KR100793560B1 - Halogenated Aromatic Compound, Polymer Thereof, and Proton-Conductive Membrane Comprising the Polymer - Google Patents

Abstract

The present invention has a high toughness because it has a flexible structure in the main chain and does not easily degrade the mechanical and thermal properties even when sulfonated, a sulfonic acid group-containing polymer obtained by sulfonating this polymer, and a sulfonic acid group-containing polymer It is to provide a proton conductive membrane having excellent mechanical strength and excellent durability.

That is, according to the present invention, the halogenated aromatic compound represented by the formula (1m), the polymer or copolymer having the flexible structure of the compound in the main chain, the sulfonated copolymer polymer obtained by sulfonation thereof, and the proton conductive film comprising the sulfonated copolymer Is provided.

Wherein A is independently an electron withdrawing group, B is independently an electron donating atom or group, X is a chlorine atom, an iodine atom or a bromine atom, and R ¹ to R ⁸ may be the same or different and , A hydrogen atom, a fluorine atom or an alkyl group, n is a number of two or more.

Halogenated aromatic compounds, polymers, sulfonic acid group-containing polymers, proton conductive films, flexible structures

Description

Halogenated Aromatic Compounds, Polymers of the Compounds and Proton Conductive Membranes Containing the Polymers {Halogenated Aromatic Compound, Polymer Thereof, and Proton-Conductive Membrane Comprising the Polymer}

The present invention relates to a novel halogenated aromatic compound, a polyphenylene-based polymer polymerized using it as a monomer component, and a proton conductive film containing a sulfonated product of the polymer. Proton conductive membranes are known to be useful for primary battery electrolytes, secondary battery electrolytes, fuel cell polymer solid electrolytes, display devices, various sensors, signal transmission media, solid capacitors, ion exchange membranes, and the like.

Although electrolytes are commonly used as (aqueous) solutions, the tendency to change them to solid systems is increasing recently. The first reason for this tendency is to facilitate processing in the case of application to the electric and electronic materials, for example. This is because it is possible to reduce the weight and power of the device.

Conventionally, both proton conductive materials and inorganic matters are known. Examples of the inorganic substance include, for example, uranil phosphate, which is a hydrating compound, but these inorganic compounds do not have sufficient contact at the interface, and there are many problems in forming a conductive layer on a substrate or an electrode.

On the other hand, examples of the organic compound include sulfonates of polymers belonging to a so-called cation exchange resin, for example, vinyl polymers such as polystyrenesulfonic acid, perfluoroalkylsulfonic acid polymers represented by Nafion (manufactured by DuPont), and perfluoro Alkyl carboxylic acid polymers and polymers having sulfonic acid groups and phosphoric acid groups introduced into heat resistant polymers such as polybenzimidazole and polyether ether ketone [Polymer Preprints, Japan, Vol. 42, No. 7, p. 2490-2492 (1993), Polymer Preprints, Japan, Vol. 43, No. 3, p. 735 to 736 (1994), Polymer Preprints Japan, Vol. 42, no. 3, p. 730 (1993)].

Although these organic polymers are normally used in a film form, the conductive film can be bonded to an electrode by using a solvent soluble or thermoplastic. However, most of these organic polymers, in addition to the problem that the proton conductivity is not yet sufficient, the problem of poor durability and proton conductivity at high temperature (above 100 ° C), the problem of embrittlement by sulfonation and the decrease of mechanical strength, humidity There is a problem that the dependence under the condition is large, or the adhesion with the electrode is not sufficiently satisfactory, or the strength decreases due to excessive swelling during operation due to the hydrous polymer structure and the shape collapses. Therefore, these organic polymers have various problems in order to be applied to the electric and electronic materials and the like.

In US Pat. No. 5,403,675, a solid polymer electrolyte comprising sulfonated rigid polyphenylene is proposed. This polymer is mainly composed of a polymer obtained by polymerizing an aromatic compound containing a phenylene chain (structure described in column 9 of the same specification) and reacted with a sulfonating agent to introduce a sulfonic acid group. However, although the proton conductivity is improved by increasing the amount of sulfonic acid group introduced, the mechanical properties of the sulfonated polymer obtained at the same time, for example, toughness and hot water resistance such as elongation at break and bending resistance are remarkably impaired.

Therefore, the object of the present invention is to provide a polymer having a flexible structure in the main chain, which has high toughness and does not easily degrade the toughness and hot water resistance even when sulfonated, a sulfonic acid group-containing polymer obtained by sulfonating this polymer, and a sulfonic acid group-containing polymer. An object of the present invention is to provide a proton conductive film having excellent toughness and excellent durability.

That is, the present invention firstly provides a compound useful as a monomer effective for introducing a flexible structure into a polymer, which provides a halogenated aromatic compound represented by the formula (1m).

<1m>

Wherein A is independently an electron withdrawing group, B is independently an electron donating atom or group, X is a chlorine atom, an iodine atom or a bromine atom, and R ¹ to R ⁸ may be the same or different and , A hydrogen atom, a fluorine atom or an alkyl group, n is 2 or more, preferably 2 to 100, particularly preferably an integer of 2 to 80.

This halogenated aromatic compound imparts a flexible structure in the polymer and improves the toughness of the polymer.

Thus, the present invention provides a polyphenylene polymer having a repeating unit represented by the formula (1).

In the above formula, A, B, R ¹ to R ⁸ and n are as defined for the general formula (1m).

This polyphenylene type polymer may be a homopolymer, or may be a copolymer containing another repeating unit.

That is, the present invention provides a polyphenylene copolymer having a repeating unit represented by the general formula (1) and a repeating unit containing a separate divalent aromatic group.

Fourthly, the present invention provides a polyphenylene-based copolymer characterized in that the repeating unit containing the divalent aromatic group is one or more units selected from the group containing the formulas (2) to (5). This copolymer can be easily sulfonated to impart proton conductivity.

Wherein A and B are as defined for Formula 1m, R ⁹ to R ¹⁵ may be the same or different, represent a hydrogen atom, a fluorine atom or an alkyl group, Z is an aryl group, and m is 0 to Is an integer of 2.

In said formula, R <^17> -R <^24> is the same or different, and represents a hydrogen atom, an alkyl group, or an aryl group.

The present invention further provides the above copolymer having sulfonic acid groups.

This sulfonic acid group containing copolymer is useful as a material of a proton conductive membrane.

A sixth aspect of the present invention provides a proton conductive membrane comprising the sulfonic acid group-containing copolymer.

<Embodiment of the Invention>

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

[Halogenated Aromatic Compound]

The halogenated aromatic compound represented by the general formula (1m) of the present invention (hereinafter referred to as "monomer (1m)") has a function of imparting a flexible structure to a polymer containing it as a monomer unit and improving the toughness, other mechanical strength, etc. of the polymer. Has

Hereinafter, the chemical formula 1m will be described.

X includes a chlorine atom, a bromine atom, and an iodine atom.

A is an electron withdrawing group, for example -CO-, -CONH-,-(CF ₂ ) _p- (where p is an integer from 1 to 10), -C (CF ₃ ) ₂ -,- and the like - COO-, -SO-, -SO _2. In addition, an electron withdrawing group means the group which becomes a value of 0.06 or more, when it is the m position of a phenyl group, and when it is a p position, the Hammett substituent constant is 0.01 or more.

,

등을 들 수 있다. B is an electron donating group or atom, for example -O-, -S-, -CH = CH-, -C≡C-

,

Etc. can be mentioned.

As the monomer (1m) of the present invention, for example, 2,2-bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl] -1,1,1,3,3,3-hexafluoropropane And bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl] sulfone and the compound represented by the following formula.

(Wherein, X is as defined for the formula (1m).)

The monomer (1 m) can be synthesized by, for example, the following reaction.

First, in order to make the bisphenol linked with the electron withdrawing group as the alkali metal salt of the corresponding bisphenol, high dielectric constants such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenyl sulfone and dimethyl sulfoxide Alkali metals, such as lithium, sodium, potassium, a hydrogenated alkali metal, alkali metal hydroxide, alkali metal carbonate, etc. are added in a polar solvent.

Usually, alkali metal is made to react excessively with respect to a phenol hydroxyl group, and 1.1 to 2 times equivalent is normally used. Preferably, 1.2 to 1.5 times equivalents are used. At this time, a solvent which azeotropes with water, such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anitol, and phentol, coexists, Aromatic dihalogen compounds substituted with halogen atoms such as activated fluorine, chlorine, for example 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-chlorofluorobenzophenone, Bis (4-chlorophenyl) sulfone, bis (4-fluorophenyl) sulfone, 4-fluorophenyl-4'-chlorophenylsulfone, bis (3-nitro-4-chlorophenyl) sulfone, 2,6-dichloro Benzonitrile, 2,6-difluorobenzonitrile, hexafluorobenzene, decafluorobiphenyl, 2,5-difluorobenzophenone, 1,3-bis (4-chlorobenzoyl) benzene and the like are reacted. In consideration of reactivity, a fluorine compound is preferable. However, when considering an aromatic coupling reaction, it is necessary to assemble an aromatic nucleophilic substitution reaction so that the terminal becomes a chlorine atom. The active aromatic dihalogens use 2 to 4 fold moles, preferably 2.2 to 2.8 fold moles relative to bisphenol. It may be an alkali metal salt of bisphenol before the aromatic nucleophilic substitution reaction. The reaction temperature is 60 ° C to 300 ° C, preferably in the range of 80 ° C to 250 ° C. The reaction time is in the range of 15 minutes to 100 hours, preferably 1 hour to 24 hours. The most preferred method is to use a chlorofluorobody having one halogen atom with different reactivity as the active aromatic dihalogen represented by Scheme 1 below. It is perfect for obtaining chloroform.

(In the above formula, A is as defined for Formula 1m.)

Alternatively, there is a method for synthesizing a flexible compound containing a desired electron withdrawing group and an electron donating group by combining a nucleophilic substitution reaction and an electrophilic substitution reaction as described in Japanese Patent Application Laid-Open No. 2-159.

Specifically, an aromatic bis halogen activated by an electron withdrawing group, for example, bis (4-chlorophenyl) sulfone, is subjected to nucleophilic substitution with phenol to form a bisphenoxy substituent. This substituent is then obtained, for example, from the Friedel-Craft reaction with 4-chlorobenzoic acid chloride to give the desired compound. The aromatic bishalogen activated by the electron withdrawing group used here can apply the compound illustrated above. Although the phenol compound may be substituted, an unsubstituted compound is preferable from the viewpoint of heat resistance and flexibility. In addition, it is preferable to use an alkali metal salt for the substitution reaction of phenol, and the compound illustrated above can be used for the alkali metal compound which can be used. The usage-amount is 1.2-2 times mole with respect to 1 mol of phenols. The azeotropic solvent of the polar solvent and water mentioned above can be used at the time of reaction. The bisphenoxy compound is reacted with chlorobenzoic acid chloride as an acylating agent in the presence of an activator of Friedel-Craft reaction of Lewis acid such as aluminum chloride, boron trifluoride, zinc chloride. Chlorobenzoic acid chloride is used 2 to 4 times mole, preferably 2.2 to 3 times mole with respect to the bisphenoxy compound. The Friedel-Craft activator uses 1.1 to 2 times the equivalent of 1 mole of active halogen compound such as chlorobenzoic acid of the acylating agent. The reaction time is in the range of 15 minutes to 10 hours, and the reaction temperature is in the range of -20 ° C to 80 ° C. As the solvent to be used, chlorobenzene, nitrobenzene and the like which are inert to the Friedelcraft reaction can be used.

The monomer (1m) of this invention obtained in this way can confirm the structure by IR, NMR, elemental analysis, etc.

In addition to the monomer represented by n = 2, the halogen compound represented by General formula (1m) which can be used by this invention can also use oligomer or polymer whose n is larger than 2. These oligomers to polymers are, for example, bisphenol which becomes the source of etheric oxygen which is the electron donating group B in the formula (1m), and> C = O, -SO _2- , and / or> C (CF ₃ ) More specifically, a combination of _2, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-hydroxyphenyl) Substitution reaction of alkali metal salt of bisphenol, such as ketone and 2, 2-bis (4-hydroxyphenyl) sulfone, and active aromatic halogen compounds, such as excess 4, 4- dichloro benzophenone and bis (4-chlorophenyl) sulfone Can be obtained by sequential polymerization in the presence of a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane and the like according to the synthesis method of the monomer. The obtained oligomers to polymers can be carried out by the polymer in a general purification method, for example, operation of dissolution-precipitation. Adjustment of molecular weight is performed by reaction molar ratio of excess aromatic dichloride and bisphenol. Since the aromatic dichloride is excess, the molecular terminal of the oligomer and polymer obtained becomes aromatic chloride. If the molecular weight of the obtained oligomer and polymer is GPC and an oligomer, the number average molecular weight can be calculated | required by NMR.

The following are mentioned as an oligomer which has an aromatic chloride in a specific molecular terminal, or a structure of a polymer.

[polymer]

The polymer of the present invention may be a homopolymer composed of only the repeating unit represented by the above formula (hereinafter, referred to as the repeating unit (1)), or may be a copolymer composed of the repeating unit (1) and other repeating units. . In any case, the polystyrene reduced weight average molecular weight (hereinafter referred to as "weight average molecular weight") measured by gel permeation chromatography of the polymer is 10,000 to 1 million, preferably 20,000 to 800,000.

When the said polymer has another repeating unit, it is preferable that content of a repeating unit (1) is 10-80 mol%. If the repeating unit (1) is less than 10 mol%, the toughness improvement of the polymer obtained cannot be expected.

Here, the repeating unit (1) is comprised of the said monomer (1m) of this invention.

When the polymer of the present invention has other repeating units (hereinafter referred to as "other repeating units") other than the repeating unit (1), various units may be selected as other repeating units depending on the properties, functions, and the like required for the polymer. In order to obtain a polymer having conductivity, for example, the units represented by Chemical Formulas 2 to 5 (hereinafter referred to as units (2), (3), (4) and (5), respectively, and units (2) to (5) is collectively called "unit (A)". The copolymer containing this repeating unit (1) and unit (A) can be sulfonated and used as a proton conductive membrane material.

Especially as unit (A), when unit (2) sulfonates this polymer and introduces a sulfonic acid group, it is advantageous and preferable at the point which is easy to control the quantity.

In General formula (2) which shows the unit (2), R <^9> -R <^15> represents a hydrogen atom, a fluorine atom, or an alkyl group, and a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc. are illustrated as an alkyl group. The alkyl group may be fluorinated or may be a perfluoroalkyl group such as trifluoromethyl group or pentafluoroethyl group.

In addition, examples of the aryl group represented by Z include a phenyl group, a naphthyl group, and a biphenylyl group represented by the following chemical formula.

In said formula, R <^25> -R <^33> is the same or different and is a hydrogen atom, a fluorine atom, or an alkyl group, The thing illustrated about R <^9> -R <^15> in General formula (1) is mentioned as an alkyl group.

In Formulas 3 to 5 representing units (3) to (5), R ¹⁷ to R ²⁴ each represent a hydrogen atom, an alkyl group, a fluorine atom, a fluoroalkyl group and an aryl group, but the alkyl group is methyl, ethyl, propyl or butyl. A group, a hexyl group, etc. are illustrated, A perfluoromethyl group, a perfluoroethyl group, etc. are illustrated as a fluoroalkyl group, A phenyl group, a tolyl group, a xylyl group, etc. are illustrated as an aryl group.

It is preferable that the ratio of a repeating unit (A) in a polymer is the range of 10-90 mol% in a copolymer, More preferably, it is 20-80 mol%. If the unit (A) is too small, the amount of sulfonic acid groups introduced into the copolymer by sulfonation is likely to be insufficient, so that the proton conductivity obtained is not sufficient.

The polymer of the present invention may be a monomer corresponding to another repeating unit, for example, the monomer (1m) of the present invention, for example, each of the repeating units (2), (3), (4) and (5). Monomers represented by the formulas 2m, 3m, 4m, and 5m corresponding to (referred to as monomers (2m), (3m), (4m) and (5m), respectively, these monomers collectively referred to as monomer (A))) It is obtained by polymerizing or copolymerizing one or more monomers selected from the group to be present in the presence of a catalyst comprising a transition metal compound.

Wherein X, A and B are as defined for Formula 1m, R ⁹ to R ¹⁵ may be the same or different, represent a hydrogen atom, a fluorine atom or an alkyl group, and m and Z are defined in relation to Formula 2 As shown.

In the formulas, R ¹⁷ to R ²⁴ are as defined with respect to Formulas 3 to 5, and R and R 'are independently a halogen atom other than fluorine or the formula -OSO ₂ Y, wherein Y is an alkyl group, fluoroalkyl group or aryl Group).

In the formulas 3m to 5m, the halogen atom represented by R and R ', and the alkyl group, fluoroalkyl group and aryl group in Y can all exemplify the same as those exemplified for R ¹⁷ to R ²⁴ of the formulas (3) to (5).

Moreover, the sulfonic acid group containing polymer of this invention is obtained by sulfonating the polymer obtained in this way using a sulfonating agent as a precursor.

As a monomer (2m), the compound represented, for example by the following formula is mentioned.

(Wherein, x and z are as described above with respect to formula (2m).)

More specifically, examples of the monomer (2m) include compounds represented by the following chemical formulas.

As monomer (2m), in terms of solubility and high molecular weight, dichlorobenzoic acid derivatives such as 2,5-dichloro-4'-phenoxybenzophenone, 2,4-dichloro-4'-phenoxybenzophenone, 4 Preference is given to using '-phenoxyphenyl2,5-dichlorobenzoate and 4'-phenoxyphenyl2,4-dichlorobenzoate.

Monomer (2m) can synthesize | combine 2, 5- dichloro-4'- [4- (4-phenoxy) phenoxy] benzophenone, for example by the following reaction.

Namely, compound (2m) '(2,5-dichloro-4'-fluorobenzophenone) and compound (2m) "(4-phenoxyphenol) are reacted with dimethylacetamide, N as a reaction solvent in the presence of potassium carbonate or the like. Azeotropic solvents such as benzene, toluene, xylene, etc. to remove from the reaction solution by azeotropic water produced using aprotic dipolar polar solvents such as -methyl- 2-pyrrolidone and dimethyl sulfoxide And the mixture is reacted at a reaction temperature of 80 to 200 ° C. for 0.5 to 30 hours. The compound (2 m) 'per 1 mol of the compound (2 m) "

The monomer (1) of this invention obtained in this way can confirm the structure by IR, NMR, elemental analysis, etc.

Specific examples of the monomer (3m) include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, p-dimethylsulfonyloxybenzene, 2,5-dichlorotoluene, 2,5-dibromotoluene , 2,5-diiodotoluene, 2,5-dimethylsulfonyloxybenzene, 2,5-dichloro-p-xylene, 2,5-dibromo-p-xylene, 2,5-diiodine-p- Xylene, 2,5-dichlorobenzotrifluoride, 2,5-dibromobenzotrifluoride, 2,5-diiobenzobenzotrifluoride, 1,4-dichloro-2,3,5,6-tetra Fluorobenzene, 1,4-dibromo-2,3,5,6-tetrafluorobenzene, 1,4-diiodine-2,3,5,6-tetrafluorobenzene, etc. are mentioned, Preferred is p-dichlorobenzene, p-dimethylsulfonyloxybenzene, 2,5-dichlorotoluene, 2,5-dichlorobenzotrifluoride.

Specific examples of the monomer (4m) include 4,4'-dimethylsulfonyloxybiphenyl, 4,4'-dimethylsulfonyloxy-3,3'-dipropenylbiphenyl, 4,4'-dibromobi Phenyl, 4,4'-diiobibiphenyl, 4,4'-dimethylsulfonyloxy-3,3'-dimethylbiphenyl, 4,4'-dimethylsulfonyloxy-3,3'-difluorobife Nyl, 4,4'-dimethylsulfonyloxy-3,3'5,5'-tetrafluorobiphenyl, 4,4'-dibromooctafluorobiphenyl, 4,4'-dimethylsulfonyloxyoctafluoro Lobbyphenyl etc. are mentioned, Preferably 4,4'- dimethylsulfonyloxy biphenyl, 4,4'- dibromobiphenyl, 4,4'- diiod biphenyl, 4,4'- dimethylsul Phonyloxy-3,3'-dipropenylbiphenyl.

Specific examples of the monomer (5m) include m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, m-dimethylsulfonyloxybenzene, 2,4-dichlorotoluene, 2,4-dibromotoluene , 2,4-diiotoluene, 3,5-dichlorotoluene, 3,5-dibromotoluene, 3,5-diiodotoluene, 2,6-dichlorotoluene, 2,6-dibromotoluene, 2 , 6-diiodotoluene, 3,5-dimethylsulfonyloxytoluene, 2,6-dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 2,4-dibromobenzotrifluoride, 2 , 4-diiodinebenzotrifluoride, 3,5-dichlorobenzotrifluoride, 3,5-dibromotrifluoride, 3,5-diiodinebenzotrifluoride, 1,3-dibromo- 1,4,5,6-tetrafluorobenzene, etc. are mentioned, Preferably m-dichlorobenzene, 2, 4- dichloro toluene, 3, 5- dimethyl sulfonyl oxy toluene, 2, 4- dichloro benzotri Fluoride.

When synthesize | combining the copolymer containing a repeating unit (1) and a repeating unit (A), 1 chosen from the group containing the monomer (1) represented by the said Formula (1m), and the compound represented by the said Formula (2m-5m). The ratio of the monomer (A) of the species or more is the same as the ratio of the unit (1) and the unit (A) in the polymer. That is, the usage-amount of the monomer (1) is preferably 40 to 3 mol% of the shearing material, more preferably in the range of 35 to 5 mol%. As for the usage-amount of a monomer (A), 60-97 mol% of a shearing monomer is preferable, More preferably, it is 65-95 mol%.

In particular, when using monomer (2m) as monomer (A), the ratio is preferably 10 mol% or more, more preferably 20 mol% or more in the shearing body. Within this range, a good solubility high molecular weight body can be obtained.

In addition, when using a monomer (3m), the ratio is preferably 10 mol% or more, more preferably 20 mol% or more in a shearing body. Within this range, a good solubility high molecular weight body can be obtained.

In addition, when using monomer (4m), the ratio is preferably 50 mol% or less, More preferably, it is 30 mol% or less in a shearing body. Within this range, good solubility and high molecular weight can be obtained.

In addition, when using monomer (5m), the ratio is preferably 50 mol% or less, More preferably, it is 30 mol% or less in a shearing body.

The catalyst used when producing the copolymer of the present invention is a catalyst system containing a transition metal compound.

① a transition metal salt and a compound to be a ligand (hereinafter referred to as a ligand component), or a transition metal complex (including copper salt) to which the ligand is coordinated, and

(2) A reducing agent is an essential component, and "salt" may be added to increase the polymerization rate.

Here, as the transition metal salt, nickel compounds such as nickel chloride, nickel bromide, nickel iodide and nickel acetylacetonate, palladium compounds such as palladium chloride, palladium bromide and palladium iodide, iron compounds such as iron chloride, iron bromide and iron iodide, Cobalt compounds, such as cobalt chloride, cobalt bromide, and cobalt iodide, etc. are mentioned. Among these, nickel chloride and nickel bromide are particularly preferable.

Further, as the ligand component, triphenylphosphine, 2,2'-bipyridine, 1,5-cyclooctadiene, 1,3-bis (diphenylphosphino) propane, and the like can be cited, but triphenylphosphine, 2,2'-bipyridine is preferred. The compound which is the said ligand component can be used individually by 1 type or in combination of 2 or more types.

Moreover, as a transition metal complex with which the ligand previously coordinated, for example, nickel chloride (triphenylphosphine), nickel bromide (triphenylphosphine), nickel iodide (triphenylphosphine), and nickel nitrate ( Triphenylphosphine), nickel chloride (2,2'-bipyridine), nickel bromide (2,2'-bipyridine), nickel iodide (2,2'-bipyridine), nickel nitrate (2,2'- Bipyridine), bis (1,5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium, and the like. Nickel chloride (triphenylphosphine) and nickel chloride (2,2'-bipyridine) are preferable.

Examples of the reducing agent that can be used in the catalyst system usable above include iron, zinc, manganese, aluminum, magnesium, sodium, calcium, and the like, but zinc, magnesium, and manganese are preferred. These reducing agents can be used by further activating them by contact with an acid such as an organic acid.

Further, "salts" that can be used in the catalyst system include sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide and sodium sulfate, potassium compounds such as potassium fluoride, potassium chloride, potassium bromide, potassium iodide and potassium sulfate, and tetraethyl fluoride. Ammonium compounds, such as ammonium, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium sulfate, etc., but sodium bromide, sodium iodide, potassium bromide, tetraethylammonium iodide, tetraethylammonium iodide desirable.

The use ratio of each component in the catalyst system is usually 0.0001 to 10 mol, preferably 0.01 to 0.5 mol, with respect to 1 mol of the total amount of the transition metal salt or transition metal complex. If it is less than 0.0001 mole, a polymerization reaction will not progress enough, whereas if it exceeds 10 mol, there exists a problem that molecular weight falls.

When the transition metal salt and the ligand component are used in the catalyst system, the proportion of the ligand component used is usually 0.1 to 100 moles, preferably 1 to 10 moles, per 1 mole of the transition metal salt. If it is less than 0.1 mole, the catalytic activity is insufficient. On the other hand, if it is more than 100 mole, the molecular weight is lowered.

In addition, the use rate of the reducing agent in a catalyst system is 0.1-100 mol normally with respect to 1 mol of total of the said monomers, Preferably it is 1-10 mol. If it is less than 0.1 mole, the polymerization does not proceed sufficiently. On the other hand, if it exceeds 100 moles, there is a problem that purification of the polymer obtained is difficult.

In addition, when "salt" is used in the catalyst system, the use ratio is usually 0.001 to 100 moles, preferably 0.01 to 1 mole, based on 1 mole of the total of the monomers. If the amount is less than 0.001 mole, the effect of increasing the polymerization rate is insufficient. On the other hand, if the amount exceeds 100 mole, purification of the obtained polymer becomes difficult.

Examples of the polymerization solvent that can be used in the present invention include tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone. , γ-butyrolactone, γ-butyrolactam, and the like, and tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable. . It is preferable to use these polymerization solvents after fully drying.

The concentration of the total amount of the monomers in the polymerization solvent is usually 1 to 90% by weight, preferably 5 to 40% by weight.

In addition, the polymerization temperature at the time of superposing | polymerizing the copolymer of this invention is 0-200 degreeC, Preferably it is 50-120 degreeC. In addition, the polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours.

Here, the copolymer represented by a following formula can be obtained by polymerizing on condition mentioned above using monomer (1m) and monomer (2m), for example.

(Wherein A, B, Z, R ¹ to R ¹⁵ , m and n are as described above, p and q independently represent the number of each repeating unit, and the ratio of p / q (ie, 2 above) Molar ratio of two repeat units) is 99/1 to 20/80.)

The structure of the copolymer of the present invention can be confirmed, for example, by COC absorption of 1,230 to 1,250 cm ^-1 by C, O absorption of 1,640 to 1,660 cm ^-1 , etc. by infrared absorption spectrum, and also by nuclear magnetic resonance spectrum ( ¹ H-NMR) can confirm its structure at the peak of aromatic protons of 6.8 to 8.0 ppm.

Next, the copolymer which has a sulfonic acid group which can be used for the electrically conductive film of this invention can be obtained by introducing a sulfonic acid group by a conventional method using a sulfonating agent to the said copolymer which does not have a sulfonic acid group.

As a method for introducing a sulfonic acid group, for example, the copolymer having no sulfonic acid group can be sulfonated under known conditions using known sulfonating agents such as sulfuric anhydride, fuming sulfuric acid, crorosulfonic acid, sulfuric acid, and sodium hydrogen sulfite. Polymer Preprints, Japan, Vol 42, No. 3, p. 730 (1993): Polymer Preprints, Japan, Vol 43, No. 3, p. 736 (1994) Polymer Preprints, Japan, Vol. 42, No, 7 , p. 2490 to 2492 (1993).

That is, as reaction conditions for the sulfonation, the copolymer having no sulfonic acid group is allowed to react with the sulfonating agent in the absence of a solvent or in the presence of a solvent. Examples of the solvent include tetrachloroethane, in addition to hydrocarbon solvents such as n-hexane, ether solvents such as tetrahydrofuran and dioxane, aprotic polar solvents such as dimethylacetamide, dimethylformamide and dimethyl sulfoxide. And halogenated hydrocarbons such as dichloroethane, chloroform and methylene chloride. Although reaction temperature does not have a restriction | limiting in particular, Usually, it is -50-200 degreeC, Preferably it is -10-100 degreeC. The reaction time is usually 0.5 to 1000 hours, preferably 1 to 200 hours.

The amount of sulfonic acid group in the sulfonic acid group-containing copolymer of the present invention thus obtained is 0.5 to 3 mg equivalent / g, preferably 0.8 to 2.8 mg equivalent / g. If it is less than 0.5 mg equivalent / g, proton conductivity will not increase, whereas if it exceeds 3 mg equivalent / g, hydrophilicity will improve and it will become a water-soluble polymer, or durability will fall without reaching water solubility.

The quantity of said sulfonic acid group can be easily adjusted by changing the use ratio of monomer (1) and monomer (A), and also the kind and combination of monomer (A).

In addition, the polymer molecular weight of the precursor before sulfonation of the sulfonic acid group containing copolymer of this invention obtained in this way is 10,000-1 million in polystyrene conversion weight average molecular weight, Preferably it is 20,000-800,000. If it is less than 10,000, a coating film property may be inadequate, for example, a crack may generate | occur | produce in a molded film, and there also exists a problem also in strength property. On the other hand, when it exceeds 1 million, since solubility is inadequate, there exists a problem of high solution viscosity and poor workability at the same time.

In addition, the structure of the sulfone group-containing copolymer of the present invention is S30 O absorption of 1,030 to 1,045 cm ^-1 , 1,160 to 1,190 cm ^-1 by the infrared absorption spectrum, COC absorption of 1,130 to 1,250 cm ^-1 , 1,640 to 1,660 It can confirm by C = O absorption etc. of cm <^-1> , These composition ratios can be known by neutralization titration of sulfonic acid, and elemental analysis. Further, by the nuclear magnetic resonance spectra ⁽¹ H-NMR), it can be found in the structure of the aromatic protons in the 6.8 to 8.0 ppm peak.

Next, the conductive film of the present invention includes the sulfonic acid group-containing copolymer, but in addition to the sulfonic acid group-containing copolymer, inorganic acids such as sulfuric acid and phosphoric acid, organic acids containing carboxylic acid, and an appropriate amount of water may be used in combination.

In order to manufacture the electrically conductive film of this invention, the casting method, the melt-molding method, etc. which melt | dissolve the sulfonic acid group containing copolymer of this invention in a solvent, and shape | mold in a film form by casting are mentioned, for example.

In the casting method, examples of the solvent include aprotic polar solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. The solvent may further contain an alcohol solvent such as methanol.

The conductive membrane of the present invention can be used for proton conductive conductive membranes that can be used in, for example, primary battery electrolytes, secondary battery electrolytes, polymer solid electrolytes for fuel cells, display devices, various sensors, signal transmission media, solid capacitors, ion exchange membranes, and the like.

The halogenated aromatic compound of the present invention is useful for introducing a flexible structure into the polymer molecule, and the resulting aromatic polymer has a flexible structure in the main chain, and thus has high toughness. Do not. The sulfonic acid group-containing polymer obtained by sulfonating the polymer is useful as a proton conductive membrane material, and the obtained proton conductive membrane is excellent in mechanical strength and excellent in durability.

In addition, the copolymer according to a preferred embodiment of the present invention having a repeating unit represented by the formula (2) can easily control the amount of sulfonic acid groups introduced during sulfonation. The resulting sulfone group-containing copolymer is a conductive film, has a high proton conductivity over a wide temperature range, and is excellent in adhesion to a substrate and an electrode, and is excellent in that it does not break even at high strength, and also has excellent hot water resistance.

Therefore, the proton conductive membrane of the present invention can be used as a conductive membrane for a primary battery electrolyte, a secondary battery electrolyte, a fuel cell polymer solid electrolyte, a display element, various sensors, a signal transmission medium, a solid capacitor, an ion exchange membrane, and the like. Is very large.

<Example>

Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example. In addition, various measurement items in the Example were calculated | required as follows.

[Weight Average Molecular Weight]

The weight average molecular weight of the precursor polymer before sulfonation calculated | required polystyrene conversion molecular weight by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[Amount of sulfonic acid group]

The washed water of the obtained sulfonated polymer was washed until the pH was 4 to 6, the acid remaining in the free state was removed, washed with water sufficiently and dried, and then a predetermined amount was weighed and dissolved in a THF / water mixed solvent to dissolve phenolphthalein. Was used as an indicator, and titrated with a standard solution of NaOH to determine the amount of sulfonic acid groups (mg equivalent / g) at the neutralization point.

Tensile Strength Characteristics

A test piece having a width of 3 mm × length of 65 mm (25 mm between chucks) of the sulfonated polymer formed into a film having a thickness of 50 μm was prepared, and the elastic modulus, breaking strength, yield strength, and elongation at room temperature were measured using a tensile tester.

[Bending Resistance]

The sulfonated polymer film formed into a film having a thickness of 50 µm was made excellent using a bending resistance tester of 500 times or more until the number of bendings were broken under conditions of 166 bending times / minute, a load of 200 g, and a bending deformation angle of 135 ° C. Less than 500 times were made into defects.

[Measurement of Proton Conductivity]

AC resistance was obtained from the AC impedance measurement between platinum wires by holding a sample in a constant temperature and humidity apparatus with a platinum wire (0.5 mm in diameter) on the surface of a 5 mm wide monolayer membrane sample. The impedance was measured at 10 kHz AC under an environment of 85 ° C. and 90% relative humidity.

As the resistance measurement device, a chemical impedance measurement system manufactured by NF Circuit Design Block Co., Ltd. was used, and JW 241 manufactured by Yamato Chemical Industries, Ltd. was used as a constant temperature and humidity controller. Five platinum wires were placed at intervals of 5 mm, and the inter-pole distance was changed to 5 to 20 mm to measure the AC resistance.

The resistivity of the membrane was calculated from the interpolar distance and the gradient of resistance, and the AC impedance was calculated from the inverse of the resistivity.

Specific resistance R [Ωcm] = 0.5 [cm] × film thickness [cm] × gradient between resistance poles [Ω / cm]

[Thermal properties]

Pyrolysis temperature:

The decomposition temperature of the sulfonated polymer measured by TGA (20 ° C./min heating rate under nitrogen) was taken as the thermal decomposition temperature.

Glass transition temperature:

The temperature which shows the change of heat capacity by DSC (temperature increase rate of 20 degree-C / min under nitrogen) was made into glass transition temperature.

Hot water resistance:

The sulfonated polymer film having a thickness of 50 μm was immersed in hot water at 95 ° C. for 5 hours, and a case where the dimensional change after immersion was less than 50% was excellent, the dimensional change was 50% or more, and the case where the membrane was dissolved was made defective.

Example

<Example 1>

Synthesis of 2,2-bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl] -1,1,1,3,3,3-hexafluoropropane (BCPAF)

33.6 g (100 mmol) of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (bisphenol AF) was added to agitator, Dean-stark tube, cooling tube, It was put in a 1 L three-necked flask equipped with a three-way coke and a thermometer, dried, and replaced with nitrogen. 150 mL of N, N-dimethylacetamide and 75 mL of toluene were added thereto, stirred, and dissolved. After adding 30.4 g (220 mmol) of potassium carbonate, the reaction solution was heated to reflux at 130 ° C in an oil bath. The water produced by the reaction was azeotropic with toluene, and the reaction temperature was gradually raised to 150 ° C while being removed out of the system in the Dean-stark trap. After about 1 hour, when most of the toluene was removed, the reaction solution was cooled to 80 to 90 ° C. Next, 58.7 g (250 mmol) of 4-chloro-4'-fluorobenzophenone was added thereto and reacted at a reaction temperature of 115 to 120 ° C for 7 hours.

After cooling, the inorganics were removed by filtration. The filtrate was poured into 500 mL of methanol and the resulting precipitate was filtered off, washed with methanol and dried. 75 g of the obtained crude product was recrystallized in 165 mL of toluene to obtain 65 g (85%) of the title compound. Melting point 168-170 ° C.

The infrared absorption spectrum is shown in Fig. 1 and the NMR spectrum in Fig. 2.

<Example 2>

(1) 2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone and 2,2'-bis [4- (4-chlorobenzyl) phenoxy] diphenyl-1,1,1 Preparation of 50:50 Copolymers of 3,3,3-hexafluoropropane

22.8 g (35 mmol) 2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone, 2,2'-bis [4- (4-chlorobenzoyl) phenoxy] diphenyl-1,1 26.7 g (35 mmol), 1,3,3,3-hexafluoropropane, bis (triphenylphosphine) nickel dichloride 1.57 g (2.4 mmol), sodium iodide 1.56 g (10.4 mmol), triphenylphosphine 8.39 g (32 mmol) and 12.6 g (192 mmol) of zinc were placed in a flask, dried, and replaced with nitrogen. 100 ml of N-methyl-2-pyrrolidone (NMP) was added, it heated at 70 degreeC, stirred for 3 hours, and superposed | polymerized reaction. The reaction solution was poured into 3,000 ml of a mixture of methanol: concentrated hydrochloric acid (volume ratio 9: 1) and the product was coagulated and precipitated. The precipitate was filtered off, washed with methanol and then dried in vacuo to yield 35 g (95%) of the desired copolymer. The IR spectrum of the obtained copolymer is shown in FIG. The number average molecular weight of the polymer calculated | required by GPC was 29,400, and the weight average molecular weight was 60,500. The glass transition temperature of 168 degreeC and the thermal decomposition start temperature under nitrogen were 336 degreeC. In addition, the film exhibited soft tensile characteristics showing an elastic modulus of 2.6 GPa, a yield stress of 94 MPa, a yield elongation of 6%, a tensile strength of 87 MPa, and an elongation at break of 10%.

(2) 2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone and 2,2'-bis [4- (4-chlorobenzoyl) phenoxy] diphenyl-1,1,1, Preparation of Sulfonates of 50:50 Copolymers with 3,3,3-hexafluoropropane

200 ml of concentrated sulfuric acid was added to 20 g of the obtained copolymer, and the mixture was stirred at 60 ° C for 5 hours. The reaction solution was poured into water to precipitate the polymer. The polymer washing was repeated until the pH of the washing water reached 5. Drying gave 25 g (96%) of sulfonated polymer. Infrared absorption spectra are shown in FIG. 4.

The properties of the obtained sulfonated polymer are shown in Table 1.

<Example 3>

(1) 2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone and 2,2'-bis [4- (4-chlorobenzoyl) phenoxy] diphenyl-1,1,1, Preparation of 70:30 Copolymer of 3,3,3-hexafluoropropane

24.4 g (56 mmol) 2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone, 2,2'-bis [4- (4-chlorobenzoyl) phenoxy] diphenyl-1,1 Polymerization was carried out in the same manner as in Example 1 except for changing to 18.3 g (24 mmol) of 1,3,3,3-hexafluoropropane, to obtain 35 g (95%) of the copolymer. The number average molecular weight of the polymer calculated | required by GPC was 27,800, and the weight average molecular weight was 60,200. The IR spectrum of the obtained copolymer is shown in FIG. The thermal decomposition start temperature under the glass transition temperature of 155 ° C and nitrogen was 384 ° C.

(2) 2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone and 2,2'-bis [4- (4-chlorobenzoyl) phenoxy] diphenyl-1,1,1, Preparation of Sulfonates of 70:30 Copolymers of 3,3,3-hexafluoropropane

200 ml of concentrated sulfuric acid was added to 20 g of the obtained copolymer, and the mixture was stirred at 60 ° C for 5 hours. The reaction solution was poured into water to precipitate the polymer. The polymer washing was repeated until the pH of the washing water reached 5. It dried and obtained 23 g (93%) of sulfonated polymers. Infrared absorption spectrum is shown in FIG. 6.

The properties of the obtained sulfonated polymer are shown in Table 1.

Comparative Example 1

(1) Preparation of homopolymer of 2,5-dichloro-4'-phenoxybenzophenone

2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone 22.8 (35 mmol), 2,2'-bis [4- (4-chlorobenzoyl) phenoxy] diphenyl used in Example 1 Instead of 26.7 g (35 mmol) of -1,1,1,3,3,3-hexafluoropropane, only 24.0 g (70 mmol) of 2,5-dichloro-4'-phenoxybenzophenone was used. The thing superposed | polymerized similarly to Example 1 and performed the post-processing operation.

The molecular weight measured in GPC of the obtained polymer was Mn 34,800 and Mw 95,100. The 5% thermal decomposition temperature was 404 degreeC under glass transition temperature of 152 degreeC and nitrogen. In addition, the tensile properties of the film were bent and broken at an elastic modulus of 2.2 GPa, tensile strength of 2.1 MPa, and elongation at break of 3%.

(2) Preparation of sulfonates of homopolymers of 2,5-dichloro-4'-phenoxybenzophenone

200 ml of concentrated sulfuric acid was added to 20 g of the obtained homopolymer, and the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into water to precipitate the polymer. The polymer washing was repeated until the pH of the washing water reached 5. It dried and obtained 23 g (93%) of sulfonated polymers.

The properties of the obtained sulfonated polymer are shown in Table 1.

Amount of sulfonic acid group (mg equivalent / g) Tensile strength properties Bending resistance Proton Conductivity (S / cm) Thermal properties Modulus of elasticity (GPa) Yield strength (MPa) Breaking strength (MPa) Elongation (%) Pyrolysis Temperature (℃) Glass transition temperature (℃) Example 1 1.91 1.96 51 42 13 Good 0.14 300 > 250 Example 2 2.62 1.41 50 46 10 Good 0.18 250 > 250 Comparative Example 1 2.45 2.50 Do not surrender 33 3 Bad 0.20 190 > 250

<Example 4>

Preparation of 4,4'-bis [(4-chlorobenzoyl) phenoxy] diphenylsulfone (BCPES)

25.0 g (100 mmol) of 4,4'-dichlorodiphenylsulfone (Bis-S) was placed in a 1 L three-necked flask equipped with a stirrer, a Dean-stark tube, a cooling tube, a three-way coke, and a thermometer, followed by nitrogen substitution. 150 mL of N, N-dimethylacetamide and 75 mL of toluene were added thereto, stirred, and dissolved. After adding 30.4 g (220 mmol) of potassium carbonate, the reaction solution was heated to reflux at 130 ° C in an oil bath. The water produced by the reaction was azeotropic with toluene, and the reaction temperature was gradually raised to 150 ° C while being removed out of the system in the Dean-stark trap. After about 1 hour, when most of the toluene was removed, the reaction solution was cooled to 80 to 90 ° C. Next, 58.7 g (250 mmol) of 4-chloro-4'-fluorobenzophenone was added, and the reaction was carried out at a reaction temperature of 140 to 150 ° C for 7 hours.

After cooling, the inorganics were removed by filtration. The filtrate was poured into 500 mL of methanol, and the resulting precipitate was filtered, washed with methanol and dried. 66 g of the obtained crude product was recrystallized from 160 mL of toluene to obtain 58 g (85%) of the title compound. Melting point 191-195 ° C.

The infrared absorption spectrum is shown in FIG. 7, and the NMR spectrum is shown in FIG. 8.

Example 5

(1) Preparation of 60:40 copolymer of 2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone and 4,4'-bis [(4-chlorobenzoyl) phenoxy] diphenylsulfone

24.4 g (48 mmol) of 2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone, 16.3 g (32 mmol) of 4,4'-bis [(4-chlorobenzoyl) phenoxy] diphenylsulfone ), Bis (triphenylphosphine) nickel dichloride 1.57 g (2.4 mmol), sodium iodide 1.56 g (10.4 mmol), triphenylphosphine 8.39 g (32 mmol), zinc 12.6 g (192 mmol) After drying, nitrogen was substituted. 100 ml of N-methyl-2-pyrrolidone (NMP) was added, it heated at 70 degreeC, it stirred for 3 hours, and superposed | polymerized reaction. The reaction solution was poured into 3,000 ml of a mixture of methanol: conc. Hydrochloric acid (volume ratio 9: 1) and the product was coagulated and precipitated. The precipitate was filtered off, washed with methanol and then dried in vacuo to yield 35 g (95%) of the desired copolymer. The IR spectrum of the obtained copolymer is shown in FIG. The number average molecular weight of the polymer calculated | required by GPC was 29,400, and the weight average molecular weight was 60,500. The glass transition temperature of 168 degreeC and the thermal decomposition start temperature under nitrogen were 336 degreeC. In addition, the film exhibited ductile tensile properties showing an elastic modulus of 2.6 GPa, a yield stress of 94 MPa, a yield elongation of 6%, a tensile strength of 87 MPa, and a breaking elongation of 10%.

(2) 60:40 copolymers of 2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone with 4,4'-bis [(4-chlorobenzoyl) phenoxy] diphenylsulfone Preparation of Sulfonates

200 ml of concentrated sulfuric acid was added to 20 g of the obtained copolymer, and the mixture was stirred at 60 ° C for 5 hours. The reaction solution was poured into water to precipitate the polymer. The polymer washing was repeated until the pH of the washing water reached 5. It dried and obtained 25 g (96%) of sulfonated polymers. Infrared absorption spectrum is shown in FIG. 10.

The properties of the obtained sulfonated polymer are shown in Table 2.

<Example 6>

(1) Preparation of 50:50 copolymer of 2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone and 4,4'-bis [(4-chlorobenzoyl) phenoxy] diphenylsulfone

15.2 g (35 mmol) of 2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone, 22.8 g (35 mmol) of 4,4'-bis [(4-chlorobenzoyl) phenoxy] diphenylsulfone ), Bis (triphenylphosphine) nickel dichloride 1.37 g (2.1 mmol), sodium iodide 1.36 g (9.1 mmol), triphenylphosphine 7.34 g (28 mmol), zinc 110 g (168 mmol) After drying, nitrogen was substituted. 88 ml of N-methyl-2-pyrrolidone (NMP) was added, it heated at 70 degreeC, stirred for 3 hours, and performed the polymerization reaction. The reaction solution was poured into 3,000 ml of a mixture of methanol: conc. Hydrochloric acid (volume ratio 9: 1) to coagulate and precipitate the product. The precipitate was filtered off, washed with methanol and then dried in vacuo to give 32 g (95%) of the desired copolymer. The IR spectrum of the obtained copolymer is shown in FIG. The number average molecular weight of the polymer calculated | required by GPC was 29,400, and the weight average molecular weight was 60,500. The glass transition temperature of 168 degreeC and the thermal decomposition start temperature under nitrogen were 336 degreeC. The film also exhibited soft tensile properties showing an elastic modulus of 2.6 GPa, a yield stress of 94 MPa, a yield elongation of 6%, a tensile strength of 87 MPa, and a breaking elongation of 10%.

(2) 50:50 copolymer of 2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone with 4,4'-bis [(4-chlorobenzoyl) phenoxy] diphenylsulfone Preparation of Sulfonates

200 ml of concentrated sulfuric acid was added to 20 g of the obtained copolymer, and the mixture was stirred at 60 ° C for 5 hours. The reaction solution was poured into water to precipitate the polymer. The polymer washing was repeated until the pH of the washing water reached 5. It dried and obtained 25 g (96%) of sulfonated polymers. The infrared absorption spectrum is shown in FIG.

The properties of the obtained sulfonated polymer are shown in Table 2.

<Example 7>

(1) In Example 2, the amount of 2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone is 27.36 g (42 mmol) and 2,2'-bis [4- (4 -Chlorobenzoyl) phenoxy] diphenyl-1,1,1,3,3,3-hexafluoropropane was changed to 10.68 g (14 mmol), and 3.51 g of 4,4'-dichlorobenzophenone was added. A polymerization reaction was carried out in the same manner as in Example 2 except that 14 mmol) was added, to obtain 34.2 g (94%) of the copolymer.

The weight average molecular weight of the polymer determined by GPC was 109,800. The obtained infrared absorption spectrum is shown in FIG.

(2) 200 ml of concentrated sulfuric acid was added to 20 g of the obtained copolymer, followed by stirring at 60 ° C for 5 hours. The reaction solution was poured into water to precipitate the polymer. The polymer washing was repeated until the pH of the washing water reached 5. It dried and obtained 25 g (96%) of sulfonated polymers. Infrared absorption spectrum is shown in FIG. 14.

The properties of the obtained sulfonated polymer are shown in Table 2.

Amount of sulfonic acid group (mg equivalent / g) Tensile strength properties Bending resistance Proton Conductivity (S / cm) Thermal properties Modulus of elasticity (GPa) Yield strength (MPa) Breaking strength (MPa) Elongation (%) Pyrolysis Temperature (℃) Glass transition temperature (℃) Water-resistant Example 5 2.05 1.29 46 39 17 Good 0.16 240 > 200 Good Example 6 1.77 1.44 60 58 36 Good 0.11 250 > 200 Good Example 7 2.09 1.76 45 41 14 Good 0.18 250 > 200 Good

<Example 8>

(Synthesis of oligomers)

2,2-bis (4-hydroxyphenyl) -1,1,1,3,3 in a 1 L three-necked flask equipped with a stirrer, thermometer, cooling tube, Dean-Stark tube and three-way coke of nitrogen introduction 67.3 g (0.20 mol), 3-hexafluoropropane (bisphenol AF), 60.3 g (0.24 mol) of 4,4'-dichlorobenzophenone (4,4'-DCBP), 71.9 g (0.52 mol) of potassium carbonate, 300 mL of N, N-dimethylacetamide (DMAc) and 150 mL of toluene were added, and it heated and stirred in nitrogen atmosphere in an oil bath, and made it react at 130 degreeC. When the water produced by the reaction was azeotropic with toluene and reacted while being removed out of the system from the Dean-Stark tube, almost no water was produced in about 3 hours. The reaction temperature was gradually raised from 130 deg. C to 150 deg. Thereafter, most of the toluene was removed while gradually raising the reaction temperature to 150 ° C., and the reaction was continued at 150 ° C. for 10 hours, and then 4,4′-DCBP 10.0 g (0.40 mol) was added and the reaction was further performed for 5 hours. . After cooling the obtained reaction liquid, the precipitate of the by-produced inorganic compound was filtered out, and the filtrate was poured into 4 L of methanol. The precipitated product was filtered off, collected and dried, and then dissolved in 300 mL of tetrahydrofuran. This was reprecipitated in 4 L of methanol, and the target compound 95g (yield 85%) was obtained.

The number average molecular weight of polystyrene conversion calculated | required by GPC (THF solvent) of the obtained polymer was 4,200, and the weight average molecular weight was 8,300. Infrared absorption spectrum is shown in FIG. 15. Moreover, the obtained polymer was soluble in THF, NMP, DMAc, sulfolane, etc., and Tg was 110 degreeC, and the thermal decomposition temperature was 498 degreeC.

The obtained polymer was estimated to have a structure represented by the formula (6), and the average value of n was 7.8 from this structure and the number average molecular weight described above.

Example 9

(Synthesis of oligomers)

The initial dose of the monomer used in Example 8 was 67.3 g (0.20 mol) of bisphenol AF, 58.3 g (0.232 mol) of 4,4'-DCBP, and 2 g (0.029 mol) of 4,4'-DCBP added thereto. Polymerization was carried out in the same manner as in Example 8 except for changing to). The polymer was obtained 71 g in the yield of 88%. The number average molecular weight of polystyrene conversion calculated | required by GPC (THF solvent) was 7,300, and the weight average molecular weight was 16,400. In addition, the obtained polymer was soluble in THF, NMP, DMAc, sulfolane, etc., and Tg was 129 degreeC, and the thermal decomposition temperature was 516 degreeC. The obtained polymer is represented by the formula (6) and n = 13.9 (average).

<Example 10>

(Synthesis of oligomers)

The initial dose of the monomer used in Example 8 was 67.3 g (0.20 mol) of bisphenol AF, 53.5 g (0.214 mol) of 4,4'-DCBP, and 3.3 g (0.0133 mol) of 4,4'-DCBP added thereto. ) And polymerization were carried out in the same manner as in Example 8 except that the amount of potassium carbonate used was changed to 34.6 g (0.251 mol). The polymer was obtained by 98 g in 93% yield.

The number average molecular weight of polystyrene conversion calculated | required by GPC (THF solvent) was 9,900, and the weight average molecular weight was 22,000. Moreover, the obtained polymer was soluble in THF, NMP, DMAc, sulfolane, etc., Tg was 151 degreeC, and the thermal decomposition temperature was 524 degreeC. The obtained polymer is represented by the formula (6) and n = 18.9 (average).

<Example 11>

(Synthesis of oligomers)

67.3 g (0.20 mol) of bisphenol AF, 50.2 g (0.20 mol) of 4,4'-DCPB, in a 1 L three-necked flask equipped with a stirrer, thermometer, cooling tube, Dean-Stark tube, three-way coke of nitrogen introduction, 71.9 g (0.52 mol) of potassium carbonate, 300 ml of sulfolane and 150 ml of toluene were added, and heated in an oil bath under a nitrogen atmosphere to react at 130 ° C under stirring. When the water produced by the reaction was azeotropic with toluene and reacted while being removed out of the system from the Dean-Stark tube, water was not found in about 3 hours. The reaction temperature was gradually raised from 130 ° C. to 160 ° C. Thereafter, most of the toluene was removed while the reaction temperature was raised to 180 ° C., and the reaction was continued at 180 ° C. for 16 hours, followed by addition of 10.0 g (0.040 mol) of 4,4′-DCPB and further reaction for 4 hours. . After cooling the obtained reaction liquid, the precipitate of the inorganic compound produced | generated additionally was filtered out, and the filtrate was poured into 4 L of methanol. The precipitated product was filtered off, collected and dried and dissolved in 300 ml of THF. This was reprecipitated in 4 L of methanol, and the target compound 82.5g (yield 80.2%) was obtained.

The number average molecular weight of polystyrene conversion calculated | required by GPC (THF solvent) of the obtained polymer was 16,400, and the weight average molecular weight was 37,400. Moreover, the obtained polymer was soluble in THF, NMP, DMAc, sulfolane, etc., Tg was 162 degreeC, and the thermal decomposition temperature was 535 degreeC. The obtained polymer is represented by the formula (6) and n = 31.6 (average).

<Example 12>

In Example 8, the initial dose of 53.5 g (0.214 mol) was added using bis (4-chlorophenyl) sulfone (BCPS) instead of 4,4'-DCBP, and 3.3 g (0.0133 mol) was added thereto. ) And polymerization was carried out in the same manner as in Example 8 except that the amount of potassium carbonate was changed to 58.0 g (0.42 mol). 120g of polymer was obtained with a yield of 96%.

The number average molecular weight of polystyrene conversion calculated | required by GPC (THF solvent) was 4,600, and the weight average molecular weight was 7,600. Infrared absorption spectrum is shown in FIG. 16. Moreover, the obtained polymer was soluble in THF, NMP, DMAc, sulfolane, etc., and Tg was 158 degreeC, and the thermal decomposition temperature was 513 degreeC.

The obtained polymer is assumed to have a structure represented by the formula (7) and n was 8.0 in an average value in the same manner as in the case of Example 8.

Example 13

(1) Synthesis of Polymer

28.4 g (2.87 mmol), 2,5-dichloro-4 '-(4-phenoxy) phenoxybenzophenone (DCPPB) 29.2 g (67.1 mmol), bis (triphenylphosphine) nickel obtained in Example 10 1.37 g (2.1 mmol) of dichloride, 1.36 g (9.07 mmol) of sodium iodide, 7.34 g (28.0 mmol) of triphenylphosphine, and 11.0 g (168 mmol) of zinc powder were placed in a flask, dried and nitrogen-substituted. 130 ml of N-methyl-2-pyrrolidone was added, heated to 80 ° C., stirred for 4 hours, and polymerized. The polymerization solution was diluted in THF, solidified and recovered with hydrochloric acid / methanol, methanol washing was repeated, dissolved in THF, purified by reprecipitation with methanol, filtered and the collected polymer was vacuum dried to give 50.7 g of the desired copolymer. (96%) was obtained. The number average molecular weight of polystyrene conversion calculated | required by GPC (THF) was 40,000, and the weight average molecular weight was 145,000. Infrared absorption spectrum is shown in FIG. 17.

(2) Preparation of Sulfonated Polymer

25 g of the copolymer obtained in the above (1) was placed in a 500 ml separable flask and 250 ml of 96% sulfuric acid was added, followed by stirring for 24 hours under a nitrogen stream. The obtained solution was put in a large amount of ion-exchanged water to precipitate a polymer. The polymer washing was repeated until the pH of the washing water reached 5. Drying gave 29 g (96%) of sulfonated polymer. Infrared absorption spectrum is shown in FIG. 18.

The obtained sulfonated polymer was dissolved in NMP to prepare a film by the cast method. The sulfonated equivalent weight of the sulfonated polymer was 172 mg equivalent / g. The properties of the sulfonated polymers are shown in Table 3.

<Example 14>

(1) Synthesis of Polymer

13.8 g of the oligomer obtained in Example 12 and 11.75 g (27 mmol) of DCPPB were dissolved in a monomer, 0.589 g (0.9 mmol) of bis (triphenylphosphine) nickel chloride, 0.585 g (3.9 mmol) of sodium iodide, and 3.148 g of triphenylphosphine. (12 mmol) and 4.701 g (72 mmol) of zinc powder were placed in a reflux tube and a three-necked flask with three-way coke, and subjected to nitrogen substitution three times in an oil bath at 70 ° C., and then placed under reduced pressure for 1 hour. Thereafter, the mixture was returned to a nitrogen atmosphere, and 60 ml of N-methyl-2-pyrrolidone was added, and polymerization was performed at 80 ° C. After reacting for 10 hours, the mixture was diluted with 50 ml of N-methyl-2-pyrrolidone and reprecipitated with 1:10 hydrochloric acid / methanol to precipitate a polymer to obtain a white powder. The polymer was recovered and dried in vacuo at 60 ° C. The yield was 22.5 g (96% yield). The number average molecular weight of polystyrene conversion calculated | required by GPC (THF) was 33,000, and the weight average molecular weight was 138,000. The infrared absorption spectrum is shown in FIG. 19.

(2) Preparation of Sulfonated Polymer

250 ml of concentrated sulfuric acid was added to 25 g of the polymer obtained in the above (1), and the mixture was stirred at room temperature for 24 hours in a nitrogen atmosphere to perform sulfonation. This was reprecipitated in pure water to precipitate the sulfonated polymer. The water was changed several times and polymer washing was performed until it became pH5. The sulfonated polymer was recovered and hot air dried at 80 deg. The yield of sulfonated polymer was 29 g (95%). Infrared absorption spectrum is shown in FIG. 20. The obtained sulfonated polymer was dissolved in NMP, and a film was prepared by the cast method. The sulfonated equivalent of sulfonated polymer was 1.95 mg equivalent / g. The properties of the sulfonated polymers are shown in Table 3.

Tensile strength properties Bending resistance Proton Conductivity (S / cm) Thermal properties Modulus of elasticity (GPa) Yield strength (MPa) Breaking strength (MPa) Elongation (%) Pyrolysis Temperature (℃) Glass transition temperature (℃) Example 13 1.87 2.05 48 35 Good 0.22 300 > 250 Example 14 2.02 1.87 45 24 Good 0.18 300 > 250

1 is 2,2-bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl] -1,1,1,3,3,3- which is a halogenated aromatic compound of the present invention obtained in Example 1; IR chart of hexafluoropropane (BCPAF).

2 shows an NMR spectrum of the same compound.

3 is an IR chart of a copolymer obtained in Example 2. FIG.

4 is an IR chart of a sulfonated copolymer obtained in Example 2. FIG.

5 is an IR chart of a copolymer obtained in Example 3. FIG.

6 is an IR chart of a sulfonated copolymer obtained in Example 3. FIG.

Fig. 7 is an IR chart of 4,4'-bis [(4-chlorobenzoyl) phenoxy] diphenylsulfone (BCPES) which is a halogenated aromatic compound of the present invention obtained in Example 4.

8 shows an NMR spectrum of the same compound.

9 is an IR chart of a copolymer obtained in Example 5. FIG.

10 is an IR chart of a sulfonated copolymer obtained in Example 5. FIG.

11 is an IR chart of a copolymer obtained in Example 6. FIG.

12 is an IR chart of a sulfonated copolymer obtained in Example 6. FIG.

13 is an IR chart of a copolymer obtained in Example 7. FIG.

14 is an IR chart of a sulfonated copolymer obtained in Example 7. FIG.

15 is an IR chart of an oligomer which is a halogenated aromatic compound of the present invention obtained in Example 8. FIG.

16 is an IR chart of an oligomer which is a halogenated aromatic compound of the present invention obtained in Example 12.

17 is an IR chart of a copolymer obtained in Example 13 (1).

18 is an IR chart of a sulfonated copolymer obtained in Example 13 (2).

19 is an IR chart of a copolymer obtained in Example 14 (1).

20 is an IR chart of a sulfonated copolymer obtained in Example 14 (2).

Claims (3)

Halogenated aromatic compounds represented by the following formula (6). <Formula 6>

In said formula, n is an integer of 1 or more. The compound of claim 1, which is 2,2-bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl] -1,1,1,3,3,3-hexafluoropropane. Halogenated aromatic compounds represented by the following formula (7). <Formula 7>

In said formula, n is an integer of 1 or more.

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