5-methacryloyloxypentylphosphonic acid, 6-acryloyloxyhexylphosphonic acid, 6-methacryloyloxyhexylphosphonic acid, 7-acryloyloxyheptylphosphonic acid, 7-methacryloyloxyheptylphosphonic acid, 8-acryloyloxyoctylphosphonic acid , 8-
Examples thereof include methacryloyloxyoctylphosphonic acid, 9-acryloyloxynonylphosphonic acid, 9-methacryloyloxynonylphosphonic acid, 10-acryloyloxydecylphosphonic acid, and 10-methacryloyloxydecylphosphonic acid.

The method for producing the above-mentioned phosphonic acid compound having a (meth) acrylic group is not particularly limited, and widely known methods can be used. One example of which is shown by the present applicant. Reacting hypophosphorous acid or hypophosphite with an unsaturated alcohol in an alcohol solvent in the presence of a radical initiator to obtain hydroxyalkylphosphinic acid, and then oxidizing the resulting hydroxyalkylphosphinic acid Then, after obtaining the hydroxyalkylphosphonic acid, it can be easily obtained by reacting the hydroxyalkylphosphonic acid with a (meth) acrylic acid halide (Japanese Patent Application No. Hei 10-187017).

<Compound having a (meth) acrylic group> The compound having a (meth) acrylic group represented by the general formula (7) is represented by the following general formula (10)

[0063]

Embedded image Ethylene glycols having a (meth) acrylic group represented by the following general formula (11):

[0064]

Embedded image Is a sulfonic acid compound having a (meth) acryl group.

In the formulas of the compounds having a (meth) acrylic group represented by the general formulas (10) and (11), R ⁴ is
It is a hydrogen atom or a methyl group.

[0066] wherein the ethylene glycols having the formula (meth) acrylic group in the general formula (10), X ¹
Represents a hydrogen atom or a methyl group, and X ² has 1 to 1 carbon atoms.
6 represents lower alkyl. Specific examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. t is 2 to 300, preferably 2 to 1
0. The ethylene glycols are, specifically,
Methoxy diethylene glycol methacrylate, methoxy diethylene glycol acrylate, methoxy triethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate, and the like. These compounds are commercially available as Kyoeisha Chemical Co., Ltd .; light ester series. ing.

In the formula of the sulfonic acid compound having a (meth) acrylic group represented by the general formula (11), Z is a linear or branched alkylene group having 1 to 10 carbon atoms;
For example, methylene, ethylene, propylene, butylene, hexylene, octylene, decylene, 2
-Methylpropylene group, 2-methylbutylene group, 3-methylbutylene group and the like. As a specific compound, in the present invention, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) is preferably used.

Next, the reaction conditions will be described. In the method for producing a fluoroalkyl group-containing phosphonic acid oligomer represented by the general formula (1), a fluoroalkanoyl peroxide represented by the general formula (5) and a fluoroalkanoyl peroxide represented by the general formula (6) ( The molar ratio with the phosphonic acid compound having a (meth) acryl group is usually in the range of 1: 1 to 100, and preferably in the range of 1: 1 to 50.

In the method for producing a fluoroalkyl group-containing phosphonic acid oligomer represented by the general formula (2), a fluoroalkanoyl peroxide represented by the general formula (5) is combined with a fluoroalkanoyl peroxide represented by the general formula (6). A phosphonic acid compound having a (meth) acrylic group represented by the general formula (7):
The molar ratio with the compound having a (meth) acrylic group represented by is usually in the range of 1: 1 to 100: 1 to 100,
Preferably it is in the range of 1: 1 to 50: 1 to 50.

The above reaction can be carried out at normal pressure. The reaction temperature is generally 100 ° C or lower, preferably 10 to 50 ° C. If the reaction temperature is too low, the reaction tends to take a long time. On the other hand, if the temperature is higher than 100 ° C., the pressure in the reaction system increases, and the reaction operation tends to be difficult. The reaction time is usually 20
Within hours, preferably 2 to 5 hours.

This reaction can be carried out in the absence of a solvent. However, in order to carry out the reaction with fluoroalkanoyl peroxides more smoothly, it is desirable to carry out the reaction in a solvent. As the reaction solvent, a halogenated aliphatic solvent is particularly preferably used. For example, methylene chloride, chloroform,
-Chloro-1,2-dibromo-1,1,2-trifluoroethane, 1,2-dibromohexafluoropropane,
1,2-dibromotetrafluoroethane, fluorotrichloromethane, heptafluoro-2,3,3-trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,2-trichlorotrifluoropropane, 1,1,2-trichlorotrifluoroethane,
1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,2,2,3,3-
One or more kinds such as pentafluoropropane can be used. Among them, in particular, 1,1-dichloro-2,
A mixed solvent of 2,3,3,3-pentafluoropropane and 1,3-dichloro-1,2,2,3,3-pentafluoropropane is preferably used.

The concentration of the alkanoyl peroxide in these solvents is preferably in the range of 0.5 to 30% by weight.

In this way, the desired fluoroalkyl group-containing phosphonic acid oligomer can be easily obtained, but in the present invention, if desired, purification can be carried out by conventional purification means such as dialysis, recrystallization, distillation, column chromatography and the like. Can be.

The fluoroalkyl group-containing phosphonic acid oligomer of the present invention is useful as a solid polymer electrolyte because it has a non-aqueous surfactant and excellent ionic conductivity. It can be used as an agent.

Next, the surfactant of the present invention will be described. The surfactant of the present invention is characterized by containing a fluoroalkyl group-containing phosphonic acid oligomer represented by the general formula (1) or (2) as an active ingredient.

Preferred compounds are those represented by the above general formula
(1) or (2), wherein R ¹ , R^Two Is before
Fluorine represented by the general formula (8) and the general formula (9)
In the alkyl group, Y is a fluorine atom, and m1 is preferably
And m2 is preferably 1 to 10.
You.

The effect of surface activity is affected by the length of the fluoroalkyl group of R ¹ and R ^2. For example, in the case of the fluoroalkyl group represented by the general formula (9), as m2 increases, The effect of surface activity tends to increase. Also, R ¹ and R ² are preferably the same group. R ³ is a hydrogen atom or a methyl group. The range of n is preferably 1 to 50, particularly preferably 1 to 10.

The surfactant of the present invention exhibits an excellent surfactant effect when the concentration is usually 0.5 g / dm ³ or more, preferably 1 g / dm ³ or more.

The surfactant of the present invention can be used in a usual manner, and can be used in combination with a known surfactant. The surfactant that can be used in combination is not particularly limited, and includes an anionic surfactant, a nonionic surfactant, and a cationic surfactant.

Examples of the anionic surfactant include sulfonate, sulfate, carboxylate and the like.

Examples of the sulfonate-based surfactant include alkylbenzene sulfonates having 9 to 15 carbon atoms.
Examples thereof include alkyl sulfonates having 12 to 16 carbon atoms, alkenes and hydroxyalkane sulfonates, disulfonates, α-olefin sulfonates, and the like. Examples of the sulfate surfactant include primary alcohols such as tallow fatty alcohol, oleic alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol, and / or 10 to 2 carbon atoms.
And sulfuric acid monoesters of secondary alcohols such as oxo alcohol of 0, hydroxycarboxylic acid, aminocarboxylic acid, hydroxysulfonic acid, aminosulfonic acid, alkyl sulfosuccinic acid, sulfosuccinate, and sulfosuccinic alcohol. Also, soaps such as lauric acid, myristic acid, palmitic acid, stearic acid, coconut oil, palm kernel oil, tallow fatty acid and the like can be mentioned.

As the nonionic surfactant, fatty alcohols, alkylphenols, fatty acids, fatty acid amines, fatty acid amides, ethylene oxide-propylene oxide block copolymers, polyethylene carboxylic acid amides, amino oxides and sulfoxides can be used. .

Examples of the cationic surfactant include an organic acid salt or an inorganic acid salt of an aliphatic amine having at least one alkyl group having 12 to 18 carbon atoms, and a quaternary ammonium salt and an alkyl group such as a benzyl group. And heterocyclic quaternary ammonium salts such as aromatic quaternary ammonium salts, pyridium salts and imidazolium salts, and onium salts such as sulfonyl salts and phosphonium salts.

One or more of these compounds, and these compounds may be present as an organic acid salt such as sodium salt, potassium salt, ammonium salt, mono-, di- or triethanolamine.

Other components of ordinary detergents such as a foam stabilizer, a foam inhibitor, a calcium complexing or precipitating agent, a softening agent, an alkaline agent or an electrolyte,
Bleaching agents, bleach activators, redeposition inhibitors, corrosion inhibitors, bactericidal substances, enzymes, enzyme stabilizers, brighteners, coloring agents, fluorescent agents and the like can be used in combination.

The surfactant of the present invention has excellent characteristics such as water repellency and oil repellency caused by fluorine atoms, and therefore has a high stability vesicles, auxiliaries for pharmaceuticals and agrochemicals, medical materials, oxygen-enriched films, It can be used as an additive for various lubricants, a leveling agent for paints and inks, a paint mover, a resist remover, a foaming agent for cleaning, a fiber treatment agent, a fluorine resin surface modifier, and the like.

Next, the solid polymer electrolyte of the present invention will be described. The polymer solid electrolyte of the present invention is obtained by gelling an aprotic solvent containing the fluoroalkyl group-containing phosphonic acid oligomer represented by the general formula (1) as an electrolyte.

The aprotic solvent that can be used is not particularly limited, but includes, for example, γ-butyrolactone, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolan, sulfolane, dimethyl carbonate, diethyl carbonate, methyl acetate, 1,2-dimethoxyethane, tetrahydrofuran,
Propylene carbonate, ethylene carbonate, butylene carbonate, formamide, dimethylformamide, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxymethane, sulfolane, 3-methyl-2-oxazolidinone, diethyl ether, 1,3- Ether compounds and ester compounds such as propane sultone;
Used in more than species.

The addition amount of the fluoroalkyl group-containing phosphonic acid oligomer represented by the general formula (1) or (2) to the aprotic solvent is usually 0.1
-80 wt%, preferably 1-50 wt%.

Further, the polymer solid electrolyte of the present invention is
It can be used in combination with an electrolyte. Other electrolytes include:
It is not particularly limited as long as it is soluble in an aprotic solvent.
No, but for example, LiClO_Four , LiCl, LiBr,
LiI, LiBF_Four , LiPF₆ , LiCF_Three SO_Three,
LiAsF₆ , LiAlCl_Four , LiB (C₆ H₆ )
_Four , CF_ThreeSO_ThreeLi, LiSbF₆ , LiB_TenC
l_Ten, LiSiF₆ , LiN (SO_Two CF_Three )_Two , Li
C (SO_Two CF_Three )_Two , LiN (CF_Three SO_Three )_Two , Low
Lithium fatty acid carboxylate, lithium chloroborane and
And lithium 4-phenylborate.
One or more kinds of the titanium salts are used. these
The preferable addition amount of the lithium salt is 1 kg of the solvent.
0.1 to 3 mol, preferably 0.5 to 2 mol.

The solid polymer electrolyte of the present invention can be used as an electrolyte for a lithium ion polymer battery or as a plasticizer.

[0092]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 2 equipped with a condenser, a thermometer, a stirrer, and a dropping funnel
In a 00 ml four-necked flask, 3.65 g (19 mmol) of 3-acroyloxypropylphosphonic acid was added to AK-2.
25 (trade name, manufactured by Asahi Glass Co., Ltd., Cl ₂ CHCF ₂ CF
₃ and CClF ₂ CF ₂ CHClF 1: 1 mixed solution, hereinafter the same) was dissolved in 80 g, at room temperature peroxide di perfluoroalkyl butyryl 0.81 g (1.9 mmol) in the above solution,
In a nitrogen stream, the solution was quickly dropped. Heat to 45 ° C and 5
Allowed to stir for hours. After the reaction, the solvent was distilled off under reduced pressure,
The obtained crude product was purified by dialysis using water as a solvent.
Thereafter, the residue was dried under vacuum to obtain 0.36 g (yield: 8%) of an oligomer. FT-IR, ¹ H-
The fluoroalkyl group-containing phosphonic acid oligomer was confirmed by NMR and ¹⁹ F-NMR.

<FT-IR (KBr, cm ⁻¹ )> 347
0 (OH), 1725 (C = O), 1310 (C
F ₃ ), 1245 (CF ₂ ) < ¹ H-NMR (δ, D ₂ O + NaOD)> 1.02-
1.89 (CH ₂ , CH), 1.95-3.15 (C
H ₂ ), 4.64 to 4.73 (CH ₂ ) < ¹⁹ F-NMR (δ, D ₂ O + NaOD, ext. CF ₃
COOH)> − 5.60 (6F), −44.12 (4
F), -54.32 (4F)

From the above analysis results, it was confirmed that the obtained product was a fluoroalkyl group-containing phosphonic acid oligomer having the structure of Sample A in Table 1 represented by the following general formula (1a).

Example 2 5.02 g of 3-acryloyloxypropylphosphonic acid
(25.8 mmol), 1.70 g (2.6 mm) of diperfluoro-2-methyl-3-oxahexanoyl peroxide
ol), except that 0.1 g of the oligomer was obtained (7% yield). FT-
The product was confirmed by IR, ¹ H-NMR and ¹⁹ F-NMR.

<FT-IR (KBr, cm ⁻¹ )> 348
3 (OH), 1731 (C = O), 1308 (C
_{F 3), 1281 (CF 2} ) <1 H-NMR (δ, D 2 O + NaOD)> 1.00~
1.91 (CH ₂ , CH), 1.93 to 3.18 (C
H ₂ ), 4.64 to 4.73 (CH ₂ ) < ¹⁹ F-NMR (δ, D ₂ O + NaOD, ext. CF ₃
COOH)>-5.58 to -7.66 (16F), -4
8.18 (6F)

From the above analysis results, it was confirmed that the obtained product was a fluoroalkyl group-containing phosphonic acid oligomer having the structure of Sample B in Table 1 represented by the following general formula (1a).

Example 3 4.06 g of 3-acroyloxypropylphosphonic acid
(21 mmol), 2.08 g of diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide (2.
Except for using 1 mmol), the synthesis was carried out in the same manner as in Example 1 to obtain 0.29 g of an oligomer (yield: 5%). By FT-IR, ¹ H-NMR and ¹⁹ F-NMR,
The product was confirmed.

<FT-IR (KBr, cm ⁻¹ )> 346
7 (OH), 1635 (C = O), 1261 (C
F ₃ ), 1112 (CF ₂ ) < ¹ H-NMR (δ, D ₂ O + NaOD)> 1.03 to
_{1.71 (CH 2), 2.00 (} CH), 4.67~
4.79 (CH ₂ ) < ¹⁹ F-NMR (δ, D ₂ O + NaOD, ext. CF ₃
COOH)>-5.76 to -6.93 (26F), -4
7.51 (6F)

From the above analysis results, it was confirmed that the obtained product was a fluoroalkyl group-containing phosphonic acid oligomer having the structure of Sample C in Table 1 represented by the following general formula (1a).

Example 4 3.57 g of 3-acroyloxypropylphosphonic acid
(18 mmol), diperfluoro-2,5,8 peroxide
Example 1 except for using 2.38 g (1.8 mmol) of -trimethyl-3,6,9-trioxadodecanoyl
0.32 g of oligomer by synthesizing
(5% yield). FT-IR, ¹ H-NMR, ¹⁹ F
-The product was confirmed by NMR.

<FT-IR (KBr, cm ⁻¹ )> 345
3 (OH), 1633 (C = O), 1248 (C
F ₃ ), 1198 (CF ₂ ) < ¹ H-NMR (δ, D ₂ O + NaOD)> 1.02-
_{1.86 (CH 2), 1.97~2.02 (} CH),
3.00~3.25 (CH _2), 4.67~4.73
(CH ₂ ), < ¹⁹ F-NMR (δ, D ₂ O + NaOD, ext. CF ₃
COOH)>-4.80 to -8.72 (36F), -4
7.50 (6F), -56.59 (4F)

From the results of the above analysis, it was confirmed that the obtained product was a fluoroalkyl group-containing phosphonic acid oligomer having the structure of Sample D in Table 1 represented by the following general formula (1a).

Comparative Example 1 Instead of fluorine peroxide, V-50 manufactured by Wako Pure Chemical Industries, Ltd.
Using 0.68 g (2.5 mmol), 4.85 g (25 mmol) of 3-acroyloxypropylphosphonic acid
Synthesis was performed according to Example 1 except that was used,
0.57 g (yield 10.32%) of 3-acryloyloxypropyl phosphonic acid oligomer was obtained. The purification was performed by a reprecipitation method using a methanol / water system.

The synthesis reaction of the above product is shown below.

[0107]

Embedded image

[0108]

[Table 1]

Example 5 A condenser equipped with a condenser, a thermometer, a stirrer and a dropping funnel was prepared.
In a 00 ml four-necked flask, 3.65 g (19 mmol) of 3-acryloyloxypropylphosphonic acid, 0.93 g of methoxynonylethylene glycol methacrylate
(1.9 mmol) was dissolved in 100 g of the AK-225 solution and 10 g of water, and 0.85 g (1.9 mmol) of diperfluorobutyryl peroxide was added to 20 g of AK-225.
The solution was quickly added dropwise at room temperature in a nitrogen stream. 45
C. and stirred for 5 hours. After the reaction, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by dialysis using water as a solvent. Thereafter, the residue was dried under vacuum to obtain 0.26 g (yield: 5%) of cooligomers. F
The product was confirmed by T-IR, ¹ H-NMR, and ¹⁹ F-NMR.

The molar polymerization ratio (3-acryloyloxypropylphosphonic acid: methoxynonylethylene glycol methacrylate) determined from ¹ H-NMR was 72:
28.

<FT-IR (KBr, cm ⁻¹ )> 345
0 (OH), 1719 (C = O), 1315 (C
F ₃ ), 1242 (CF ₂ ), 1030 (—O —) < ¹ H-NMR (δ, D ₂ O + NaOD)> 0.68 (C
_{H 3), 0.98~1.78 (CH 2} ), 1.91 (C
_{H), 3.25~3.40 (CH 2)} , 4.70~4.
73 (CH ₂ ) < ¹⁹ F-NMR (δ, D ₂ O + NaOD, ext. CF ₃
COOH)> − 5.65 (6F), −45.01 (4
F), -54.52 (4F)

From the analysis results, it was confirmed that the obtained product was a fluoroalkyl group-containing phosphonic acid oligomer having the structure of Sample F in Table 2 represented by the following general formula (2a).

Example 6 5.02 g of 3-acryloyloxypropylphosphonic acid
Example 5 except that (26 mmol), 1.41 g (2.6 mmol) of methoxynonylethylene glycol methacrylate, and 1.71 g (2.6 mmol) of diperfluoro-2-methyl-3-oxahexanoyl peroxide were used.
1.45 g of co-oligomer by synthesis
(18% yield). FT-IR, ¹ H-NMR, ¹⁹
The product was confirmed by F-NMR.

The molar polymerization ratio (3-acryloyloxypropylphosphonic acid: methoxynonylethylene glycol methacrylate) determined from ¹ H-NMR was 68:
32.

<FT-IR (KBr, cm ⁻¹ )> 345
6 (OH), 1731 (C = O), 1240 (C
F ₃ ), 1180 (CF ₂ ), 1016 (—O —) < ¹ H-NMR (δ, D ₂ O + NaOD)> 0.91
_{0.97 (CH 3), 1.06~1.32 (} CH 2),
1.88 to 1.99 (CH), 3.12 to 3.24 (C
H ₂ ), 4.71 to 4.77 (CH ₂ ) < ¹⁹ F-NMR (δ, D ₂ O + NaOD, ext. CF ₃
COOH)> − 5.71 to −7.66 (16F), −4
8.83 (6F)

From the results of the analysis, it was confirmed that the obtained product was a fluoroalkyl group-containing phosphonic acid oligomer having the structure of Sample G in Table 2 represented by the following general formula (2a).

Example 7 4.06 g of 3-acryloyloxypropylphosphonic acid
(21 mmol), 1.04 g (2.1 mmol) of methoxynonylethylene glycol methacrylate, and 2.07 g (2.1 mmol) of diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide. By synthesizing in the same manner as in Example 5, 0.22 g (yield 3%) of a co-oligomer was obtained. FT-IR, ¹ H-N
The product was confirmed by MR and ¹⁹ F-NMR.

The molar polymerization ratio (3-acryloyloxypropylphosphonic acid: methoxynonylethylene glycol methacrylate) determined from ¹ H-NMR was 45:
55.

<FT-IR (KBr, cm ⁻¹ )> 343
6 (OH), 1721 (C = O), 1341 (C
F ₃ ), 1245 (CF ₂ ), 1029 (—O —) < ¹ H-NMR (δ, D ₂ O + NaOD)> 0.73 (C
_{H 3), 0.99~1.72 (CH 2} ), 1.96 (C
_{H), 3.21~3.34 (CH 2)} , 4.64~4.
69 (CH ₂ ) < ¹⁹ F-NMR (δ, D ₂ O + NaOD, ext. CF ₃
COOH)>-4.48 to -6.90 (26F), -1
7.37 (6F), -70.76 (2F)

From the results of the analysis, it was confirmed that the obtained product was a fluoroalkyl group-containing phosphonic acid oligomer having the structure of Sample H in Table 2 represented by the following general formula (2a).

Example 8 3.57 g of 3-acryloyloxypropylphosphonic acid
(18 mmol), 0.91 g (1.8 mmol) of methoxynonyl ethylene glycol methacrylate, diperfluoro-2,5,8-trimethyl peroxide 3,6,9
2.38 g of trioxadodecanoyl (1.8 mmo)
Except for using l), the synthesis was carried out in the same manner as in Example 5 to obtain 0.39 g of a co-oligomer (yield 6%). FT
The product was confirmed by -IR, ¹ H-NMR and ¹⁹ F-NMR.

The molar polymerization ratio (3-acryloyloxypropylphosphinic acid: methoxynonylethylene glycol methacrylate) determined from ¹ H-NMR was 4
5:55.

<FT-IR (KBr, cm ⁻¹ )> 346
9 (OH), 1731 (C = O), 1253 (C
F ₃ ), 1170 (CF ₂ ), 1024 (—O —) < ¹ H-NMR (δ, D ₂ O + NaOD)> 0.70
_{0.80 (CH 3), 1.01~1.84 (} CH 2),
1.98 (CH), 3.23~3.36 (CH 2),
4.60 to 4.73 (CH ₂ ) < ¹⁹ F-NMR (δ, D ₂ O + NaOD, ext. CF ₃
COOH)>-6.72 to -8.70 (36F), -4
7.43 (6F), -56.38 (4F)

From the results of the analysis, it was confirmed that the obtained product was a fluoroalkyl group-containing phosphonic acid oligomer having the structure of Sample I in Table 2 represented by the following general formula (2a).

[0125]

Embedded image

[0126]

[Table 2]

Example 9 0.91 g of 3-acroyloxypropylphosphonic acid
(4.7 mmol), 0.97 g (4.7 mmol) of 2-acrylamido-2-methylpropanesulfonic acid, and 0.62 g (1.0 mmol) of diperfluoro-2-methyl-3-oxahexanoyl peroxide. Was synthesized in the same manner as in Example 5 to give the co-oligomer 1.3.
3 g (51% yield) were obtained. FT-IR, ¹ H-NM
The product was confirmed by R, ¹⁹ F-NMR.

Further, the molar polymerization ratio (3-acryloyloxypropylphosphonic acid: 2-acrylamido-2-methylpropanesulfonic acid) determined from ¹ H-NMR is 3
1:69.

<FT-IR (KBr, cm ⁻¹ )> 342
6 (OH, NH), 1641 (C = O), 1220 (C
F ₃ ), 1195 (CF ₂ ) < ¹ H-NMR (δ, D ₂ O + NaOD)> 0.81 (C
_{H 3), 1.04~1.74 (CH)} , 1.98 (C
_{H), 2.98~3.42 (CH 2)} , 4.59~4.
67 (CH ₂ ) < ¹⁹ F-NMR (δ, D ₂ O + NaOD, ext. CF ₃
COOH)>-5.48 to -7.40 (16F), -4
7.04 (6F)

From the results of the analysis, it was confirmed that the obtained product was a fluoroalkyl group-containing phosphonic acid oligomer having the structure of Sample J in Table 3 represented by the following general formula (2b).

Example 10 1.17 g of 3-acroyloxypropylphosphonic acid
(6.0 mmol), 1.24 g (6.0 mmol) of 2-acrylamido-2-methylpropanesulfonic acid, 1.19 g of diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide (1. Except for using 2 mmol), the synthesis was carried out in the same manner as in Example 5 to obtain 0.27 g of a co-oligomer (31% yield). The product was confirmed by FT-IR. In addition, the gel-forming ability is high and N
MR measurements were difficult.

<FT-IR (KBr, cm ⁻¹ )> 343
0 (OH, NH), 1639 (C = O), 1320 (C
F ₃ ), 1218 (CF ₂ )

From the results of the analysis, it was confirmed that the obtained product was a fluoroalkyl group-containing phosphonic acid oligomer having the structure of Sample K in Table 3 represented by the following general formula (2b).

[0134]

Embedded image

[0135]

[Table 3]

<Evaluation as Surfactant> Example 1
With respect to the fluoroalkyl group-containing phosphonic acid oligomers of the samples obtained in Nos. 1 to 10, solubility in various solvents was tested. Table 4 shows the results. The symbols in the table indicate the following. ○; very soluble, △; not very soluble, ×;
Does not dissolve at all, G; gelation

2. Samples of B, C, D and E obtained in Examples 2, 3, 4 and Comparative Example 1 were allowed to stand at 30 ° C. overnight, and then dissolved in m-xylene to prepare samples of various concentrations. . The surface tension of each sample was measured at a constant temperature of 30 ° C. using a surface tensiometer. The result is shown in FIG.

[0138]

[Table 4]

(Note) The abbreviations in the table are as follows. AK-255; Cl ₂ CHCF ₂ CF ₃ and CCIF ₂ CF ₂
CHClF 1: 1 mixed solution, THF; tetrahydrofuran, DMSO; dimethyl sulfoxide, DE; dichloroethane

<Geling properties> Examples 1-4, 6, 7,
Regarding the fluoroalkyl group-containing phosphonic acid oligomers of the samples obtained in 8 and 9, 3
The minimum gelling concentration (C _min ) at 0 ° C. was measured. Table 5 shows the results.

[0141]

[Table 5]

<Polymer Solid Electrolyte> For Samples J and K obtained in Examples 9 and 10, the ionic conductivity was measured. Table 6 shows the results.

The measurement of the ionic conductivity was performed as follows. Table 6 shows the amount of DMSO to gel the oligomer.
The Li salt was added at the ratio shown in
g was added to prepare a gel for measurement. The gel for measurement was put into a pyrex glass cell, and the conductivity was measured by sandwiching the upper electrode and the lower electrode made of brass. Further, the thickness of the gel was measured using a microhead, and the ionic conductivity was calculated based on the measured thickness.

[0144]

[Table 6]

(Note) Li salt is LiN (CF ₃ SO ₃ )
_2. DMSO was used as the solvent.

[0146]

As described above, the fluoroalkyl group-containing phosphonic acid oligomer of the present invention is a novel compound, is useful as a non-aqueous surfactant, and has excellent ionic conductivity. Can be used as an electrolyte or a plasticizer for lithium ion polymer batteries.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the concentration of fluoroalkyl group-containing phosphinic acid oligomers of the present invention and surface tension.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08F 290/06 C08F 290/06 H01M 10/40 H01M 10/40 B F term (Reference) 4H050 AA01 AA02 AB68 AB80 AC20 4J015 BA06 4J027 AC03 AC06 AC09 BA07 BA13 BA16 CB03 4J100 AL08P AL08Q BA04Q BA05Q BA08Q BA28Q BA56Q BA64P CA01 CA04 FA03 JA15 JA43 5H029 AM00 AM03 AM04 AM05 AM07 AM16 DJ09 EJ11

Claims (6)

[Claims] 1. A fluoroalkyl group-containing phosphonic acid oligomer represented by the following general formula (1). Embedded image (Wherein R ¹ and R ² are — (CF ₂ ) _m1 Y or —CF (C
F ₃₎ - [OCF ₂ CF (CF _3)] is an _m2 -OC ₃ F _7. ｛Wherein, Y represents a hydrogen atom, a fluorine atom or a chlorine atom. m1 represents an integer of 1 to 10, and m2 represents an integer of 0 to 10. ｝ R ³ represents a hydrogen atom or a methyl group. B represents an alkylene group. n shows the integer of 1-1000. ) 2. A fluoroalkyl group-containing phosphonic acid oligomer represented by the following general formula (2). Embedded image (Wherein R ¹ and R ² are — (CF ₂ ) _m1 Y or —CF (C
F ₃₎ - [OCF ₂ CF (CF _3)] is an _m2 -OC ₃ F _7. ｛Wherein, Y represents a hydrogen atom, a fluorine atom or a chlorine atom. m1 represents an integer of 1 to 10, and m2 represents an integer of 0 to 10. ｝ R ³ and R ⁴ represent a hydrogen atom or a methyl group. B represents an alkylene group. A is the following general formula (3): ＸIn the formula, X ¹ is a hydrogen atom or a methyl group, and X ² is carbon atom 1
And t represents an integer of 2 to 300. An alkylene oxide group having an ester bond represented by｝, or the following general formula (4): ＺIn the formula, Z represents an alkylene group.ス ル ホ ン represents a sulfonic acid group. n shows the integer of 1-1000. a: b
Is from 1:99 to 99: 1. ) 3. The following general formula (5): (Wherein R ¹ and R ² have the same meanings as described above) and a fluoroalkanoyl peroxide represented by the following general formula (6): (Wherein, R ³ and B are as defined above).
Reacting with a phosphonic acid compound having an acrylic group, represented by the following general formula (1): (Wherein, R ¹ , R ² , R ³ , B and n have the same meanings as defined above). 4. The following general formula (5): (Wherein R ¹ and R ² have the same meanings as described above) and a fluoroalkanoyl peroxide represented by the following general formula (6): (Wherein, R ³ and B are as defined above).
A phosphonic acid compound having an acrylic group, and a compound represented by the following general formula (7): (Wherein, R ⁴ and A are as defined above).
Reacting a compound having an acryl group with a compound having the following general formula (2): (Wherein R ¹ , R ² , R ³ , R ⁴ , A, B, a, b and n have the same meanings as described above). Method. 5. A surfactant comprising the fluoroalkyl group-containing phosphonic acid oligomer according to claim 1 as an active ingredient. 6. A solid polymer electrolyte comprising the fluoroalkyl group-containing phosphonic acid oligomer according to claim 1 or 2.