JP2007210919A - Aromatic sulfonic acid ester and sulfonated polyarylene-based polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sulfonated polymer having excellent hot water resistance and mechanical characteristics even on increasing the amount of introduction of sulfonic acid group, and an aromatic sulfonic acid ester derivative. <P>SOLUTION: This aromatic sulfonic acid ester is expressed by general formula (1) [wherein, X is an atom or a group selected from a group consisting of a halogen atom excluding F, -OSO<SB>2</SB>CH<SB>3</SB>and -OSO<SB>2</SB>CF<SB>3</SB>; Y is -CO- or -SO<SB>2</SB>-; Z is O, S, -CO-, -SO<SB>2</SB>- or -SO-; (l) is 0 to 4; (m) is ≥0 integer; Ar is a structure expressed by general formula (2) or (3); U is -CO-, -SO<SB>2</SB>- or -SO-; (n) is 0 to 4; (o) is 0 to 4, provided that (l+n+o)≥1; V is O, S, -CR'<SB>2</SB>-, -CO-, -SO<SB>2</SB>- or -SO-; (p) is 0 to 3; and (q) is 0 to 4, provided that the R' is a hydrocarbon group and (l+p+q)≥1]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel aromatic sulfonate ester and a sulfonated polyarylene polymer.

  The electrolyte is usually used in a (water) solution. However, in recent years, there is an increasing tendency to replace this with a solid system. The first reason is, for example, the ease of processing when applied to the above-mentioned electric / electronic materials, and the second reason is the shift to light, thin, small, and power saving.

  Conventionally, both proton-conducting materials made of inorganic substances and organic substances are known. Examples of inorganic substances include uranyl phosphate, which is a hydrated 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 electrode.

On the other hand, as examples of organic compounds, polymers belonging to so-called cation exchange resins, for example, sulfonated products of vinyl polymers such as polystyrene sulfonic acid, Nafion (trade name,
Perfluoroalkyl sulfonic acid polymers such as Dupont), perfluoroalkyl carboxylic acid polymers, and polymers in which sulfonic acid groups or phosphoric acid groups are introduced into heat-resistant polymers such as polybenzimidazole and polyether ether ketone ( Examples thereof include organic polymers such as Non-Patent Documents 1 to 3).

The organic polymer is usually used in the form of a film, but a conductive film can be bonded on the electrode by utilizing its solubility in a solvent or thermoplasticity. However, many of these organic polymers have high proton conductivity in addition to high temperature (1
(00 ° C. or higher) durability, proton conductivity and mechanical properties, particularly, the elastic modulus is greatly reduced, the dependency on the humidity condition is large, the adhesion to the electrode is not sufficient, and the water-containing polymer structure There are problems such as reduction in strength and collapse of shape due to excessive swelling during operation. Therefore, these organic polymers have various problems when applied to the above-mentioned electric / electronic materials.

Further, Patent Document 1 proposes a solid polymer electrolyte made of sulfonated rigid polyphenylene. This polymer is mainly composed of a polymer obtained by polymerizing an aromatic compound composed of a phenylene chain, and this is 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 groups introduced, at the same time, the mechanical properties of the resulting sulfonated polymer, such as toughness such as elongation at break and bending resistance, and hot water resistance are significantly impaired. There was a problem.
US Pat. No. 5,403,675 Polymer Preprints, Japan, Vol.42, No.7, p.2490-2492 (1993) Polymer Preprints, Japan, Vol.43, No.3, p.735〜736 (1994) Polymer Preprints, Japan, Vol.42, No.3, p.730 (1993)

  An object of the present invention is to provide a sulfonated polymer having excellent hot water resistance and mechanical properties even when the amount of sulfonic acid groups introduced is increased, and an aromatic sulfonate derivative which is a raw material thereof.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above problems can be solved by a sulfonated polyarylene having a specific structural unit, and the present invention has been completed.

Embodiments of the present invention are shown in [1] to [7] below.
[1] An aromatic sulfonic acid ester derivative represented by the following general formula (1).

[In the formula (1), X a halogen atom except fluorine (chlorine, bromine, iodine), - indicates OSO ₂ CH ₃ and atom or a group selected from the group consisting of -OSO ₂ CF _3, Y is -CO- Or -S
Represents O ₂ —, Z represents an oxygen atom, a sulfur atom, —CO— or —SO ₂ — or —SO
-And R independently represents a hydrocarbon group having 4 to 20 carbon atoms. l represents an integer of 0 to 4, and m represents an integer of 0 or more.
Ar represents a structure represented by the following general formula (2) or (3).

In the formula (2), U represents —CO— or —SO ₂ — or —SO—, and R independently represents 4 carbon atoms.
N represents an integer of 0 to 4, and o represents an integer of 0 to 4. However, l + n + o ≧ 1.

In the formula (3), V represents an oxygen atom, a sulfur atom, -CR ' ₂ -or -CO-, -SO ₂ -or -SO-, R' represents a hydrocarbon group having 1 to 20 carbon atoms, R independently represents a hydrocarbon group having 4 to 20 carbon atoms, p represents an integer of 0 to 3, and q represents an integer of 0 to 4. However, l + p + q ≧ 1. ]
[2] A polyarylene polymer having a structural unit represented by the following general formula (1 ′).

[In the formula (1 ′), Y represents —CO— or —SO ₂ —, and Z represents an oxygen atom, a sulfur atom, —CO—, —SO ₂ — or —SO—. l represents an integer of 0 to 4, and m represents an integer of 0 or more.

Ar ′ represents a structure represented by the following general formula (2 ′) or (3 ′). In the formula (2 ′), U represents —CO— or —SO ₂ — or —SO—. n represents an integer of 0 to 4, and o represents an integer of 0 to 4. However, l + n + o ≧ 1. In the formula (3 ′), V represents an oxygen atom, a sulfur atom, —CR ′ ₂ —, —CO— or —SO ₂ —, p represents an integer of 0 to 3, and q represents an integer of 0 to 4. Show. However, R 'shows a C1-C20 hydrocarbon group and it is l + p + q> = 1. ]

[3] The polyarylene copolymer of [2] further having a structural unit represented by the general formula (4).

[4] The polyarylene copolymer of [2] or [3], wherein the general formula (1 ′) is a structural unit represented by the following general formula (1′a).

[In the formula (1′a), Z represents an oxygen atom, a sulfur atom, —CO—, —SO ₂ — or —S.
O- is shown. l represents an integer of 0 to 4, and m represents an integer of 0 or more. Ar is represented by the following general formula (
The structure represented by 2′a) or (3′a) is shown.

In formula (2′a), U represents —CO— or —SO ₂ — or —SO—, n represents an integer of 0 to 4, and o represents an integer of 0 to 4. However, l + n + o ≧ 1. In formula (3′a), V represents an oxygen atom, a sulfur atom, —CR ′ ₂ — or —CO—, —SO ₂ — or —SO—, p represents an integer of 0 to 3, and q represents 0 Represents an integer of ~ 4. However, R ′ represents a hydrocarbon group having 1 to 20 carbon atoms, and 1 + p + q ≧ 1. ]
[5] The polyarylene copolymer of [2] to [4], wherein the structural unit is a structural unit represented by the following general formulas (1′b) to (1′e).

[In the formula (1′b), Z represents an oxygen atom, a sulfur atom, —CO— or —SO ₂ — or —
Indicates SO-, U is -CO- or -SO ₂ - shows the or -SO-. l represents an integer of 0 to 4, n represents an integer of 0 to 4, and o represents an integer of 0 to 4. However, l + n + o ≧ 1.

In formula (1′c), U represents —CO— or —SO ₂ — or —SO—. n represents an integer of 0 to 4, and o represents an integer of 0 to 4. However, n + o ≧ 1.
In formula (1′d), Z represents an oxygen atom, a sulfur atom, —CO—, —SO ₂ — or —SO—, and V represents an oxygen atom, a sulfur atom, —CR ′ ₂ —, —CO— or —. S
O ₂ — or —SO— is shown. l represents an integer of 0 to 4, p represents an integer of 0 to 3, and q represents an integer of 0 to 4. However, R 'shows a C1-C20 hydrocarbon group and is l + p + q> = 1.

In formula (1′e), V represents an oxygen atom, a sulfur atom, —CR ′ ₂ —, —CO—, —SO ₂ — or —SO—. l represents an integer of 0 to 4, p represents an integer of 0 to 3, q
Represents an integer of 0 to 4. However, R 'shows a C1-C20 hydrocarbon group and it is l + p + q> = 1. ]
[6] A polyarylene copolymer of [2] or [3], which is a structural unit represented by the following general formulas (1′f) to (1′i).

[In the formula (1′f), Z represents an oxygen atom, a sulfur atom, —CO— or —SO ₂ — or —
Indicates SO-, U is -CO- or -SO ₂ - shows the or -SO-. l represents an integer of 0 to 1, n represents an integer of 0 to 1, and o represents an integer of 0 to 2. However, l + n + o ≧ 1.

In the formula (1′g), U represents —CO— or —SO ₂ — or —SO—. n represents an integer of 0 to 1, and o represents an integer of 0 to 2. However, n + o ≧ 1.
In formula (1′h), Z represents an oxygen atom, a sulfur atom, —CO—, —SO ₂ — or —SO—, and V represents an oxygen atom, a sulfur atom, —CR ′ ₂ —, —CO— or —. SO ₂ — or —SO— is shown. l represents an integer of 0 to 1, p represents an integer of 0 to 1, and q represents 0.
An integer of ~ 2 is shown. However, R 'shows a C1-C20 hydrocarbon group and it is l + p + q> = 1.

In the formula (1′i), V represents an oxygen atom, a sulfur atom, —CR ′ ₂ —, —CO—, —SO ₂ — or —SO—. p represents an integer of 0 to 1, and q represents an integer of 0 to 2. However, R 'shows a C1-C20 hydrocarbon group and is p + q> = 1. ]
[7] A solid polymer electrolyte comprising the polyarylene copolymer according to [3].

According to the present invention, a copolymer having an aromatic compound having a plurality of sulfonic acid ester groups, an aromatic unit having a plurality of sulfonic acid groups derived from the compound, and a unit having no sulfonic acid group Can be provided. Due to the effect of the aromatic unit having a plurality of sulfonic acid groups of the present invention, a copolymer having a high sulfonic acid concentration can be synthesized, and a material design with high proton conductivity can be achieved. Further, by using such an aromatic unit having a plurality of sulfonic acid groups, a copolymer having a high sulfonic acid concentration can be obtained even when the composition ratio of units having no sulfonic acid group in the copolymer is increased. It is possible to synthesize and design materials with excellent hot water resistance and mechanical properties.

Hereinafter, the aromatic sulfonic acid ester derivative of the present invention will be described in detail.
<Aromatic sulfonic acid ester derivative>
The aromatic sulfonic acid ester derivative of the present invention is represented by the following general formula (1).

In the formula (1), X is a halogen atom other than fluorine (chlorine, bromine, iodine), - indicates OSO ₂ CH ₃ and atom or a group selected from the group consisting of -OSO ₂ CF _3, halogen atoms are preferred. Y represents —CO— or —SO ₂ —, preferably —CO—. Z represents an oxygen atom, a sulfur atom, —CO—, —SO ₂ — or —SO—.

l represents an integer of 0 to 4, m represents an integer of 0 or more, and is preferably 0 or 1. Ar represents a structure represented by the following general formula (2) or (3).
In formula (2), U represents —CO— or —SO ₂ — or —SO—, n represents an integer of 0 to 4, and o represents an integer of 0 to 4. However, l + n + o ≧ 1.

In formula (3), V represents an oxygen atom, a sulfur atom, —CR ′ ₂ —, —CO— or —SO ₂ —, p represents an integer of 0 to 3, and q represents an integer of 0 to 4. . R ′ represents a hydrocarbon group having 1 to 20 carbon atoms, and l + p + q ≧ 1.

  R independently represents a hydrocarbon group having 4 to 20 carbon atoms. Specifically, t-butyl group, sec-butyl group, isobutyl group, n-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, heptyl group, octyl group, 2- Ethylhexyl group, cyclopentylmethyl group, adamantyl group, cyclohexylmethyl group, adamantylmethyl group, tetrahydrofurfuryl group, 2-methylbutyl group, 3,3-dimethyl-2,4-dioxolanemethyl group, bicyclo [2.2.1] Examples thereof include straight chain hydrocarbon groups such as heptyl group and bicyclo [2.2.1] heptylmethyl group, branched hydrocarbon groups, and alicyclic hydrocarbon groups.

  In the case of a copolymer described later, among these, a neopentyl group, a tetrahydrofurfuryl group, a cyclopentylmethyl group, a cyclohexylmethyl group, an adamantylmethyl group, a bicyclo [2.2.1] heptylmethyl group are preferable, and a neopentyl group Is more preferable.

  Examples of such aromatic sulfonic acid esters include the following.

  The method for synthesizing such an aromatic sulfonic acid ester derivative is not particularly limited as long as the compound represented by the formula (1) can be synthesized. For example, a sulfate group may be introduced after reacting a specific chlorobenzophenone and hydroxybenzophenone. It can also be synthesized by reacting a compound that induces a functional group represented by formula (1) or (2) with a chlorosulfonated product. It is also possible to synthesize a compound that induces a functional group represented by the formula (1) or (2), introduce a sulfate ester group, and then perform an oxidation reaction.

The obtained aromatic sulfonic acid ester derivative is purified as necessary, and terminal Na is transesterified.
The identification method of the aromatic sulfonic acid ester derivative is not particularly limited, and a known method such as NMR is employed.

<Sulfonated polyarylene>
The polyarylene polymer according to the present invention has a structural unit represented by the following general formula (1 ′).

In formula (1 ′), Y represents —CO— or —SO ₂ —, preferably —CO—. Z represents an oxygen atom, a sulfur atom, —CO—, —SO ₂ — or —SO—.
l represents an integer of 0 to 4, m represents an integer of 0 or more, and is preferably 0 or 1. Ar ′ represents a structure represented by the following general formula (2 ′) or (3 ′).

In formula (2), U represents —CO— or —SO ₂ — or —SO—, n represents an integer of 0 to 4, and o represents an integer of 0 to 4. However, l + n + o ≧ 1. In formula (3), V represents an oxygen atom, a sulfur atom, —CR ′ ₂ —, —CO— or —SO ₂ —, p represents an integer of 0 to 3, and q represents an integer of 0 to 4. . However, R ′ represents a hydrocarbon group having 1 to 20 carbon atoms, and l + p + q ≧ 1.

<Sulfonated polyarylene copolymer>
The polyarylene polymer according to the present invention may be a homopolymer of a structural unit represented by the above formula (1 ′), and usually contains a structural unit represented by the general formula (4). desirable. When such a structural unit is contained, the strength and water resistance of the polymer can be improved.

In formula (4), A and D are each independently a direct bond, —O—, —S—, —CO—, —SO ₂ —, —SO—, —CONH—, —COO—, — (CF ₂ ) _i - (i is an integer of 1 to _{10), - (CH 2) j} - (j is an integer of 1 to _{10), - CR '2 - (} R' is an aliphatic hydrocarbon group,
An aromatic hydrocarbon group or a halogenated hydrocarbon group is shown. ), At least one structure selected from the group consisting of a cyclohexylidene group and a fluorenylidene group. Among these, a direct bond, —O—, —CO—, —SO ₂ —, —CR ′ ₂ —, a cyclohexylidene group and a fluorenylidene group are preferable. Examples of R ′ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, octyl group, decyl group, octadecyl group, ethylhexyl group, phenyl group, trifluoro group. Examples thereof include a methyl group and a substituent in which some or all of hydrogen atoms in these substituents are halogenated.

B independently represents an oxygen atom or a sulfur atom, preferably an oxygen atom.
R ^{1 to} R ¹⁶ may be the same as or different from each other, and are a hydrogen atom, a fluorine atom, an alkyl group, a halogenated alkyl group, an allyl group, an aryl group, a nitro group, and a nitrile group, which are partially or completely halogenated. At least one atom or group selected from the group consisting of

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a cyclohexyl group, and an octyl group.
Examples of the halogenated alkyl group include a trifluoromethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.

As said allyl group, a propenyl group etc. are mentioned, for example. Examples of the aryl group include a phenyl group and a pentafluorophenyl group.
s and t show the integer of 0-4. r shows 0 or an integer greater than or equal to 1, and an upper limit is 100 normally, Preferably it is 1-80.

As a preferable structure of the structural unit (4), in the above formula (4),
(1) s = 1 and t = 1, A is —CR ′ ₂ —, a cyclohexylidene group or a fluorenylidene group, B is an oxygen atom, and D is —CO— or —SO ₂ —. , R ^{1 to} R ¹⁶ are hydrogen atoms or fluorine atoms,
(2) a structure in which s = 1 and t = 0, B is an oxygen atom, D is —CO— or —SO ₂ —, and R ^{1 to} R ¹⁶ are a hydrogen atom or a fluorine atom,
(3) s = 0 and t = 1, A is —CR ′ ₂ —, a cyclohexylidene group or a fluorenylidene group, B is an oxygen atom, and R ^{1 to} R ¹⁶ are a hydrogen atom, a fluorine atom or a nitrile group The structure which is is mentioned.

The monomer or oligomer (hereinafter also referred to as “compound (4 ′)”) that can be the structural unit (4) can be synthesized, for example, by referring to the method described in JP-A No. 2004-137444.

<Method for producing sulfonated polyarylene>
The sulfonated polyarylene of the present invention can be synthesized, for example, by the method described in JP-A No. 2004-137444.

  Specifically, first, an aromatic sulfonic acid ester derivative represented by the above formula (1) and a compound represented by the following general formula (4 ′) which is a precursor of the above compound (4) are present in the presence of a catalyst. It can be synthesized by copolymerizing under the above to produce a polyarylene having a sulfonate group, deesterifying the sulfonate group, and converting the sulfonate group to a sulfonate group.

Wherein (4 '), X is a halogen atom other than fluorine (chlorine, bromine, iodine), - OSO ₂ CH ₃ and -OSO ₂ CF ₃ shows an atom or a group selected from the group consisting of chlorine or bromine preferable. ^{A, B, D, R 1} ~R 16, s, t, r is, A, in the formula (4) B, which is ^{D, R 1 ~R 16, s} , t, synonymous with r.

  The catalyst used in the above polymerization is a catalyst system containing a transition metal compound, and such a catalyst system includes (i) a compound that becomes a transition metal salt and a ligand (hereinafter referred to as `` ligand component ''). Or a transition metal complex coordinated with a ligand (including a copper salt) and (ii) a reducing agent as essential components, and a salt is added to increase the polymerization rate. May be.

  Specific examples of these catalyst components, use ratio of each component, polymerization conditions such as reaction solvent, concentration, temperature, time, etc. are used with reference to the compounds and conditions described in JP-A No. 2001-342241. Or can be set.

  The ion exchange capacity of the sulfonated polyarylene produced by the above method is usually 0.3 to 5 meq / g, preferably 0.5 to 4 meq / g, more preferably 0.8 to 3.5 meq / g. It is. If the ion exchange capacity is lower than the above range, proton conductivity tends to be low and power generation performance tends to be low, and if it exceeds the above range, water resistance tends to be greatly reduced.

  However, the amount of ion exchange could be significantly increased by using the newly sulfonated monomer compared to the case of using a conventional monosulfonated monomer. For this reason, the polymer synthesized this time tends to have a higher proton conductivity than the conventional polymer.

  The ion exchange capacity can be adjusted, for example, by changing the types, use ratios, combinations, and the like of the compound (1 ′) and the compound (4 ′). In the sulfonated polyarylene of the present invention, the structural unit (1) is 0.5 to 100 mol%, preferably 10 to 99.999 mol%, and the structural unit (4) is 99.5 to 0 mol. %, Preferably 90 to 0.001 mol%.

  The weight average molecular weight of the sulfonated polyarylene thus obtained is 10,000 to 1,000,000, preferably 20,000 to 500,000, more preferably 30,000 to 30 in terms of polystyrene by gel permeation chromatography (GPC). It is ten thousand.

  Such a polyarylene polymer has high proton conductivity, and can be suitably used as a proton conductive membrane, an electrode electrolyte, and a binder for a fuel cell. An electrode electrolyte containing such a polyarylene polymer is also suitable as a membrane electrode assembly.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. The various measurement items in the examples were determined as follows.

(Molecular weight)
As for the molecular weight of the polymer, the weight average molecular weight in terms of polystyrene was determined by GPC. N-methyl-2-pyrrolidone to which lithium bromide was added was used as a solvent.

(Ion exchange capacity)
The obtained sulfonated polymer is washed with water until the pH becomes 4 to 6, the free remaining acid is removed and washed thoroughly, and after drying, a predetermined amount is weighed, and THF / water It was dissolved in a mixed solvent, phenolphthalein was used as an indicator, titrated with a standard solution of NaOH, and the ion exchange capacity was determined from the neutralization point.

<Synthesis Example 1>
2,5-dichloro-4'-fluorobenzophenone 53.8 g (0.2 mol), 4-hydroxybenzophenone 39.6 g (0.2 mol), potassium carbonate 35.9 g (0.26 mol) were placed in a flask, and dimethylacetamide was added. 200 ml was added. After stirring the reaction solution at 100 ° C. for 10 hours, water was added to the reaction solution. The organic substance was extracted using ethyl acetate. Magnesium sulfate was added to the extracted solution and dried, and then the solvent was distilled off using an evaporator. Recrystallization isolation purification was carried out using a mixed solvent of hexane and ethyl acetate to obtain 54.5 g of 4- (2,5-dichlorobenzoyl) -4′-benzoyldiphenyl ether.

4- (2,5-dichlorobenzoyl) -4'-benzoyldiphenyl ether 38.0 g (0.08
5 mol) was placed in a three-necked flask equipped with a condenser, a three-way cock, and a thermometer, and nitrogen substitution was performed. To this, 149 g (1.28 mol) of chlorosulfonic acid was added and dissolved by stirring. The reaction solution was heated to 100 ° C. in an oil bath and stirred for 10 hours. After the completion of the reaction, the reaction solution was allowed to cool to room temperature and then poured into ice water. The organics were extracted with ethyl acetate. The obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution until the washing solution became neutral, and further washed with brine. After drying with magnesium sulfate, the solvent was distilled off using an evaporator to obtain 57.3 g of a chlorosulfonated product.

The obtained chlorosulfonated product 49 g (0.066 mol) was placed in a three-necked flask equipped with a three-way cock, 200 ml of pyridine was added, and the mixture was cooled to 0 ° C. To this, 17.4 g (0.198 mol) of 2,2-dimethyl-1-propanol was gradually added and stirred for 4 hours under ice cooling. After completion of the reaction, the reaction solution was added to an aqueous hydrochloric acid solution. The organic material was extracted with ethyl acetate. The organic layer was washed with 5% aqueous sodium hydrogen carbonate solution and then with saturated brine, dried over magnesium sulfate, and then the solvent was distilled off using an evaporator. Recrystallization from methanol / hexane gave 40.5 g of the desired compound. The obtained compound was a compound represented by the following formula (I). The NMR chart of the obtained compound is shown in FIG.

<Synthesis Example 2>
18.63 g (0.100 mol) of diphenylthioether was placed in a flask, and 8.00 g (0.060 mol) of aluminum chloride was added. After the mixture was cooled to 5 ° C., 10.5 g (0.050 mol) of 2,5-dichlorobenzoyl chloride was added dropwise over 30 minutes.

  The reaction solution was stirred at room temperature for 3 hours, and then the reaction solution was added to ice water. The organic substance was extracted using ethyl acetate. After extraction, the organic layer was washed with an aqueous sodium hydrogen carbonate solution until neutral, and further washed with brine. Magnesium sulfate was added to the extracted solution and dried, and then the solvent was distilled off using an evaporator. Recrystallization isolation and purification were performed using a mixed solvent of hexane and ethyl acetate to obtain 12.4 g of 4- (2,5-dichlorobenzoyl) -diphenylthioether.

4- (2,5-dichlorobenzoyl) -diphenylthioether 10.06 g (0.028 mol)
Was placed in a three-necked flask equipped with a condenser, a three-way cock, and a thermometer, and nitrogen substitution was performed. To this, 8.3 g of sulfuric acid was added and dissolved by stirring. To the sulfuric acid solution, 21.0 g of 30% fuming sulfuric acid was added and heated to 80 ° C. and heated for 6 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, poured into ice water, neutralized with an aqueous sodium hydroxide solution, and insoluble matter was filtered off. After the filtrate was concentrated, dimethyl sulfoxide was added. Insoluble matter was filtered, and the filtrate was concentrated to obtain 15.0 g of a trisulfonated product.

  In a three-necked flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, a cooling tube and a dropping funnel, 39.9 g (0.06 mol) of trisulfonated product and 420 ml of acetic acid were weighed. Thereto was added 46.2 g (0.271 mol) of sodium perborate tetrahydrate. After stirring at 60 ° C for 7 hours, the mixture was cooled to 0 ° C. After filtration, the solvent was distilled off. After adding 100 ml of water, an aqueous sodium hydroxide solution was added until the pH was 6-7. After concentration, the concentrated solution was added to a diisopropyl ether solution and solidified to obtain 38.8 g of Compound (II).

In a three-necked flask equipped with a nitrogen introduction tube and a stirrer, 31.9 g of compound (II) (0.
0457 mol), 10 g of sulfolane and 69.9 g (0.46 mol) of phosphoryl chloride.
Added at room temperature. After stirring at 50 ° C. for 2 hours, the reaction mixture was added to ice water and extracted with ethyl acetate. The organic layer was washed with 5% aqueous sodium hydrogen carbonate solution and then dried over magnesium sulfate. Recrystallization from a mixed solvent of hexane and ethyl acetate gave 30.6 g of trichlorosulfonate.

In a three-necked flask equipped with a nitrogen introduction tube and a stirrer, 31.6 g (0.043 mol) of trichlorosulfonate, 11.4 g (0.143 mol) of neopentyl alcohol and 70 g of pyridine were taken and stirred at 0 ° C. for 12 hours. The reaction solution was diluted with toluene and washed twice with an aqueous hydrochloric acid solution. Further, the organic layer was washed with 5% aqueous sodium hydrogen carbonate solution and dried over magnesium sulfate. Recrystallization from methanol gave 28.2 g of neopentyl ester represented by the following formula (III). The NMR chart of the obtained compound is shown in FIG.

<Synthesis Example 3>
9.7 g (0.050 mol) of 9,9-dimethylfluorene and 8.00 g (0.060 mol) of aluminum chloride were placed in a three-necked flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, and 50 ml of methylene chloride was added. . After cooling the reaction solution to 5 ° C., 10.5 g (0.050 mol) of 2,5-dichlorobenzoyl chloride was added dropwise over 30 minutes. After stirring the reaction solution for 5 hours at room temperature, the reaction solution was added to ice water. The organic substance was extracted using ethyl acetate. After extraction, the organic layer was washed with an aqueous sodium hydrogen carbonate solution until neutral, and further washed with brine. Magnesium sulfate was added to the extracted solution and dried, and then the solvent was distilled off using an evaporator. Recrystallization isolation and purification were performed using a mixed solvent of hexane and ethyl acetate to obtain 16.4 g of 2- (2,5-dichlorobenzoyl) -9,9-dimethylfluorene.

In a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 18.4 g (0.05 mol) of 2- (2,5-dichlorobenzoyl) -9,9-dimethylfluorene was taken.
58.3 g (0.5 mol) of chlorosulfonic acid was added and dissolved by stirring. The reaction solution was heated to 100 ° C. in an oil bath and stirred for 10 hours. After the completion of the reaction, the reaction solution was allowed to cool to room temperature and then poured into ice water. The organics were extracted with ethyl acetate. The obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution until the washing solution became neutral, and further washed with brine. After drying with magnesium sulfate, the solvent was distilled off using an evaporator to obtain 23.4 g of a chlorosulfonated product.

  A 500 ml three-necked flask equipped with a nitrogen inlet tube and a stirrer was charged with 18.0 g (0.032 mol) of chlorosulfonated product, 5.6 g (0.064 mol) of neopentyl alcohol and 40 g of pyridine, and stirred at 0 ° C. for 12 hours. . The reaction solution was diluted with toluene and washed twice with an aqueous hydrochloric acid solution. Further, the organic layer was washed with 5% aqueous sodium hydrogen carbonate solution and dried over magnesium sulfate. Recrystallization from a mixed solvent of hexane and ethyl acetate gave 19.3 g of neopentyl ester represented by the following formula (IV).

<Example 1>
In a 1 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 62.9 g (70 mmol) of neopentyl sulfonate obtained in Example 1 and Mn of 10,500 represented by the structural formula (V)
Of hydrophobic units 44.1 g (4.2 mmol), bis (triphenylphosphine) nickel dichloride 1.94 g (3 mmol), sodium iodide 0.33 g (2.22 mmol), triphenylphosphine 7.80 g (30 mmol), 11.7 g (178 mmol) of zinc was weighed and replaced with dry nitrogen.

  N, N-dimethylacetamide (DMAc) (320 mL) was added thereto, and stirring was continued for 3 hours while maintaining the reaction temperature at 80 ° C., and then DMAc (750 mL) was added for dilution, and insoluble matters were filtered.

  The obtained solution was put into a 2 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, heated and stirred at 115 ° C., and 44 g (506 mmol) of lithium bromide was added. After stirring for 7 hours, the product was precipitated by pouring into 5 L of acetone. Subsequently, after washing with 1N hydrochloric acid and pure water in this order, it was dried to obtain 18 g of the desired sulfonated polymer. The weight average molecular weight (Mw) of the obtained polymer was 170,000. The obtained polymer is presumed to be a sulfonated polymer represented by the formula (VI). The ion exchange capacity of this polymer was 2.3 meq / g.

<Example 2>
In a 1 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 55.0 g (65.3 mmol) of neopentyl sulfonate obtained in Example 2 and Mn9 represented by the following structural formula (VII)
, 500 hydrophobic units 44.6 g (4.7 mmol), bis (triphenylphosphine) nickel dichloride 1.83 g (2.8 mmol), sodium iodide 0.32 g (2.1
mmol), 7.34 g (28 mmol) of triphenylphosphine and 11.0 g (168 mmol) of zinc were weighed and purged with dry nitrogen.

  N, N-dimethylacetamide (DMAc) (300 mL) was added thereto, and stirring was continued for 3 hours while maintaining the reaction temperature at 80 ° C. Then, DMAc (690 mL) was added to dilute, and insoluble matters were filtered.

  The obtained solution was put into a 2 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube. The mixture was heated and stirred at 115 ° C., and 17 g (196 mmol) of lithium bromide was added. After stirring for 7 hours, the product was precipitated by pouring into 5 L of acetone. Next, after washing with 1N hydrochloric acid and pure water in that order, the product was dried to obtain 70 g of the desired polymer. The weight average molecular weight (Mw) of the obtained polymer was 135,000. The obtained polymer is presumed to be a sulfonated polymer represented by the formula (VIII). The ion exchange capacity of this polymer was 2.3 meq / g.

<Example 3>
In a 1 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, 43.4 g (65.0 mmol) of the compound represented by the formula (III) obtained in Synthesis Example 3 was converted into the following structural formula (IX). Mn to show
10,500 hydrophobic units 52.6 g (5.0 mmol), bis (triphenylphosphine) nickel dichloride 1.83 g (2.8 mmol), sodium iodide 0.32 g (mmol), triphenylphosphine 7.4 g ( 28 mmol) and 11.0 g (168 mmol) of zinc were weighed and purged with dry nitrogen. Here, N, N-dimethylacetamide (DMAc)
288 mL was added and stirring was continued for 3 hours while maintaining the reaction temperature at 80 ° C. Then, 670 mL of DMAc was added for dilution, and insoluble matters were filtered.

The obtained solution was put into a 2 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, heated and stirred at 115 ° C., and 16.9 g (195 mmol) of lithium bromide was added. After stirring for 7 hours, the product was precipitated by pouring into 5 L of acetone. Next, after washing in order of 1N hydrochloric acid and pure water, it was dried to obtain 124 g of the desired sulfonated polymer. Weight average molecular weight of the obtained polymer (
Mw) was 170,000. The obtained polymer is presumed to be a sulfonated polymer represented by the formula (X). The ion exchange capacity of this polymer was 2.3 meq / g.

<Comparative Example 1>
50 g (145 mmol) of 2,5-dichloro-4′-phenoxybenzophenone was placed in a 1 L three-necked flask equipped with a condenser, a three-way cock and a thermometer, and purged with dry nitrogen. To this was added 263 g of chlorosulfonic acid, and the mixture was stirred for 3 hours while maintaining the internal temperature at 20 ° C. or lower. After completion of the reaction, the reaction solution was poured into ice water and extracted with ethyl acetate. The obtained organic layer was washed with brine until the washing solution became neutral and dried over magnesium sulfate, and then the solvent was removed to obtain 60 g of a chlorosulfonated product. Unlike Example 1, the obtained compound was a monochlorosulfonated compound.

  The obtained chlorosulfonated product was placed in a 0.5 L three-necked flask equipped with a condenser, a three-way cock and a thermometer, 75 g of pyridine was added, and the mixture was cooled to about 5 ° C. To this, 13.2 g (149 mmol) of 2,2-dimethyl-1-propanol was gradually added, followed by stirring for 4 hours under ice cooling. After completion of the reaction, the reaction mixture was diluted with toluene and washed twice with an aqueous hydrochloric acid solution. Further, the organic layer was washed with 5% aqueous sodium hydrogen carbonate solution, treated with saturated brine, and dried over magnesium sulfate. Recrystallization from methanol / hexane gave 60 g of the desired compound. The obtained compound was a compound represented by the following formula (XI).

Next, in a 1 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introducing tube, 78.1 g (121 mmol) of the compound represented by the formula (XI) obtained, [4,4 ′ having a number average molecular weight of 11,200, -Dichlorobenzophenone · 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane] polycondensate 47.8 g (4.3 mmol), bis (triphenylphosphine) Weigh 2.5 g (3.8 mmol) of nickel dichloride, 0.56 g (3.8 mmol) of sodium iodide, 13.2 g (50.2 mmol) of triphenylphosphine and 19.7 g (301 mmol) of zinc, and replace with dry nitrogen. . 295 mL of N, N-dimethylacetamide (DMAc) was added thereto, and the mixture was stirred for 3 hours while maintaining the reaction temperature at 80 ° C. Then, 300 mL of DMAc was added for dilution, and insoluble matters were filtered.

  The obtained filtrate was put into a 3 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, heated and stirred at 115 ° C., and 31.6 g (364 mmol) of lithium bromide was added. After stirring for 7 hours, the reaction solution was poured into 5 L of acetone to precipitate the product. The obtained product was washed with 1N hydrochloric acid and pure water in this order and then dried to obtain 90 g of the desired sulfonated polymer. The obtained polymer had a weight average molecular weight of 145,000 and an ion exchange capacity of 2.2 meq / g. The obtained polymer is presumed to be a sulfonated polymer represented by the following formula (XII).

<Evaluation>
Each sulfonated polymer obtained in Examples 1 to 3 and Comparative Example 1 was dissolved in NMP, and a proton conductive membrane having a thickness of 50 μm was produced by a casting method. The proton conductivity and water content of each proton conducting membrane were measured. The results are shown in Table 1.

  As shown in Table 1, the proton conducting membrane composed of the sulfonated polymer of the present invention (Examples 1 to 3) has high tensile elongation and excellent toughness even when the ion exchange capacity is increased. Since there is little weight loss due to elution in the water, it is excellent in hot water resistance.

FIG. 1 shows an NMR chart of the compound obtained in Synthesis Example 1. FIG. 2 shows an NMR chart of the compound obtained in Synthesis Example 2.

Claims (7)

An aromatic sulfonic acid ester derivative represented by the following general formula (1):

[In the formula (1), X a halogen atom except fluorine (chlorine, bromine, iodine), - indicates OSO ₂ CH ₃ and atom or a group selected from the group consisting of -OSO ₂ CF _3, Y is -CO- Or -S
Represents O ₂ —, Z represents an oxygen atom, a sulfur atom, —CO— or —SO ₂ — or —SO
-And R independently represents a hydrocarbon group having 4 to 20 carbon atoms. l represents an integer of 0 to 4, and m represents an integer of 0 or more.
Ar represents a structure represented by the following general formula (2) or (3).

In formula (2), U represents —CO— or —SO ₂ — or —SO—, n represents an integer of 0 to 4, and o represents an integer of 0 to 4. R independently represents a hydrocarbon group having 4 to 20 carbon atoms. However, l + n + o ≧ 1.
In the formula (3), V represents an oxygen atom, a sulfur atom, —CR ′ ₂ —, —CO—, —SO ₂ — or —SO—, p represents an integer of 0 to 3, and q represents 0 to 4 Indicates an integer. However, R ′ represents a hydrocarbon group having 1 to 20 carbon atoms, and R independently represents a hydrocarbon group having 4 to 20 carbon atoms. However, l + p + q ≧ 1. ] A polyarylene polymer having a structural unit represented by the following general formula (1 ′).

[In the formula (1 ′), Y represents —CO— or —SO ₂ —, and Z represents an oxygen atom, a sulfur atom, —CO—, —SO ₂ — or —SO—. l represents an integer of 0 to 4, and m represents an integer of 0 or more.
Ar represents a structure represented by the following general formula (2 ′) or (3 ′). In the formula (2 ′), U represents —CO— or —SO ₂ — or —SO—. n represents an integer of 0 to 4, and o represents an integer of 0 to 4. However, l + n + o ≧ 1. In the formula (3 ′), V represents an oxygen atom, a sulfur atom, —CR ′ ₂ —, —CO— or —SO ₂ —, p represents an integer of 0 to 3, and q represents an integer of 0 to 4. Show. However, R 'shows a C1-C20 hydrocarbon group, l + p + q> =
1. ]

Furthermore, it has a structural unit represented by General formula (4), The polyarylene-type copolymer of Claim 2 characterized by the above-mentioned.

[In Formula (4), A and D are each independently a direct bond, —O—, —S—, —CO—, —SO ₂ —.
, —SO—, —CONH—, —COO—, — (CF ₂ ) _i — (i is an integer of 1 to 10), — (CH ₂ ) _j — (j is an integer of 1 to 10) , —CR ″ ₂ — (R ″ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a halogenated hydrocarbon group), a cyclohexylidene group, or a fluorenylidene group. Shows the structure of
B independently represents an oxygen atom or a sulfur atom, and R ^{1 to} R ¹⁶ may be the same or different from each other, and are a hydrogen atom, a fluorine atom, an alkyl group, or a halogenated alkyl group in which part or all of them are halogenated. , At least one atom or group selected from the group consisting of an allyl group, an aryl group, a nitro group, and a nitrile group, s and t represent an integer of 0 to 4, and r represents an integer of 0 or 1 or more . ] The polyarylene copolymer according to claim 2 or 3, wherein the general formula (1 ') is a structural unit represented by the following general formula (1'a).

[In the formula (1′a), Z represents an oxygen atom, a sulfur atom, —CO—, —SO ₂ — or —S.
O- is shown. l represents an integer of 0 to 4, and m represents an integer of 0 or more. Ar ′ represents a structure represented by the following general formula (2′a) or (3′a).

In formula (2′a), U represents —CO— or —SO ₂ — or —SO—, n represents an integer of 0 to 4, and o represents an integer of 0 to 4. However, l + n + o ≧ 1. In formula (3′a), V represents an oxygen atom, a sulfur atom, —CR ′ ₂ — or —CO—, —SO ₂ — or —SO—, p represents an integer of 0 to 3, and q represents 0 Represents an integer of ~ 4. However, R ′ represents a hydrocarbon group having 1 to 20 carbon atoms, and 1 + p + q ≧ 1. ] The polyarylene-based copolymer according to claim 2, wherein the structural unit is a structural unit represented by the following general formulas (1′b) to (1′e).

[In the formula (1′b), Z represents an oxygen atom, a sulfur atom, —CO— or —SO ₂ — or —
Indicates SO-, U is -CO- or -SO ₂ - shows the or -SO-. l represents an integer of 0 to 4, n represents an integer of 0 to 4, and o represents an integer of 0 to 4. However, l + n + o ≧ 1.
In formula (1′c), U represents —CO— or —SO ₂ — or —SO—. n represents an integer of 0 to 4, and o represents an integer of 0 to 4. However, n + o ≧ 1.
In formula (1′d), Z represents an oxygen atom, a sulfur atom, —CO—, —SO ₂ — or —SO—, and V represents an oxygen atom, a sulfur atom, —CR ′ ₂ —, —CO— or —. S
O ₂ — or —SO— is shown. l represents an integer of 0 to 4, p represents an integer of 0 to 3, and q represents an integer of 0 to 4. However, R 'shows a C1-C20 hydrocarbon group and is l + p + q> = 1.
In formula (1′e), V represents an oxygen atom, a sulfur atom, —CR ′ ₂ —, —CO—, —SO ₂ — or —SO—. l represents an integer of 0 to 4, p represents an integer of 0 to 3, q
Represents an integer of 0 to 4. However, R 'shows a C1-C20 hydrocarbon group and it is l + p + q> = 1. ] The structural unit represented by the following general formulas (1'f) to (1'i):
Or the polyarylene-type copolymer of 3.

[In the formula (1′f), Z represents an oxygen atom, a sulfur atom, —CO— or —SO ₂ — or —
Indicates SO-, U is -CO- or -SO ₂ - shows the or -SO-. l represents an integer of 0 to 1, n represents an integer of 0 to 1, and o represents an integer of 0 to 2. However, l + n + o ≧ 1.
In the formula (1′g), U represents —CO— or —SO ₂ — or —SO—. n represents an integer of 0 to 1, and o represents an integer of 0 to 2. However, n + o ≧ 1.
In formula (1′h), Z represents an oxygen atom, a sulfur atom, —CO—, —SO ₂ — or —SO—, and V represents an oxygen atom, a sulfur atom, —CR ′ ₂ —, —CO— or —. SO ₂ — or —SO— is shown. l represents an integer of 0 to 1, p represents an integer of 0 to 1, and q represents 0.
An integer of ~ 2 is shown. However, R 'shows a C1-C20 hydrocarbon group and it is l + p + q> = 1.
In the formula (1′i), V represents an oxygen atom, a sulfur atom, —CR ′ ₂ —, —CO—, —SO ₂ — or —SO—. p represents an integer of 0 to 1, and q represents an integer of 0 to 2. However, R 'shows a C1-C20 hydrocarbon group and is p + q> = 1. A solid polymer electrolyte membrane comprising the polyarylene copolymer according to claim 3.

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