JP2005350604A - Ionic liquid type functional material composed of fluorine-containing polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a functional material that is composed of a fluorine-containing polymer having liquid properties/low viscosity combined with oxidation resistance/heat resistance and is useful as an ionic liquid. <P>SOLUTION: The ionic liquid type functional material comprises a fluorine-containing polymer represented by formula (M-1):-(M1)-(M2)-(A1)-(M-1) [structural unit M1 is a structural unit derived from a fluorine-containing ethylenic monomer which has a part -D- of a fluorine-containing ether structure in a side chain and contains neither a basic functional group nor the salt of the basic functional group; M2 is a structural unit derived from an ethylenic monomer having a part Ry containing a basic functional group in the side chain or a side chain terminal; Ry is a structural unit of a 2-30C monofunctional or bifunctional organic group containing at least one of a basic functional group Y<SP>1</SP>and/or a salt Y<SP>2</SP>of the basic functional group and an aromatic ring structure; structural unit A1 is a structural unit derived from a monomer copolymerizable with a monomer providing structural units M1 and M2] in the ratio of 1-99 mol% of structural unit M1, 1-99 mol% of a structural unit M2 and 0-98 mol% of a structural unit A1. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a functional material comprising a fluorine-containing polymer comprising a structural unit having a specific fluorine-containing ether structure moiety in a polymer side chain and further having a basic functional group. Such materials are useful as functional materials such as ionic liquids, solar cell electrolytes, lubricants, deoxidizers, and actuator materials.

An ionic liquid is a molten salt that is in a liquid state from room temperature to a relatively high temperature (˜300 ° C.). Its features are
(I) In general, it exhibits high polarity and exhibits high dissolving power for low molecular organic compounds and inorganic compounds.
(Ii) Since the vapor pressure is extremely low and non-volatile, when used as a synthesis reaction medium, it can be used in a vacuum or provide a clean reaction environment.
(Iii) Since it is insoluble in several organic solvents and water, it can provide a reaction environment in a two-layer medium, etc., and it is easy to separate reaction raw materials and products, and reaction control by interfacial reaction For example, the stereoselectivity of the product of the synthesis reaction can be controlled, resulting in various novel organic synthesis reactions.

  Conventionally, various imidazolium salt compounds have been studied as ionic liquids. For example, for the purpose of reducing the viscosity, an ionicity in which an alkoxyl group is introduced into the alkyl portion of an N, N′-dialkylimidazolium salt. A liquid (Patent Document 1) has been proposed, and it has been reported that it is possible to lower the viscosity and solubilize synthetic polymers, biopolymers, molecular aggregates, and the like.

  However, even in these studies (Patent Document 1), the viscosity is still high and the reduction effect is insufficient even by introduction of an alkoxyl group. Furthermore, these ionic liquids themselves, heat resistance and oxidation resistance There are problems such as insufficient stability and durability.

  On the other hand, in applications of the above ionic liquids, improvement of separation from solvents (organic solvents and water), improvement of thermal stability, prevention of penetration and outflow from packages and devices, creation of film shapes, etc. Various studies have also been conducted on polymerizing ionic liquids (ionic liquid type polymers).

  As an ionic liquid type polymer, N-vinyl imidazolium salt polymer obtained by polymerizing N-vinyl, N′-alkyl imidazoline salt or N-vinyl imidazoline salt (Patent Document 2, Patent Document 3) is disclosed. Yes. The monomer N-vinylimidazolium salt has a form of an ionic liquid, but the polymer having an imidazolium structure obtained by polymerization is solid or rubbery and liquid. Since it does not show the properties or has extremely high viscosity, it has a poor affinity with the substrate used as an ionic liquid, for example, a reaction medium or an extraction medium, and can perform a sufficient dissolution or extraction function. There is nothing. Moreover, these ionic liquid type polymers are insufficient in oxidation resistance, heat resistance and chemical resistance.

JP 2002-3478 A Japanese Patent Laid-Open No. 10-83821 JP 2000-11754 A

  In view of the above situation, an object of the present invention is to provide a functional material that is made of a fluorine-containing polymer having liquidity / low viscosity and oxidation resistance / heat resistance, and is useful as an ionic liquid.

  Specifically, it is to provide a functional material useful as a material that exhibits a function as an ionic liquid, such as a synthesis reaction medium, an extraction medium, a deoxidizer, a solar cell electrolyte, a lubricant, and an actuator material. .

  Furthermore, this invention is providing the novel fluorine-containing polymer which can be utilized for the said ionic liquid type functional material.

  As a result of intensive studies on polymers having basic functional groups, the present inventors have found that an ethylenic monomer having a specific fluorine-containing ether chain in the side chain portion of the polymer and a basic functional group on the side of the polymer. It has been found that a fluorine-containing copolymer obtained by polymerizing a monomer mixture composed of an ethylenic monomer in the chain portion exhibits good liquidity or low viscosity, and is excellent in oxidation resistance and heat resistance. .

  In addition, the inventors have found that these polymers have excellent performance as compounds constituting high-functional materials such as ionic liquid type functional materials such as solar cell electrolytes, actuators, lubricants, deoxidizers, etc. It came to be completed.

The present invention relates to formula (M-1):
-(M1)-(M2)-(A1)-(M-1)
[Wherein, the structural unit M1 is derived from a fluorine-containing ethylenic monomer having a moiety -D- of a fluorine-containing ether structure in the side chain and not containing a basic functional group and a salt of the basic functional group. A structural unit, wherein the portion D of the fluorine-containing ether structure is represented by the formula (1):

(Wherein R is at least one selected from divalent fluorine-containing alkylene groups having 1 to 5 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; n is an integer of 1 to 20). Structural unit, except that -O-O- unit is not included in the side chain of the structural unit M1; the structural unit M2 is an ethylenic unit having a site Ry containing a basic functional group in the side chain or at the end of the side chain. A structural unit derived from a mer, wherein Ry has at least one of a basic functional group Y ¹ and / or a salt Y ² of the basic functional group, and contains an aromatic cyclic structure. A structural unit derived from a monomer copolymerizable with a monomer capable of giving structural units M1 and M2], wherein the structural unit M1 is 1 -99 mol%, structural unit M2 is 1-99 mol%, structural unit The present invention relates to an ionic liquid type functional material comprising a fluorine-containing polymer containing 0 to 98 mol% of A1.

In the fluorine-containing ether moiety -D-, -O-R- is-(OCFZ ¹ CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ )-,-(OCH ₂ CF ₂ CF ₂ )-,-(OCFZ ² )-,-(OCZ ³ ₂ )-,-(CFZ ¹ CF ₂ O)-,-(CF ₂ CF ₂ CF ₂ O)-,-(CH ₂ CF ₂ CF ₂ O)-,-(CFZ ² O)-and-(CZ ³ ₂ O)-(wherein Z ¹ and Z ² may be the same or different, H, F or CF ₃ ; Z ³ is CF ₃ ). Preferred are species of fluoroether units.

  The structural unit M1 is represented by the formula (1-2):

Wherein X ¹ , X ² , X ⁴ and X ⁵ are the same or different and are a hydrogen atom or a fluorine atom; X ³ is at least one selected from a hydrogen atom, a fluorine atom, CH ₃ and CF ₃ ; n1, n2 is the same or different and is 0 or 1; Rx is at least one selected from a hydrogen atom, a halogen atom, and a fluorine-containing alkyl group which may contain an ether bond having 1 to 20 carbon atoms, provided that in Rx And D is preferably a structural unit represented by the same formula (1).

The basic functional group Y ^{1 in} Ry or the salt Y ² of the basic functional group is at least one selected from amines, imines, enamines, ketimines, azines and salts thereof. preferable.

The present invention also provides a compound of formula (M-2):
-(M3)-(M4)-(A2)-(M-2)
[Wherein the structural unit M3 is represented by the formula (3):

{Wherein X ¹¹ , X ¹² , X ¹⁴ and X ¹⁵ are the same or different and are a hydrogen atom or a fluorine atom; X ¹³ is at least one selected from a hydrogen atom, a fluorine atom, CH ₃ and CF ₃ ; n5, n6 is the same or different and is 0 or 1; D ¹ is a part of a fluorine-containing ether structure, and the formula (3-1):

(Wherein R ¹ is at least one selected from divalent fluorine-containing alkylene groups having 1 to 5 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; m is an integer of 1 to 20) Rx ¹ is at least one selected from a hydrogen atom, a halogen atom, and a fluorine-containing alkyl group having 1 to 20 carbon atoms which may have an ether bond, provided that in Rx ¹ , the above D ¹ Is a structural unit represented by However, the unit of —O—O— is not included in the structural unit M1 and the formula (3-1); the structural unit M4 is represented by the formula (4):

{Wherein X ¹⁶ , X ¹⁷ , X ¹⁹ and X ²⁰ are the same or different and are a hydrogen atom or a fluorine atom; X ¹⁸ is at least one selected from a hydrogen atom, a fluorine atom, CH ₃ and CF ₃ ; n7, n8 is the same or different and is 0 or 1; Ry ¹ is a monovalent having 2 to 30 carbon atoms having at least one of amines Y ³ and / or salts Y ⁴ of amines and containing an aromatic ring structure A structural unit derived from a monomer copolymerizable with a monomer capable of giving structural units M3 and M4], wherein 1 to 99 mol of structural unit M3 %, The structural unit M4 is 1 to 99 mol%, the structural unit A2 is 0 to 98 mol%, and the number average molecular weight is 500 to 1,000,000.

  According to the present invention, it is excellent in oxidation resistance, ionic stability, heat resistance, lubricity, water insolubility, low viscosity, etc., and is a lubricant, deoxidizer, various ionic liquids or solid materials, solar cell electrolyte, actuator A functional material useful as a material can be provided.

The ionic liquid type functional material of the present invention has the formula (M-1):
-(M1)-(M2)-(A1)-(M-1)
[Wherein, the structural unit M1 is derived from a fluorine-containing ethylenic monomer having a moiety -D- of a fluorine-containing ether structure in the side chain and not containing a basic functional group and a salt of the basic functional group. A structural unit, wherein the portion D of the fluorine-containing ether structure is represented by the formula (1):

(Wherein R is at least one selected from divalent fluorine-containing alkylene groups having 1 to 5 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; n is an integer of 1 to 20). Structural unit, except that -O-O- unit is not included in the side chain of the structural unit M1; the structural unit M2 is an ethylenic unit having a site Ry containing a basic functional group in the side chain or at the end of the side chain. A structural unit derived from a monomer, wherein Ry has at least one of a basic functional group and / or a salt of the basic functional group, and contains an aromatic cyclic structure, A structural unit which is a divalent organic group; the structural unit A1 is a structural unit derived from a monomer copolymerizable with a monomer capable of providing the structural units M1 and M2, and the structural unit M1 is 1 to 99 mol%. 1 to 99 mol% of the structural unit M2 and the structural unit A1 It is made of fluorine-containing polymer containing 98 mol%.

The fluorine-containing polymer of the formula (M-1) is an ethylenic polymer having structural units M1 and M2 derived from an ethylenic monomer as essential components. The side chain structure of one structural unit M1 has a fluoroether unit -D-, and the side chain structure of the other structural unit M2 has a basic functional group Y ¹ and / or a salt of the basic functional group. characterized in that it has a site Ry aromatic ring structure having Y ^2.

The inventors introduce a structural unit M1 derived from an ethylenic monomer having a fluoroether structure in the side chain into a polymer having a basic functional group Y ¹ or a salt Y ² thereof (site Ry). Thus, it has been found that even a polymer compound that is usually solidified or highly viscous can be liquefied or reduced in viscosity more effectively.

  Furthermore, the introduction of the fluoroether unit effectively acts also in oxidation resistance, heat resistance and chemical resistance.

  Therefore, the feature of the fluoropolymer used for these ionic liquid type functional materials is that the side chain of the structural unit M1 contains a fluoroether unit represented by -D- in the above formula (1). Specifically, it has 1 to 20 repeating units n of-(O-R)-.

  -R- is a C1-C5 divalent fluorine-containing alkylene group having at least one fluorine atom, thereby having a conventional fluorine-free alkoxyl group or alkylene ether Compared to those having units, the polymer intended for the ionic liquid type polymer can be liquefied, and the viscosity can be further reduced.

  Further, the fluorine-containing ether unit -D- is also preferable in that the heat resistance and oxidation resistance can be greatly improved.

  The higher the fluorine content in R, the higher the fluorine-containing ether unit -D-, the higher the effects on viscosity reduction, heat resistance and oxidation resistance. The fluorine content in the fluorine-containing alkylene group R is preferably 45 to 76. % By mass, more preferably 55 to 76% by mass, particularly preferably 65 to 76% by mass, and most preferably R is a perfluoroalkylene group (76% by mass).

— (O—R) — or — (R—O) — in —D— is specifically, — (OCF ₂ CF ₂ CF ₂ ) —, — (CF ₂ CF ₂ CF ₂ O) —, -(OCFZ ¹ CF ₂ )-,-(OCF ₂ CFZ ¹ )-,-(OCFZ ² )-,-(CFZ ² O)-,-(OCH ₂ CF ₂ CF ₂ )-, (OCF ₂ CF ₂ CH _{2) -, - (OCH 2} CH 2 CF 2) -, - (OCF 2 CH 2 CH 2), - (OCF 2 CF 2 CF 2 CF 2) -, - (CF 2 CF 2 CF 2 CF 2 O) _{^{-, - (OCFZ 2 CH 2}} ) -, - (CH 2 CFZ 2 O) -, - (OCH (CH 3) CF 2 CF 2) -, - (OCF 2 CF 2 CH (CH 3)) -, - (OCZ ³ ₂ )-and-(CZ ³ ₂ O)-(Z ¹ and Z ² are the same or different, H, F or CF ₃ , Z ³ is CF ₃ ), etc. of Is preferably a species or two or more repeating units.

Among them, -D- is-(OCFZ ¹ CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ )-,-(OCH ₂ CF ₂ CF ₂ )-,-(OCFZ ² )-,-(OCZ ³ ₂ )-,-(CFZ ¹ CF ₂ O)-,-(CF ₂ CF ₂ CF ₂ O)-,-(CH ₂ CF ₂ CF ₂ O)-,-(CFZ ² O)-and-(CZ ³ ₂ One or more repeating units selected from O)-are preferred, and in particular,-(OCFZ ¹ CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ )-, and-(OCH ₂ CF ₂ CF ₂ )-,-(CFZ ¹ CF ₂ O)-,-(CF ₂ CF ₂ CF ₂ O)-and-(CH ₂ CF ₂ CF ₂ O)- Furthermore,-(OCFZ ¹ CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ )-,-(CFZ ¹ CF ₂ O)-and-(CF ₂ It is preferably one or two or more repeating units selected from CF ₂ CF ₂ O) —.

  However, in the fluorine-containing ether unit -D- and in the structural unit M1 of the fluorine-containing polymer of the formula (M-1), -O-O- (specifically, -R-O-O- R—, —O—O—R—, —R—O—O— and the like) are not included.

  These preferred fluorine-containing ethers, especially perfluoroethers, can effectively liquefy or lower the viscosity of polymers intended for ionic liquid type polymers, and also have higher ionic properties with higher heat resistance and higher oxidation resistance. Liquid functional materials can be provided.

  The number n of repeating fluorine-containing ether units in -D- is appropriately selected depending on the purpose, aim and application, and is selected from 1 to 20 repeating numbers.

  The larger the n number, the more effective it is to reduce the viscosity. However, if it exceeds 20, the effect on the basicity and dielectric constant based on the aromatic cyclic site Ry containing the basic functional group described later is lowered, which is not preferable. .

  In applications such as ionic liquids, actuators, and solar cell electrolytes described later, the effects of basicity and dielectric constant derived from Ry of this compound are important. In such a case, the repeating number n of the fluorine-containing ether unit is preferably 1 to 10, more preferably 1 to 5.

  Further, for example, an anionic polymer may be used as a deoxidizing material for removing acid in the waste liquid from the viewpoint of ease of separation from water and ease of regeneration. However, since the deoxidation process is a liquid / solid reaction, it is not always efficient. Since this compound containing a fluorine-containing ether is itself liquid, the deoxidation process becomes a liquid / liquid reaction, and the efficiency is high. However, when the fluorine-containing ether chain is short, the present compound may be dissolved in an acidic aqueous solution and separation may be difficult. From this viewpoint, the longer fluorine-containing ether chain is preferable.

  Therefore, it is preferable that the number n of repeating fluorine-containing ether units is larger in materials such as deoxidizers and lubricants, which are applications that make use of the characteristics of the fluorine-containing ether units themselves, and is preferably 5 to 20, more preferably 10 to 20 .

The side chain structure of the structural unit M1 in the polymer of the formula (M-1) of the present invention is
-D-Rx (1-1)
(Wherein Rx is at least one selected from a hydrogen atom, a halogen atom, and a fluorine-containing alkyl group that may contain an ether bond having 1 to 20 carbon atoms; D is the same as the above formula (1)). Having at the end of the side chain is preferred.

  Introduction of Rx to the side chain end of the structural unit M1 is preferable in that the fluoropolymer (M-1) can be reduced in viscosity and liquefied, and oxidation resistance can be imparted.

  When Rx is a fluorine-containing alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and is preferable in terms of viscosity reduction, liquefaction and oxidation resistance.

  Further, Rx having a high fluorine content is preferable from the viewpoint of oxidation resistance, and the fluorine content is 40% by mass or more, more preferably 50% by mass or more, particularly 60% by mass or more, and most preferably perfluoro. It is an alkyl group.

  In particular,

Among them, preferably,
_{H, F, C 3 F 7} -, CF 3 -, C 2 F 5 -, CF 3 CH 2 -, HCF 2 CF 2 CH 2 -,
_{CF 3 CF 2 CH 2 -,} (CF 3) 2 CH-, C 3 F 7 O-, CF 3 O-, C 2 F 5 O-, CF 3 CH 2v -, HCF 2 CF 2 CH 2 O-, CF ₃ CF ₂ CH ₂ O—, (CF ₃ ) ₂ CHO—
Etc.

  Specifically, the structural unit M1 is represented by the formula (1-2):

(Wherein X ¹ , X ² , X ⁴ and X ⁵ are the same or different and are a hydrogen atom or a fluorine atom; X ³ is at least one selected from a hydrogen atom, a fluorine atom, CH ₃ and CF ₃ ; n1 , N2 are the same or different, 0 or 1; D and Rx are structural units represented by the same formula (1-1)), liquefaction and low viscosity can be achieved more effectively, Furthermore, it is preferable in terms of excellent oxidation resistance and heat resistance.

  Specifically, the structural unit M1 in the formula (1-2) is

Among them, the structural unit of the formula (1-2) is preferably the formula (1-3):

In particular, the oxidation resistance and heat resistance are structural units represented by the formula (X ¹ , X ² , X ³ , X ⁴ , X ⁵ , D, Rx and n1 are the same as those in the formula (1-2)). In terms of chemical properties and chemical resistance.

  The structural unit of formula (1-3) is more specifically

Are preferred, and in particular,

These structural units are more preferred in terms of oxidation resistance, heat resistance and chemical resistance.

  These preferred structural units M1 are more specifically,

(Wherein p is an integer of 2 to 15)

(Wherein q is an integer of 2 to 15)
Etc. can be preferably exemplified.

In the fluorine-containing polymer of the formula (M-1) used for the ionic liquid type functional material of the present invention, the other essential component structural unit M2 contains a basic functional group in the side chain or at the end of the side chain. A structural unit derived from an ethylenic monomer having a site Ry, wherein Ry has at least one of a basic functional group Y ¹ and / or a salt Y ² of the basic functional group, and has an aromatic cyclic structure It is a monovalent or divalent organic group having 2 to 30 carbon atoms.

The basic functional group Y ^{1 in} Ry may be selected from functional groups having a pKa value larger than that of water, but is usually selected from 20 or more functional groups in pKa. The functional group is preferably 20 or more by pKa, more preferably 25 or more by pKa, and particularly preferably 28 or more by pKa.

  If the basicity is too low (pKa is too low), when it is reacted with an acid to form a salt, the ionic function as an ionic liquid cannot be sufficiently exhibited, which is not preferable.

  For example, when used as a reaction medium or as a part thereof, it becomes difficult to dissolve the target reaction substrate, the target reaction does not occur, or the selectivity of the target reaction product cannot be obtained. To do. Moreover, when used as a deoxidizer, the target acid cannot be trapped or the acid cannot be separated and extracted. In addition, when used for actuator applications, the target motion performance may not be obtained.

Specifically, the basic functional group Y ^{1 in} Ry is phosphoric acid amides, phosphoric acid imides, amines, imines, enamines, ketimines, hydroxylamines, amidines, azines, hydrazine. At least one selected from the group consisting of amines, oximes, and amine oxides, among which amines, imines, enamines, ketimines, and azines are preferable, and amines are particularly preferable. is there.

When an amine is bonded to an aromatic cyclic carbon atom described later as a substituent, a primary amino group (—NH ₂ ), a secondary amino group (—NR ¹ H), a tertiary amino group (—NR) ² R ³ ) can be used, but usually a secondary amino group or a tertiary amino group has a hydrocarbon group having a small number of carbon atoms (R ¹ , R ² , R ³ ). A lower amino group is preferred in terms of oxidation resistance. For example, it is a C1-C10 hydrocarbon group, Preferably it is a C1-C5 hydrocarbon group, More preferably, it is a methyl group or an ethyl group. Among these, a primary amino group (—NH ₂ ) is most preferable in terms of oxidation resistance.

  When the nitrogen atoms forming the amino group simultaneously constitute an aromatic ring, it can usually take the form of a secondary or tertiary amino group. These cyclic amino groups themselves are excellent in oxidation resistance. However, when a monovalent hydrocarbon group is further bonded to the nitrogen atom of the cyclic amino group, it may be a hydrocarbon group having a small number of carbon atoms as described above. preferable. For example, it is a C1-C10 hydrocarbon group, Preferably it is a C1-C5 hydrocarbon group, More preferably, it is a methyl group or an ethyl group. Among these, a cyclic amino group in which a monovalent hydrocarbon group is not bonded to a nitrogen atom is most preferable in terms of oxidation resistance.

In the ionic liquid-type functional material of the present invention, or functional groups contained in Ry is a salt Y ² of the basic functional group, preferably contains a salt Y ² of the basic functional groups.

The salt Y ² of the basic functional group can be selected without particular limitation as long as it is a salt of the basic functional group Y ¹ described above and an anion (anion species), and the type, function, and purpose of the aromatic compound It is appropriately selected depending on the use and the like.

Furthermore, the basic functional group salt Y ² may be a salt obtained by quaternizing the basic functional group Y ¹ , for example, a salt of a quaternary ammonium cation obtained by quaternizing an amine. It may be.

Examples of the anion in the basic functional salt Y ² include anions derived from halogen atoms such as Cl ⁻ , Br ⁻ and F ⁻ , HSO ₃ ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ^- such anions derived from inorganic _{^{acids, CF 3 SO 3 -, -}} N (SO 2 CF 3) 2, - C (SO 2 CF 3) 2, - such as an anion derived from organic acids such as OCOCF ₃ is available.

Among them, the anion preferable as an ionic liquid type functional material is selected from the group consisting of an anion derived from an inorganic acid and an anion derived from an organic acid because it can easily be liquefied and can be reduced in viscosity. Particularly preferred is an anion derived from an inorganic acid. Furthermore, an anion capable of forming a Lewis acid is preferable, and for example, PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ^{− and the} like are preferable.

In the ionic liquid type functional material of the present invention, Ry has an aromatic cyclic structure in addition to the basic functional group Y ¹ and the salt Y ² of the basic functional group.

  The part of the aromatic ring structure may be an aromatic ring structure formed only from carbon atoms, or an aromatic ring structure formed from carbon atoms and hetero atoms such as nitrogen atoms, sulfur atoms, and phosphorus atoms. Further, it may be a monocyclic structure or a polycyclic structure (fused ring).

  As a specific example of the site of the aromatic cyclic structure,

Etc.

  The presence of these aromatic ring structures is preferable in that the ionic liquid type functional material of the present invention provides improved oxidation resistance and improved dielectric constant.

  In the ionic liquid type functional material of the present invention, the presence of the structural unit M1 containing the fluorine-containing ether unit -D- described above is usually disadvantageous in terms of dielectric constant, but by introducing these aromatic cyclic structures. , Can improve the dielectric constant.

  Specifically, the improvement in dielectric constant is particularly preferable for ionic liquid applications and solar cell electrolyte applications.

  Further, the presence of the aromatic cyclic structure is preferable in that the interaction (affinity) is high with respect to various inorganic compounds, hydrocarbon compounds, polymer compounds, and the like, and the adsorptivity can be increased.

  In the ionic liquid type functional material of the present invention, the presence of the structural unit M1 containing the fluorine-containing ether unit -D- described above is usually disadvantageous in terms of adsorption power, but by introducing an aromatic cyclic structure, Good adsorptivity to various inorganic and organic materials can be improved. This improvement in the adsorption force can be a material suitable for a functional material such as a lubricant that requires adhesion to a base material.

Bonding of basic functional group Y ¹ or basic functional group salt Y ² (hereinafter Y ¹ and Y ² will be collectively referred to as functional group Y) to the aromatic ring structure is replaced with the aromatic ring structure. A group bonded outside the ring as a group, or a hetero atom forming a functional group Y (cation moiety in the case of a salt) may simultaneously form an aromatic ring.

The functional group Y bonded to the aromatic ring structure as a substituent may be one in which Y ¹ or Y ² is bonded directly to the aromatic cyclic carbon, or the aromatic cyclic carbon and the functional group Y are bonded to each other. You may couple | bond together through the joint (spacer) of a bivalent organic group.

  The divalent organic machine serving as a bond is preferably selected from a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a divalent alkylene group having 1 to 5 carbon atoms, particularly a methylene group, An ethylene group is preferred. A hydrocarbon group having a too long chain length is not preferable because it reduces oxidation resistance.

  When forming an aromatic ring structure from a carbon atom and a hetero atom, the hetero atom which forms the said functional group Y (cation part) may comprise the aromatic ring simultaneously.

  Furthermore, as indicated above, the functional group Y is present as one or more substituents in the aromatic ring structure or in the ring structure, and may be present in two or more. .

In particular,
(I) A functional group Y bonded as a substituent to an aromatic cyclic carbon atom

Etc.
(Ii) An atom in which the functional group Y (a cation moiety in the case of the salt Y ² ) forms an aromatic ring at the same time. Specifically, when the functional group Y is an amine,

Etc.
(Iii) A functional group Y further bonded as a substituent to the aromatic cyclic carbon of (ii). Specifically,

Etc. are preferred.

  Among these sites of aromatic cyclic structures (i) to (iii), the functional group amount (concentration) can be improved, the function as an ionic liquid type functional material, and the solute as a reaction medium or extraction medium. The atom which forms the functional group Y (cation part) of the above (ii) simultaneously constitutes an aromatic ring in terms of improving the kinetic performance when it is used as a dissolving power, an acid collecting power and an actuator, What further substituted the functional group of iii) is preferable.

  Moreover, these (ii) and (iii) sites are also preferred from the standpoint of oxidation resistance.

  Furthermore, the ring structure of the site Ry of the aromatic ring structure of the present invention is preferably a monocyclic structure, whereby low viscosity and liquefaction can be effectively achieved.

  In the fluoropolymer (M-1), Ry is bonded to the main chain portion or bonded to a site -S- other than Ry in the side chain of the structural unit M2.

  The main chain moiety or side chain moiety -S- and Ry are bonded to each other by the fact that Ry as exemplified in the above (i), (ii) or (iii) is directly linked to the main chain moiety or side chain moiety (-S-). In the case of bonding, the second is a case where there is a bond (spacer) between Ry and the main chain or -S-, and Ry and the main chain or side chain site via the bond. When -S- is bonded, a bond (-A-) is included in Ry (when Ry has a bond -A-, Ry is -A-Ry ").

  A direct bond between Ry and the main chain portion or side chain portion (-S-) is particularly preferable in terms of heat resistance and oxidation resistance.

  In the case of using a bond, the bond (-A-) is not particularly limited as long as it is a divalent bond bonded by a covalent bond, and is selected from a divalent hetero atom and a divalent organic group.

  Among them, ether bonds (—O—), thioether bonds (—S—), divalent alkylene groups, divalent fluorine-containing alkylene groups, ester bonds, sulfonate ester bonds, phosphate ester bonds, acid amide bonds, An amidine bond or the like is more preferable in that it does not lower the oxidation resistance.

In particular,
(A) When the bond -A- is a divalent alkylene group or a divalent fluorine-containing alkylene group, the divalent alkylene group is preferably selected from a divalent alkylene group having 1 to 10 carbon atoms, more preferably. Is preferably a divalent alkylene group having 1 to 5 carbon atoms, particularly a methylene group or an ethylene group. A hydrocarbon group having a too long chain length is not preferable because it reduces oxidation resistance.

  The divalent fluorine-containing alkylene group is one in which part or all of the hydrogen atoms of the above-mentioned alkylene group are substituted with fluorine atoms, and those in which more fluorine atoms are substituted with respect to oxidation resistance are preferred. Is preferably a perfluoroalkylene group.

  In particular,

(Where m1 is 0 or 1)
Etc. are preferred.

  These are particularly preferable in terms of oxidation resistance.

(B) When the bond -A- is an ether bond (-O-) or a thioether bond (-S-)
-(S) _m1 -O-Ry ",-(S) _m1 -S-Ry"
(Where m1 is 0 or 1)
Etc.

  In particular, an ether bond is preferable in terms of oxidation resistance, heat resistance, and chemical resistance.

(C) When the bond -A- is an ester bond, a sulfonate bond, or a phosphate bond, specifically,

(Where m1 is 0 or 1)
Etc.

(D) When the bond -A- is an amide bond Specifically,

(Wherein R ′ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; m1 is 0 or 1)
Especially, it is preferable that R 'is a hydrogen atom or a C1-C5 alkyl group at the point which does not reduce oxidation resistance and heat resistance. Particularly preferred is a hydrogen atom or a methyl group.

  In particular,

(Where m1 is 0 or 1)
Is mentioned.

  These are preferable in terms of excellent oxidation resistance and heat resistance.

(E) When the bond -A- is a sulfonamide bond or a phosphoric acid amide bond Specifically,

(Wherein, R ′ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; m1 is 0 or 1).

  Among these, R ′ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms from the viewpoint of not reducing oxidation resistance and heat resistance. Particularly preferred is a hydrogen atom or a methyl group.

  In particular,

(Where m1 is 0 or 1)
Etc. are preferred.

(F) When the bond -A- is an amidine bond Specifically,

(Wherein, R ′ and R ″ are the same or different and are each a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; m1 is 0 or 1).

  Among these, R ′ and R ″ are preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms from the viewpoint of not reducing the oxidation resistance and heat resistance. Particularly preferred is a hydrogen atom or a methyl group.

  In particular,

(Where m1 is 0 or 1)
Etc. are preferred.

  Among the bonds exemplified in (a) to (f), a divalent alkylene group, a divalent fluorine-containing alkylene group, an ether bond, an amide bond, and an amidine bond are particularly preferable in terms of oxidation resistance.

  Specifically, the structural unit M2 is represented by the formula (2):

Wherein X ⁶ , X ⁷ , X ⁹ and X ¹⁰ are the same or different and are a hydrogen atom or a fluorine atom; X ⁸ is at least one selected from a hydrogen atom, a fluorine atom, CH ₃ and CF ₃ ; n3, n4 is the same or different and 0 or 1; m1 is 0 or 1; S is a divalent organic group having 1 to 20 carbon atoms; Ry is a basic functional group Y ¹ and / or a salt Y of the basic functional group A structural unit represented by a C2-C30 monovalent or divalent organic group having at least one of ² and containing an aromatic cyclic structure). It is preferable in that the above functions can be effectively expressed and oxidation resistance and heat resistance are excellent.

  Specifically, the structural unit M2 of the formula (2) is

(Where m1 is 0 or 1)
Among them, the structural unit of the formula (2) is preferably the formula (2-1):

(Wherein, X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , S, Ry, n3 and m1 are the same as those in the above formula (2)). Preferred in heat resistance and chemical resistance.

  More specifically, the structural unit of the formula (2-1) is

(Where m1 is 0 or 1)
Are preferred, and in particular,

(Where m1 is 0 or 1)
These structural units are more preferred in terms of oxidation resistance, heat resistance and chemical resistance.

  In the side chain structure of the structural unit M2 shown in the above formula (2-1), the bond -S- with the main chain portion excluding Ry is directly bonded to the main chain portion without having it. You may do it.

  -S- is appropriately selected from divalent organic groups having 1 to 20 carbon atoms, but is usually preferably selected from those which do not decrease oxidation resistance and heat resistance. Of these, a divalent hydrocarbon group and a fluorine-containing alkylene group having 1 to 10 carbon atoms which may contain an ether bond are preferred. Especially, a C1-C10 bivalent hydrocarbon group is a C1-C5 alkylene group, Most preferably, they are a methylene group and ethylene group. The C1-C10 fluorine-containing alkylene group that may contain an ether bond is preferably one that does not contain the fluoroether unit -D-, and particularly preferably a C1-C5 fluorine-containing alkylene group, particularly Those selected from perfluoroalkylene groups having 1 to 5 carbon atoms are preferred.

  Furthermore, those not containing the side chain moiety -S- (m1 = 0) are preferred in that they are excellent in oxidation resistance and heat resistance.

  These preferred structural units M2 are more specifically,

Etc. are preferred.

  The polymer of (M-1) of this invention should just contain 1 mol% or more of structural unit M1 and structural unit M2, respectively, and is a copolymer which has structural unit A1 derived from a copolymerizable monomer. It does not matter.

  Moreover, you may be the binary copolymer of structural unit M1 and M2 which does not contain structural unit A1.

  The structural unit A1 is a structural unit derived from a monomer that can be copolymerized with the monomer that can give the structural unit M1 and the monomer that can give M2, so that the fluorinated polymer is usually an amorphous polymer. Selected.

  Thereby, liquefaction and low viscosity can be achieved.

  The structural unit A1 is preferably one that does not deteriorate the performance derived from the structural unit M1, such as oxidation resistance, heat resistance, liquidity, and low viscosity.

  Furthermore, it is preferable that the structural unit A1 does not deteriorate the performance derived from the structural unit M2, such as the function as an ionic liquid, oxidation resistance, and heat resistance.

  In this respect, the structural unit A1 is preferably a structural unit derived from a fluorine-containing ethylenic monomer.

The structural unit derived from a fluorinated ethylenic monomer is an ethylenic monomer having 2 or 3 carbon atoms, and a structural unit derived from a fluorinated ethylenic monomer having at least one fluorine atom. Those selected from 1 are preferable. The structural unit A1-1 is preferable in that it can improve oxidation resistance and heat resistance.

In particular,
_{CF 2 = CF 2, CF 2} = CFCl, CH 2 = CF 2, CFH = CH 2, CFH = CF 2, CF 2 = CFCF 3, CH 2 = CFCF 3, CH 2 = CHCF 3
Among them, tetrafluoroethylene (CF ₂ = CF ₂ ), chlorotrifluoroethylene (CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CF ₂ = CFCl) is preferred.

  The abundance ratio of each structural unit in the fluorine-containing polymer of the formula (M-1) is appropriately selected according to the structure of the structural units M1, M2 and A1, the intended function, and the use, but preferably M1 + M2 is 30. ~ 100 mol%, A1 is 0 to 70 mol%, more preferably M1 + M2 is 40 to 100 mol%, A1 is 0 to 60 mol%, particularly preferably M1 + M2 is 60 to 100 mol%, and A1 is 0 to 40 mol%. More preferably, M1 + M2 is 70 to 100 mol%, and A1 is 0 to 30 mol%.

  Further, when M1 + M2 = 100 mol%, the abundance ratio of M1 / M2 is appropriately selected from the range of 1/99 to 99/1 mol ratio depending on the structure of the structural units M1 and M2, the intended function, and the use. However, the molar ratio is preferably 2/98 to 90/10, more preferably 5/95 to 70/30, and particularly preferably 10/90 to 50/50.

  If the abundance ratio of M1 is too low, the fluoropolymer is not liable to be liquefied or tends to be highly viscous, which is not preferable.

  On the other hand, if the M2 abundance ratio is too low, the target function as the ionic liquid cannot be sufficiently exhibited, which is not preferable.

  For example, when used as a reaction medium or as a part thereof, it becomes difficult to dissolve the target reaction substrate, the target reaction does not occur, or the selectivity of the target reaction product cannot be obtained. To do. Moreover, when used as a deoxidizer, the target acid cannot be trapped or the acid cannot be separated and extracted. In addition, when used for actuator applications, the target motion performance may not be obtained.

  The molecular weight of the fluorine-containing polymer of the formula (M-1) is 500 to 1,000,000, preferably 1000 to 100,000, more preferably 1000 to 50,000, particularly 2000 to 20000 in terms of number average molecular weight.

  If the molecular weight is too low, there may be a problem that the heat resistance is lowered or the mechanical properties are lowered. Also, if the molecular weight is too high, there is a possibility of increasing the viscosity, which is not preferable.

  The fluorine-containing polymer of the formula (M-1) of the present invention has various characteristics and functions as described above, and is an ionic liquid type functional material alone or mixed with other components. Can be used as Their usage is appropriately selected according to the intended function and application.

  Examples of the ionic liquid type functional material include an ionic liquid, a solar cell electrolyte, a lubricant, a deoxidizer, and an actuator material.

  Other components that can be blended may be appropriately selected depending on the intended functional material. For example, when used as a lubricant or actuator material, an organic acid or an inorganic acid may be blended. In the case of the battery electrolyte, an organic solvent or an inorganic acid may be blended. Moreover, when using as an ionic liquid, you may mix | blend another ionic liquid, an organic solvent, etc.

The organic and inorganic acids as referred to herein, includes both the Lewis acid is an acid that does not release a Bronsted type of acid and H ⁺ that emits H ^+.

The acid may be any, but the Bronsted acid that releases H ⁺ includes tetrafluoroboric acid, tungstic acid, chromic acid, hexafluorophosphoric acid, perchloric acid, hexafluoroarsenic acid, nitric acid. Inorganic acids such as sulfuric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, thiocyanic acid; trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropylsulfonic acid, bis (trifluoromethanesulfonyl) Imido acid, acetic acid, trifluoroacetic acid, propionic acid, benzenesulfonic acid, toluenesulfonic acid, n-hexanesulfonic acid, n-octylsulfonic acid, cetylsulfonic acid, p-chlorobenzenesulfonic acid, phenolsulfonic acid, 4-nitrotoluene- 2-sulfonic acid, 2-sulfobenzoic acid, nitrobenzene Sulfonic acid, sulfosuccinic acid, and organic acids such as Suruhosebashin acid, and the like. In addition, acrylic acid, methacrylic acid, styrene having carboxylic acid in the side chain, styrene having sulfonic acid in the side chain, perfluorosulfonic acid system containing sulfonic acid in the side chain represented by Nafion (trademark of Deyupon) Polymer, perfluorocarboxylic acid polymer containing carboxylic acid in the side chain represented by Flemion (trademark of Asahi Glass Co., Ltd.), perfluorophosphoric acid polymer containing phosphoric acid in the side chain, main chain Alternatively, a solid polymer acid such as a perfluoroimide polymer containing a sulfonylimide in the side chain can be used.

Lewis acids that do not release H ⁺ include boron, aluminum, silica, and transition metals such as molybdenum, tungsten, antimony, chromium, titanium, cobalt, iron, manganese, nickel, vanadium, tantalum, osmium, copper , Oxides such as zinc, inorganic acids such as halides (fluoride, chloride, bromide, iodide) of the metal, m, or p-nitrotoluene, nitrobenzene, p-nitrofluorobenzene, p-nitrochlorobenzene, 2 , 4-dinitrotoluene, 2,4-dinitrofluorobenzene, 2,4,6-trinitrotoluene, 2,4,6-trichlorobenzene, and other organic acids.

  The fluorine-containing polymer of the formula (M-1) decreases in viscosity when mixed with the above acid, and is suitable as a polymer of a low viscosity salt as a polymer ionic liquid in addition to an electrolyte of a solar cell. .

  Moreover, the composition of a solid high molecular weight organic acid or inorganic acid and the fluoropolymer of the formula (M-1) of the present invention is a material suitable as an actuator.

The fluorine-containing polymer of the formula (M-1) and the acid can be mixed at an arbitrary ratio, but the number of basic functional groups Y ¹ (or salts Y ² thereof) in the fluorine-containing polymer (Nb1) / The number of acid groups (Na1) in the organic or inorganic acid is preferably 0.01 to 100, more preferably 0.1 to 10.

Examples of components other than acids include organic solvents and ionic liquids other than the fluoropolymer of the present invention. Examples of organic solvents include highly polar organic solvents such as nitrites such as acetonitrile and benzonitrile; carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate; ethers such as tetrahydrofuran, triglyme and tetraglyme; dimethylformamide and dimethyl Amides such as acetamide and dimethylsulfamide are desirable. In addition, ionic liquids other than the fluoropolymer of the present invention include imidazole and pyridine derivative cations and Cl ⁻ , Br ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , ⁻ _{N (SO 2 CF 3) 2} , - C (SO 2 CF 3) 2, - ionic liquid comprising an anion of OCOCF ₃ and the like.

  Next, specific application forms of the functional material of the present invention will be described individually, but the functional material of the present invention is not limited to such specific examples.

  As an advantage of the polymer, for example, an ionic liquid used as an electrolyte for electrochemical use (for example, an electrolyte for a Li secondary battery, an electrolyte for a capacitor, etc.), a reaction solvent, a separation / extraction solvent, etc. It is preferable that the polymer be a polymer, because of its separability, thermal stability, and ease of film formation. In addition, since the function as the ionic liquid can be used to develop a functional membrane such as a gas separation membrane or a selective permeable membrane, it is preferable to use a polymer form. In addition, the solar cell electrolyte is preferably a polymer because sealing stability and moldability are improved.

  Among these, the fluorine-containing polymer of the present invention is particularly preferable in terms of the above points.

(Ionic liquid polymer)
Currently, organic salts that are liquid at room temperature are attracting attention as ionic liquids. Since these salts are liquids having salt characteristics such as high polarity and no vapor pressure, they are considered to lead to innovative reform of conventional organic solvents, such as electrochemical electrolytes (for example, electrolytes for Li secondary batteries, Applications are expected in various fields such as capacitor electrolytes, reaction solvents, and separation / extraction solvents (ionic liquid, CMC Publishing, 2003).

  Various derivatives of ionic liquid cations have been studied with imidazole and pyridine as their basic skeleton, but the basic skeleton of cation that can effectively reduce the melting point and reduce viscosity is changed to derivatives of imidazole and pyridine. This is because it is limited, and the types that can be selected are limited.

  According to the present invention, by including a structural unit having a fluorinated ether in an ethylenic polymer, the glass transition point (or melting point) of the polymer can be reduced, and liquefaction becomes possible. Furthermore, the viscosity can be lowered. These are suitable as cation materials for ionic liquids because of their low glass transition point (melting point) and low viscosity. If the fluorine-containing ether chain is long, the melting point and viscosity are lowered, but the dielectric constant is also lowered, making it unsuitable as an ionic liquid member. Therefore, when used as an ionic liquid, the number of fluorine-containing ether units is desirably 1 to 10, more desirably 1 to 5. In addition, the polymer of the present invention containing a basic functional group can be easily liquefied by mixing with an acid, and the composition of the acid and the polymer of the present invention can easily be an ionic liquid type polymer.

  Such an ionic liquid type polymer is useful as the above-mentioned electrochemical electrolyte, reaction solvent, separation / extraction solvent, and the like.

(Solar cell electrolyte)
As described above, the use of the aromatic compound of the present invention includes a solar cell electrolyte. The dye-sensitized solar cell electrolyte currently uses acetonitrile as a solvent. However, acetonitrile has problems such as (i) deterioration of sealing properties due to thermal swelling and shrinkage, and (ii) oxidation due to direct excitation of TiO ₂ used for electrodes. For this reason, research using ionic liquids and gel electrolytes has been carried out (Japanese Patent Laid-Open No. 2000-58891; latest technology of dye-sensitized solar cells, Chapter 28 (CMC Publishing, 2001)), but still Sufficient performance (conductivity, life, etc.) has not been obtained.

The fluorine-containing polymer of the present invention can be used as an electrolyte for a dye-sensitized solar cell. The electrolyte of the dye-sensitized solar cell needs to conduct a salt of I ⁻ / I ₃ ⁻ , but the material of the present invention can be obtained by setting the counter anion of the salt of the fluoropolymer of the present invention to I ^−. Functions as an excellent electrolyte.

  It is low in volatility due to the polymer compound of the present invention, can reduce thermal swelling and shrinkage, can reduce viscosity and improve oxidation resistance by containing fluorine-containing ether, etc. There are benefits.

Further, in order to increase the conductivity of I ⁻ / I ₃ ⁻ , it is necessary to improve the salt concentration. From this point, the salt derived from the aromatic cyclic structure having a higher basic functional group concentration in the structural unit M2 It is preferable that Accordingly, one Ry containing a polyfunctional basic functional group, specifically, the above-mentioned atoms forming the basic functional group simultaneously formed an aromatic ring structure (in the above (ii) and (iii) Examples of Ry shown) are more preferred as the aromatic cyclic structure.

(lubricant)
Perfluoropolyethers have long been used as lubricants. Since perfluoropolyether has no adhesion to the base material, in order to enhance the adhesion, a technique of introducing a functional group such as a hydroxyl group or a carboxylic acid group or increasing the adhesion as a salt of carboxylic acid has been taken. . For example, as a lubricant used as a magnetic recording medium, a report that a ester compound of a perfluoropolyether having a hydroxyl group or a carboxyl group is used as a lubricant (JP-A-5-194970), a carboxylic acid group is terminated, or There have been reports (such as JP-A-5-143975 and JP-A-2001-216625) that an amine salt compound of perfluoropolyether at both ends is used as a lubricant. However, the acidity of the carboxylic acid at the end of the perfluoropolyether is higher than that of a normal hydrocarbon carboxylic acid. Therefore, in the case of an ester, it is easily hydrolyzed, and there is a problem in long-term stability. Even when an amine salt compound of a carboxylic acid having a perfluoropolyether terminal is used, the base material is affected by the influence of a free carboxylic acid because the acidity of the carboxylic acid having a perfluoropolyether terminal is strong. For this reason, excess aromatic amine must be contained in the presence of salt, and there is a problem in long-term stability due to sliding off and evaporation of the low-molecular aromatic amine from the base.

  When the fluorine-containing polymer of the present invention is used as a lubricant, the polymer itself has a basic property and thus adversely affects the base material. Therefore, when used as a lubricant, it must be a composition with an acid. . However, since the fluorinated ether chain in the fluorinated polymer of the present invention is basic, it can be used as a lubricant component in the form of a composition with a weak acid that does not affect the substrate as an acid component, and is stable for a long time. It has the effect that the adhesiveness with a base material is high since it has high property and also contains an aromatic cyclic structure.

(Deoxidizer)
While environmental issues are regarded as important, the treatment of wastewater and waste solvents generated during chemical synthesis is becoming a problem. Especially when wastewater contains acid components with strong environmental impact such as organic acid, phosphoric acid, osmium, tin oxide, and halides, it cannot be treated simply by neutralizing the acid. Removal is required. An anionic polymer may be used as a deoxidizer for removing the acid in the wastewater from the viewpoint of ease of separation from water and ease of regeneration. However, there are few kinds of anionic polymers having good separation properties from water, and oxidation resistance is not always good, so the number of recycling is limited. Furthermore, since the process of deoxidation from wastewater and the process of deoxidation for regeneration are liquid / solid reactions, the efficiency is not necessarily high. Since the fluorinated polymer of the present invention containing a fluorinated ether is itself liquefied, the deoxidation process becomes a liquid / liquid reaction, and the efficiency is high.

  In addition, the fluoropolymer of the present invention does not worry about volatilization and can be easily recycled.

(Actuator)
Actuators are expected to be applied to artificial muscles and microrobots, but are materials that deform by external stimuli such as heat, light, and electricity. Among actuators, a material that swells and contracts in response to electricity has a high expectation for practical use because an electric signal can be controlled relatively easily (Science and Industry, 72 (4), p162). p167 (1998)).

  In such an actuator, it is preferable that the displacement is larger with respect to the potential because the actuator can be deformed at a small potential. Currently, solid polymer acids such as perfluorosulfonic acid membranes and perfluorocarboxylic acid membranes are swollen with water and used as actuator materials, but studies are being made to increase the deformation with respect to potential.

  In the present invention, for example, when the fluoropolymer of the present invention containing a basic functional group is added to a solid polymer acid such as a perfluorosulfonic acid film or a perfluorocarboxylic acid film swollen with water, There is an effect that the deformation becomes larger than in the case where it is not.

  The functional material of the present invention can be used or mixed in the liquid state or in the solid state as described above, but can also be formed as a solid film.

  As a method for forming the solid film, for example, any known method such as casting, impregnation, and heat press may be used.

When forming a solid film, the combination of an acid and a fluoropolymer is
(i) impregnating a solid acid with the liquid fluoropolymer of the present invention,
(ii) impregnating the solid fluoropolymer of the present invention with a liquid acid,
(iii) combining the solid fluorine-containing polymer of the present invention with a solid acid,
(iv) A combination of impregnating the composition of the fluoropolymer of the present invention and an acid into another solid film is exemplified.

The second of the present invention relates to a novel fluoropolymer, that is, the fluoropolymer of the present invention has the formula (M-2):
-(M3)-(M4)-(A2)-(M-2)
[Wherein the structural unit M3 is represented by the formula (3):

{Wherein X ¹¹ , X ¹² , X ¹⁴ and X ¹⁵ are the same or different and are a hydrogen atom or a fluorine atom; X ¹³ is at least one selected from a hydrogen atom, a fluorine atom, CH ₃ and CF ₃ ; n5, n6 is the same or different and is 0 or 1; D ¹ is a part of a fluorine-containing ether structure, and the formula (3-1):

(Wherein R ¹ is at least one selected from divalent fluorine-containing alkylene groups having 1 to 5 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; m is an integer of 1 to 20) Rx ¹ is at least one selected from a hydrogen atom, a halogen atom, and a fluorine-containing alkyl group having 1 to 20 carbon atoms which may have an ether bond, provided that in Rx ¹ , the above D ¹ Is a structural unit represented by However, the unit of —O—O— is not included in the structural unit M1 and the formula (3-1); the structural unit M4 is represented by the formula (4):

{Wherein X ¹⁶ , X ¹⁷ , X ¹⁹ and X ²⁰ are the same or different and are a hydrogen atom or a fluorine atom; X ¹⁸ is at least one selected from a hydrogen atom, a fluorine atom, CH ₃ and CF ₃ ; n7, n8 is the same or different and is 0 or 1; Ry ¹ is a monovalent having 2 to 30 carbon atoms having at least one of amines Y ³ and / or salts Y ⁴ of amines and containing an aromatic ring structure A structural unit derived from a monomer copolymerizable with a monomer capable of giving structural units M3 and M4], wherein 1 to 99 mol of structural unit M3 %, Structural unit M4 is 1 to 99 mol%, structural unit A2 is 0 to 98 mol%, and the number average molecular weight is 500 to 1,000,000. It is.

In the fluorine-containing polymer of the formula (M-2), the structural unit M3 is characterized by having a fluoroether unit -D ¹ -in the side chain, thereby liquefying and reducing the viscosity of the polymer as described above. In addition, it has excellent oxidation resistance and heat resistance.

In the structural unit M3 represented by the formula (3), the fluoroether unit -D ¹ -is a fluoroether unit having one or more fluorine atoms represented by the formula (3-1) or a repeating unit of the fluoroether. It is.

Specifically, -D ¹ -is preferably the same as the fluoroether unit -D- in the fluorine-containing polymer of the formula (M-1) used for the ionic liquid type functional material described above. The same as the preferred specific examples of -D- are preferred.

Rx ¹ constituting the side chain end in the structural unit M3 is selected from a fluorine-containing alkyl group that does not contain a hydrogen atom, a halogen atom, and the unit of -D ^1- and may contain an ether bond having 1 to 20 carbon atoms. It is what

Specifically, Rx ¹ is preferably the same as Rx described in the preferred structural unit M1 of the fluoropolymer of formula (M-1) described above, and specific examples are also preferred specific examples of Rx. The same thing is mentioned preferably, whereby excellent oxidation resistance and heat resistance can be imparted to the fluoropolymer.

  Specifically, the structural unit M3 represented by the formula (3) is

And the like. Among them, the formula (3-2):

It is particularly preferred that the structural unit is a structural unit represented by the formula (wherein X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , D ¹ , Rx ¹ and n5 are the same as those in the formula (3)). In terms of chemical properties and chemical resistance.

  More specifically, the structural unit of the formula (3-2) is

Are preferred, and in particular,

These structural units are more preferred in terms of oxidation resistance, heat resistance and chemical resistance.

  More specifically, these preferred structural units M3 are preferably the same as the preferred specific examples of the structural unit M1 of the formula (M-1).

The structural unit M4 in the fluorine-containing polymer of the formula (M-2) has a functional group selected from amines Y ³ and / or a salt Y ^{4 of} amines, and further has an aromatic cyclic structure. Thus, various functions of the ionic liquid type functional material described above can be effectively expressed, and oxidation resistance and heat resistance can be imparted.

Ry ¹ in the structural unit M4 is a monovalent organic group having 2 to 30 carbon atoms having at least one of amines and / or salts of amines and containing an aromatic cyclic structure, and specifically Ry ¹ is that in the Ry in the structural unit M2 in the fluorine-containing polymer of the formula (M-1), the functional groups Y ¹ and Y ² are selected from amines Y ³ and salts Y ⁴ thereof; What was illustrated by Ry in the fluoropolymer of the above-mentioned formula (M-1) except that it does not have a side chain portion -S- (m1 = 0) can be preferably exemplified.

  Specifically, the structural unit M4 represented by the formula (4) is

Among them, the structural unit M4 of the formula (4) is preferably the formula (4-1):

In particular, the structural unit represented by the formula (X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ , X ²⁰ , Ry ¹ and n7 is the same as the above formula (4)) is particularly resistant to oxidation, heat and resistance. It is preferable in terms of chemical properties.
More specifically, the structural unit of the formula (4-1) is

Are preferred, and in particular,

These structural units are more preferred in terms of oxidation resistance, heat resistance and chemical resistance.

  These preferred structural units M4 are more specifically,

Etc. are preferred.

  The fluorine-containing polymer of (M-2) of the present invention only needs to contain 1 mol% or more of structural units M3 and M4, and is a copolymer having a structural unit A2 derived from a copolymerizable monomer. They may be combined.

  Further, it may be a binary copolymer of the structural units M3 and M4.

  The structural unit A2 is preferably one that does not lower the performance derived from the structural unit M3, such as oxidation resistance, heat resistance, liquidity, and low viscosity.

  Furthermore, it is preferable that the structural unit A2 does not deteriorate the performance derived from the structural unit M4, for example, the function as an ionic liquid, oxidation resistance, and heat resistance.

  Also in that respect, the structural unit A2 is preferably a structural unit derived from a fluorine-containing ethylenic monomer.

The structural unit derived from a fluorine-containing ethylenic monomer is a structural unit A2- derived from a fluorine-containing ethylenic monomer having 2 or 3 carbon atoms and having at least one fluorine atom. Those selected from 1 are preferable. The structural unit A2-1 is preferable in that it can improve oxidation resistance and heat resistance.

  Specific examples of the structural unit A2-1 preferably include those preferred for A1 in the fluorine-containing polymer of the formula (M-1) and those similar to the structural unit A1-1.

  The abundance ratio of each structural unit in the fluorine-containing polymer of the formula (M-2) is appropriately selected according to the structure of the structural units M3 and M4, the intended function, and the use, but preferably the structural unit M3 + M4 is 30. To 100 mol%, the structural unit A2 is 0 to 70 mol%, more preferably the structural unit M3 + M4 is 40 to 100 mol%, the structural unit A2 is 0 to 60 mol%, and particularly preferably the structural unit M3 + M4 is 60 to 100 mol%. The structural unit A2 is 0 to 40 mol%, more preferably the structural unit M3 + M4 is 70 to 100 mol%, and the structural unit A2 is 0 to 30 mol%.

  Further, when M3 + M4 = 100 mol%, the abundance ratio of M3 / M4 is appropriately selected from the range of 1/99 to 99/1 molar ratio depending on the structure of the structural units M3 and M4, the intended function, and application. However, the molar ratio is preferably 2/98 to 90/10 molar ratio, more preferably 5/95 to 70/30 molar ratio, and particularly preferably 10/90 to 50/50 molar ratio.

  If the abundance ratio of M3 is too low, the fluorinated polymer is not liable to be liquefied or tends to be highly viscous, which is not preferable.

  On the other hand, if the ratio of M4 is too low, the target function as an ionic liquid cannot be sufficiently exerted, which is not preferable.

  For example, when used as a reaction medium or as a part thereof, it becomes difficult to dissolve the target reaction substrate, the target reaction does not occur, or the selectivity of the target reaction product cannot be obtained. To do. Moreover, when used as a deoxidizer, the target acid cannot be trapped or the acid cannot be separated and extracted. In addition, when used for actuator applications, the target motion performance may not be obtained.

  The molecular weight of the fluorine-containing polymer of the formula (M-2) is 500 to 1,000,000, preferably 1000 to 100,000, more preferably 1000 to 50,000, particularly 2000 to 20000 in terms of number average molecular weight.

  If the molecular weight is too low, there may be a problem that the heat resistance is lowered or the mechanical properties are lowered. Also, if the molecular weight is too high, there is a possibility of increasing the viscosity, which is not preferable.

  The polymer of the formula (M-2) of the present invention is most preferable as the above-mentioned ionic liquid type functional material, but besides that, it is also used for applications such as an epoxy curing agent, a water retention agent, and a surface protection agent. Can be preferably used.

  Next, the present invention will be specifically described based on examples, but the present invention is not limited to the examples.

Example 1 (Synthesis of a polymer having a fluorine-containing ether structure in the side chain)
In a 100 ml glass eggplant-shaped flask equipped with a stirrer, the following compound containing fluorine-containing ether in the side chain (n = 7):

9 g, 2-fluoro-N-pyrimidin-2-yl-acrylamide:

1.0 g

After adding 8 g of the 8.0 wt% perfluorohexane solution and 20 g of HCFC141b and sufficiently purging with nitrogen, the mixture was stirred at 20 ° C. for 24 hours under a nitrogen stream. The obtained high-viscosity liquid was poured into hexane, separated and vacuum-dried to obtain 7.2 g of a colorless and transparent polymer. When this polymer was analyzed by ¹⁹ F-NMR and ¹ H-NMR analysis, the ratio of units whose side chain ends were fluorine-containing vinyl ether / units whose side chain ends were pyrimidine was 45/55 (mole% ratio). there were.

¹⁹ F-NMR (CD ₃ COCD ₃ ): -84 to -91 ppm (14.4 F), -128 to -134 ppm (7.2 F), -164 to -173 pm (1 F)
¹ H-NMR (CD ₃ COCD ₃ ): 2.5 to 3.3 ppm (4H), 7.4 to 8.7 ppm (1.7H), 9.1 ppm (0.6H)

Synthesis Example 1 (Synthesis of a polymer having a fluorine-containing ether structure in the side chain)
In a 100 ml glass eggplant-shaped flask equipped with a stirrer, the following compound containing fluorine-containing ether in the side chain (n = 7):

9 g, 2-fluoro-acryloyl fluoride:
CH ₂ = CFCOF
0.5g

After adding 8 g of the 8.0 wt% perfluorohexane solution and 20 g of HCFC141b and sufficiently purging with nitrogen, the mixture was stirred at 20 ° C. for 24 hours under a nitrogen stream. The obtained high viscosity liquid was poured into hexane, separated and vacuum dried to obtain 9.1 g of a colorless and transparent polymer. When this polymer was analyzed by ¹⁹ F-NMR and ¹ H-NMR analysis, the ratio of units whose side chain ends were fluorine-containing vinyl ether / units whose side chain ends were acid fluoride was 45/55 (mol%). there were.

Example 2
In a 100 ml four-necked flask, 20 ml of DMF and 5 g of pyrimidine are placed, put in an ice bath, and a mixed solution of 8 g of the polymer obtained in Synthesis Example 1 and 10 ml of THF is added dropwise under a nitrogen atmosphere. After dropping, the mixture was stirred at room temperature for 4 hours, reprecipitated with water, and then dried to obtain 5.1 g of a white viscous polymer. When this polymer was analyzed by ¹⁹ F-NMR and ¹ H-NMR analyses, the ratio of units having a side chain terminal of fluorine-containing vinyl ether / side chain terminal of pyrimidine was 45/55 (mol%). It was.

¹⁹ F-NMR (CD ₃ COCD ₃ ): -84 to -91 ppm (14.4 F), -128 to -134 ppm (7.2 F), -164 to -173 pm (1 F)
¹ H-NMR (CD ₃ COCD ₃ ): 2.5 to 3.3 ppm (4H), 7.4 to 8.7 ppm (1.7H), 9.1 ppm (0.6H)

Claims (7)

Formula (M-1):
-(M1)-(M2)-(A1)-(M-1)
[In the formula, the structural unit M1 has a fluorine-containing ether-structure moiety -D- in the side chain, and does not contain the basic functional group Y ¹ and the basic functional group salt Y ^2. A structural unit derived from a monomer, wherein the portion D of the fluorine-containing ether structure is represented by the formula (1):

(Wherein R is at least one selected from divalent fluorine-containing alkylene groups having 1 to 5 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; n is an integer of 1 to 20). Structural unit, except that -O-O- unit is not included in the side chain of the structural unit M1; the structural unit M2 is an ethylenic unit having a site Ry containing a basic functional group in the side chain or at the end of the side chain. A structural unit derived from a mer, wherein Ry has at least one of a basic functional group Y ¹ and / or a salt Y ² of the basic functional group, and contains an aromatic cyclic structure. A structural unit derived from a monomer copolymerizable with a monomer capable of giving structural units M1 and M2], wherein the structural unit M1 is 1 -99 mol%, structural unit M2 is 1-99 mol%, structural unit An ionic liquid type functional material comprising a fluorine-containing polymer containing 0 to 98 mol% of A1. In the formula (1), —O—R— represents — (OCFZ ¹ CF ₂ ) —, — (OCF ₂ CF ₂ CF ₂ ) —, — (OCH ₂ CF ₂ CF ₂ ) —, — (OCFZ ² ). -,-(OCZ ³ ₂ )-,-(CFZ ¹ CF ₂ O)-,-(CF ₂ CF ₂ CF ₂ O)-,-(CH ₂ CF ₂ CF ₂ O)-,-(CFZ ² O) -And-(CZ ³ ₂ O)-(wherein Z ¹ and Z ² may be the same or different, H, F or CF ₃ ; Z ³ is CF ₃ ). The ionic liquid type functional material comprising a fluoropolymer according to claim 1, wherein the ionic liquid type functional material comprises a fluoroether unit, wherein -D- does not contain a structure of -O-O-. In the formula (M-1), the structural unit M1 having a fluorine-containing ether structure moiety is represented by the formula (1-1):
-D-Rx (1-1)
(In the formula, Rx is at least one selected from a hydrogen atom, a halogen atom, and a fluorine-containing alkyl group that may contain an ether bond having 1 to 20 carbon atoms, provided that D does not exist in Rx. The ionic liquid type functional material according to claim 1 or 2, wherein D is a structural unit derived from an ethylenic monomer having a site represented by the formula (1) at the side chain end. The structural unit M1 is represented by the formula (1-2):

Wherein X ¹ , X ² , X ⁴ and X ⁵ are the same or different and are a hydrogen atom or a fluorine atom; X ³ is at least one selected from a hydrogen atom, a fluorine atom, CH ₃ and CF ₃ ; n1, The ionic liquid type functional material according to any one of claims 1 to 3, wherein n2 is the same or different and is 0 or 1; and D and Rx are structural units represented by the same formula (1-1). . The structural unit M1 is represented by the formula (1-3):

The structural unit represented by the formula (wherein X ¹ , X ² , X ³ , X ⁴ , X ⁵ , D, Rx and n1 are the same as those in the formula (1-2)). The ionic liquid type functional material described in 1. The basic functional group or a salt of the basic functional group possessed by Ry is at least one selected from amines, imines, enamines, ketimines, azines and salts thereof. The ionic liquid type functional material according to any one of the above. Formula (M-2):
-(M3)-(M4)-(A2)-(M-2)
[Wherein the structural unit M3 is represented by the formula (3):

{Wherein X ¹¹ , X ¹² , X ¹⁴ and X ¹⁵ are the same or different and are a hydrogen atom or a fluorine atom; X ¹³ is at least one selected from a hydrogen atom, a fluorine atom, CH ₃ and CF ₃ ; n5, n6 is the same or different and is 0 or 1; D ¹ is a part of a fluorine-containing ether structure, and the formula (3-1):

(Wherein R ¹ is at least one selected from divalent fluorine-containing alkylene groups having 1 to 5 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; m is an integer of 1 to 20) Rx ¹ is at least one selected from a hydrogen atom, a halogen atom, and a fluorine-containing alkyl group having 1 to 20 carbon atoms which may have an ether bond, provided that in Rx ¹ , the above D ¹ Is a structural unit represented by However, the unit of —O—O— is not included in the structural unit M1 and the formula (3-1); the structural unit M4 is represented by the formula (4):

{Wherein X ¹⁶ , X ¹⁷ , X ¹⁹ and X ²⁰ are the same or different and are a hydrogen atom or a fluorine atom; X ¹⁸ is at least one selected from a hydrogen atom, a fluorine atom, CH ₃ and CF ₃ ; n7, n8 is the same or different and is 0 or 1; Ry ¹ is a monovalent having 2 to 30 carbon atoms having at least one of amines Y ³ and / or salts Y ⁴ of amines and containing an aromatic ring structure A structural unit derived from a monomer copolymerizable with a monomer capable of giving structural units M3 and M4], wherein 1 to 99 mol of structural unit M3 %, 1 to 99 mol% of the structural unit M4, 0 to 98 mol% of the structural unit A2, and a number average molecular weight of 500 to 1,000,000.