CN1318475C

CN1318475C - Polyarylidene and its preparation method, and polymer solid electrolyte and proton conductive film

Info

Publication number: CN1318475C
Application number: CNB2005100976147A
Authority: CN
Inventors: I·罗占斯奇; 高桥昌之; 后藤幸平; 今野洋助; 大月敏敬; 山川芳孝; 门田敏明
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2002-08-22
Filing date: 2003-08-22
Publication date: 2007-05-30
Anticipated expiration: 2023-08-22
Also published as: CN1737032A

Abstract

Disclosed is an aromatic sulfonic acid ester derivative represented by the formula (1); in the formula, X is an atom or a group selected from a halogen atom excluding fluorine, -OSO3CH3 and -OSO3CF3, A is a divalent electron attractive group, B is a divalent electron donating group or a direct bonding, R<a> is a hydrocarbon group of 1 to 20 carbon atoms, Ar is an aromatic group having a substituent of -SO3R<b> (wherein R<b> is a hydrocarbon group of 1 to 20 carbon atoms), m is an integer of 0 to 10, n is an integer of 0 to 10 and k is an integer of 1 to 4. Also disclosed is a process for producing a polyarylene having a sulfonic acid group, which process comprises the steps of coupling polymerization of an aromatic compound containing the derivative of the formula (1), to prepare a polyarylene and hydrolysis of the polyarylene, and which process has high safety and is easily capable of controlling the amount of sulfonoc acid group introduced into a polymer and the introducing position thereof.

Description

Polyarylene and preparation method thereof, and copolymer solid electrolyte and proton conductive membrane

Patent application of the present invention is to be on August 22nd, 2003 applying date, application number is 03155160.2, denomination of invention is the dividing an application of application for a patent for invention of " aromatic sulfonic acid ester derivative, polyarylene and preparation method thereof, and copolymer solid electrolyte and proton conductive membrane ".

Technical field

The present invention relates to the novel aromatic sulfonate derivatives, comprise polyarylene, have sulfonic polyarylene of the described polyarylene preparation of hydrolysis and preparation method thereof from the repeated structural unit of described derivative, the invention still further relates to copolymer solid electrolyte and proton conductive membrane, described ionogen comprises and contains sulfonic polyarylene, and described conducting film comprises described copolymer solid electrolyte.

Background technology

Ionogen uses with the state of (water) solution usually.But recently, described aqueous solution state replaces with solid state, and this is that described solid state has the performance of easy processing because when it being applied on the Electrical and Electronic material.And there is trend light-duty, thin, short and small-sized and that save electric energy recently.

Usually, known mineral compound and organic compound all can be used as proton conducting material.The example of described mineral compound is a uranyl phosphate, is hydrate.These mineral compound contact on its interface and insufficient, and have many problems when forming conducting film on substrate or electrode.

On the other hand, the example of described organic compound is the polymkeric substance that belongs to Zeo-karb, for example, sulfonated ethylene based polyalcohol such as sulfonic acid polystyrene, the perfluoro alkyl sulfonic acid polymkeric substance (is represented (trade(brand)name by Nafion, Do Pont Co., Ltd.)), the perfluoro carboxylic acid polymkeric substance, with by sulfonic group or phosphate are introduced thermally stable polymer (as, polybenzimidazole or polyether-ether-ketone) the middle polymkeric substance (polymerpreprints for preparing, Japan, Vol.42, No.7, PP.2490-2492 (1993), polymer preprints, Japan, Vol.43 No.3, PP.735-736 (1994), polymer preprints, Japan, Vol.42No.3, PP.730 (1993)).

But there is the relatively poor problem of chemical stability (durability degree) in sulfonated ethylene based polyalcohol such as sulfonic acid polystyrene etc.The perfluorinated sulfonic acid electrolytic film is difficult to preparation, and very expensive.For this point, be difficult to be used in the general application, as vehicle, household fuel unit etc., be only applicable to the special application that limits.After it used, also there was very big environmental problem in the perfluorinated sulfonic acid electrolytic film in waste treatment, and this is because a large amount of fluorine atoms is arranged in its molecule.Also exist hot water tolerance and the relatively poor problem of durability degree by polymkeric substance preparation in sulfonic group or phosphoric acid introducing thermally stable polymer such as polybenzimidazole, the polyether-ether-ketone etc.

On the other hand, sulfonated aromatic polymers is known to proton conducting material, is that low-cost industry is made, and has good hot water resistance energy and durability degree.Described sulfonated aromatic polymers prepares polymkeric substance by the polymerization aromatic substance usually, make the reaction of described polymkeric substance and sulphonating agent then, sulfonic group is introduced described polymkeric substance prepares.

But ordinary method has many problems, as owing to use a large amount of sulphonating agents such as the vitriol oil, oleum, chlorsulfonic acid etc. introducing sulfonic acid, and its production risk height, and industrial raw material is restricted the load height of liquid waste disposal in reclaiming polymkeric substance.And there is the problem of controlling the size and described sulfonic group being introduced the position in the polymkeric substance of being not easy in ordinary method.

Summary of the invention

The invention is intended to solve the above-mentioned problem relevant with prior art, the purpose of this invention is to provide the proton conducting material with good hot water resistance energy and durability degree, it is made with low-cost industry.

Another object of the present invention provides and is used to prepare the method with sulfonic polyarylene, described method can prepare under the condition of not using a large amount of sulphonating agents and has sulfonic polyarylene, and it is low to handle load in reclaiming polymkeric substance, is convenient to control the sulfonic amount of introducing in the described polymkeric substance and introduces the position.

Another object of the present invention provides by described method and obtains to have sulfonic polyarylene.

A further object of the present invention provides and is applicable to the described novel aromatic sulfonate derivatives with sulfonic polyarylene of preparation, and polyarylene is provided.

A further object of the present invention provides and comprises the copolymer solid electrolyte with sulfonic polyarylene, and the proton conductive membrane that comprises described copolymer solid electrolyte.

The invention provides following novel aromatic sulfonate derivatives, polyarylene, have sulfonic polyarylene and preparation method thereof, the present invention also provides copolymer solid electrolyte, proton conductive membrane and manufacture method thereof.Therefore, above-mentioned purpose of the present invention can realize.

In the present invention, polyarylene is to have the dihalide of aromatic ring or have two by-OSO by use ₃(R is CH to R ₃, CF ₃Deng) aromatic substance of group of expression is as raw material, and carry out the polymkeric substance that obtains with the direct-connected polyreaction of aromatic ring.

(1) the aromatic sulfonic acid ester derivative shown in the general formula (1);

In the formula, X be selected from halogen atom beyond the defluorination ,-OSO ₃CH ₃With-OSO ₃CF ₃Atom or group, A is divalence electrophilic (electron attRactive) group, B is the divalence electron-donating group or directly connects R ^aBe the alkyl of 1-20 carbon atom, Ar has by-SO ₃R ^bThe substituent aryl of expression, wherein, R ^bBe the alkyl of 1-20 carbon atom, m is the integer between the 0-10, and n is the integer between the 0-10, and k is the integer of 1-4.

(2) comprise polyarylene from the repeated structural unit of aromatic substance, it comprises the repeated structural unit shown in the general formula (1 ') at least;

In the formula, A is that divalence electron-withdrawing group, B are the divalence electron-donating groups or directly connect R ^aBe the alkyl of 1-20 carbon atom, Ar has by-SO ₃R ^bThe substituent aryl of expression, wherein, R ^bBe the alkyl of 1-20 carbon atom, m is the integer between the 0-10, and n is the integer between the 0-10, and k is the integer of 1-4.

(3) comprise the polyarylene of repeated structural unit shown in repeated structural unit shown in the 0.5-100 mole % general formula (1 ') and the following general formula of 0-99.5 mole % (A ');

In the formula, R ¹-R ⁸Be selected from least one atom or group in hydrogen, fluorine atom, alkyl, fluorine substituted alkyl, allyl group and the aryl in the same manner or differently, W is that divalence electron-withdrawing group, T are the divalence electron-donating groups, and P is 0 or positive integer.

(4) preparation have the method for sulfonic polyarylene, said method comprising the steps of: the described aromatic substance that comprises aromatic sulfonic acid ester derivative shown in the general formula (1) of coupling polymerization, the preparation polyarylene, and hydrolysis polyarylene.

(5) copolymer solid electrolyte, it comprises by what method (4) made and has a sulfonic polyarylene.

(6) comprise the proton conductive membrane of copolymer solid electrolyte.

On the one hand, the invention provides a kind of polyarylene, it comprises the repeated structural unit from aromatic substance, and comprises the repeated structural unit by general formula (1 ') expression at least:

In the formula, A is that divalence electron-withdrawing group, B are the divalence electron-donating groups or directly connect R ^aBe the alkyl of 1-20 carbon atom, Ar has by-SO ₃R ^bThe substituent aryl of expression ,-SO ₃R ^bIn, R ^bBe the alkyl of 1-20 carbon atom, m is the integer between the 0-10, and n is the integer between the 0-10, and k is the integer of 1-4.

One preferred embodiment, described polyarylene comprises repeated structural unit shown in the repeated structural unit shown in the 0.5-100 mole % general formula (1 ') and the 0-99.5 mole % general formula (A ');

In the formula, R ¹-R ⁸Identical or different, be at least one atom or the group that is selected from hydrogen, fluorine atom, alkyl, fluorine substituted alkyl, allyl group and the aryl, W is that divalence electron-withdrawing group, T are divalent organic groups, P is 0 or positive integer.

On the other hand, the invention provides the method that a kind of preparation has sulfonic polyarylene, said method comprising the steps of: the coupling polymerization comprises the aromatic substance of the aromatic sulfonic acid ester derivative shown in the general formula (1), preparation polyarylene, and the described polyarylene of hydrolysis:

In the formula, X be selected from halogen atom beyond the defluorination ,-OSO ₃CH ₃With-OSO ₃CF ₃Atom or group, A is the divalence electron-withdrawing group, B is the divalence electron-donating group or directly connects R ^aBe the alkyl of 1-20 carbon atom, Ar has by-SO ₃R ^bThe substituent aryl of expression ,-SO ₃R ^bIn, R ^bBe the alkyl of 1-20 carbon atom, m is the integer between the 0-10, and n is the integer between the 0-10, and k is the integer of 1-4.

Again on the one hand, the invention provides a kind of copolymer solid electrolyte, described ionogen comprises by what aforesaid method made and has a sulfonic polyarylene.

On the one hand, the invention provides a kind of fuel cell proton conductive membrane again, described film comprises above-mentioned copolymer solid electrolyte.

Description of drawings

Fig. 1 is the IR spectrum of the white powder of preparation among the embodiment 1 (1).

Fig. 2 is the NMR spectrum of the white powder of preparation among the embodiment 1 (1).

Fig. 3 is the NMR spectrum of the white powder of preparation among the embodiment 1 (1).

Fig. 4 is the IR spectrum of the white crystals of preparation among the embodiment 1 (2).

Fig. 5 is the NMR spectrum of the white crystals of preparation among the embodiment 1 (2).

Fig. 6 is the NMR spectrum of the white crystals of preparation among the embodiment 1 (2).

Fig. 7 is the IR spectrum of the white crystals of preparation among the embodiment 1 (3).

Fig. 8 is the NMR spectrum of the white crystals of preparation among the embodiment 1 (3).

Fig. 9 is the NMR spectrum of the white crystals of preparation among the embodiment 1 (3).

Figure 10 is the IR spectrum of the white crystals of preparation among the embodiment 2.

Figure 11 is the NMR spectrum of the white crystals of preparation among the embodiment 2.

Figure 12 is the NMR spectrum of the white crystals of preparation among the embodiment 2.

Figure 13 is the IR spectrum of the polyarylene of preparation among the embodiment 3.

Figure 14 is the NMR spectrum of the polyarylene of preparation among the embodiment 3.

Figure 15 is the IR spectrum of the polyarylene of preparation among the embodiment 4.

Figure 16 is the NMR spectrum of the polyarylene of preparation among the embodiment 4.

Figure 17 is the NMR spectrum of the polyarylene of preparation among the embodiment 4.

Figure 18 is the NMR spectrum of the polyarylene of preparation among the embodiment 5.

Figure 19 is the IR spectrum with sulfonic polyarylene of preparation among the embodiment 6.

Figure 20 is the NMR spectrum with sulfonic polyarylene of preparation among the embodiment 6.

Figure 21 is the IR spectrum with sulfonic polyarylene of preparation among the embodiment 7.

Figure 22 is the NMR spectrum with sulfonic polyarylene of preparation among the embodiment 7.

Figure 23 is the IR spectrum with sulfonic polyarylene of preparation among the embodiment 8.

Figure 24 is the IR spectrum of the multipolymer of preparation among the embodiment 9.

Figure 25 is the NMR spectrum of the multipolymer of preparation among the embodiment 9.

Figure 26 is the IR spectrum with sulfonic polyarylene of preparation among the embodiment 9.

Figure 27 is the NMR spectrum with sulfonic polyarylene of preparation among the embodiment 9.

Figure 28 is the NMR spectrum of the phenoxy phenyl disulfonic acid compound of preparation among the embodiment 10.

Figure 29 be among the embodiment 10 preparation 2, the NMR spectrum of 5-two chloro-4 '-(4-phenoxy phenyl) benzophenone disulfonic acid compound.

Figure 30 is the S-2 of preparation among the embodiment 10, the NMR spectrum of 5-DCPPB chloro-sulfonated compound.

Figure 31 is the S-2 of preparation among the embodiment 10, the IR spectrum of 5-DCPPB neo-pentyl ester.

Figure 32 is the S-2 of preparation among the embodiment 10, the NMR spectrum of 5-DCPPB neo-pentyl ester.

Embodiment

Below will describe aromatic sulfonic acid ester derivative, polyarylene in detail, have sulfonic polyarylene and preparation method thereof, and copolymer solid electrolyte and proton conductive membrane.

(aromatic sulfonic acid ester derivative)

Aromatic sulfonic acid ester derivative of the present invention is represented by general formula (1).

In the formula, X be selected from halogen atom (chlorine, bromine and iodine) beyond the defluorination ,-OSO ₃CH ₃With-OSO ₃CF ₃Atom or group.

A is the divalence electron-withdrawing group, its example is-CO-,-CONH-,-(CF ₂) _P-(wherein, P is an integer between the 1-10) ,-C (CF ₃) ₂-,-COO-,-SO-and-SO ₂-.

B is the divalence electron-donating group or directly connects, its example is-O-,-S-,-CH=CH-,-C ≡ C-,

With

Described electron-withdrawing group is meant that the Hammett substituent constant is not less than 0.06 group when phenyl during in position; Refer to that the Hammett substituent constant is not less than 0.01 group when phenyl during in contraposition.

R ^aIt is the alkyl of 1-20 carbon atom, be preferably the alkyl of 4-20 carbon atom, its example is a straight-chain alkyl, branched hydrocarbyl, alicyclic alkyl and alkyl with five-membered ring, as methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl, isobutyl-, normal-butyl, sec-butyl, neo-pentyl, cyclopentyl, hexyl, cyclohexyl, cyclopentyl-methyl, cyclohexyl methyl, adamantyl (adamantyl), the adamantyl methyl, the 2-ethylhexyl, two rings (2,2,1) heptyl, two rings (2,2,1) heptyl methyl, tetrahydrofurfuryl, the 2-methyl butyl, 3,3-dimethyl-2,4-diox (dioxoRane) methyl, cyclohexyl methyl, diamantane methyl and two rings (2,2,1) heptyl methyl.Wherein, preferred normal-butyl, neo-pentyl, tetrahydrofurfuryl, cyclopentyl, cyclohexyl, cyclohexyl methyl, adamantyl methyl and two ring (2,2,1) heptyl methyl, and, be more preferably neo-pentyl.

Ar has by-SO ₃R ^bThe substituent aryl of expression, exemplary aryl comprises phenyl, naphthyl, anthryl and phenanthryl (phenathyl).Wherein, preferred phenyl and naphthyl.

As for described substituting group-SO ₃R ^b, described phenanthryl has-individual or two or more substituting groups, and when it has two or more substituting group-SO ₃R ^bThe time, these substituting groups each other can be identical or different.

R ^bBe the alkyl of 1-20 carbon atom, be preferably the alkyl of 4-20 carbon atom, its example is the alkyl of an above-mentioned 1-20 carbon atom.Wherein, preferred normal-butyl, neo-pentyl, tetrahydrofurfuryl, cyclopentyl, cyclohexyl, cyclohexyl methyl, adamantyl methyl and two ring (2,2,1) heptyl methyl, and, be more preferably neo-pentyl.

M is the integer between the 0-10, is preferably 0-2, and n is the integer between the 0-10, is preferably 0-2, and k is the integer of 1-4.

The more concrete example of aromatic sulfonic acid ester derivative shown in the general formula of the present invention (1) comprises the compound shown in the following type (a)-(c).

Compound shown in the type (a)

Compound shown in the type (a) is the compound shown in the following general formula (1-a).

In the formula (1-a), X, A and R ^bHave and the identical meaning of general formula (1).

In the aromatic sulfonic acid ester derivative shown in the general formula (1-a), A is preferably-CO-or-SO ₂-.R ^bBe preferably neo-pentyl, tetrahydrofurfuryl, cyclopentyl-methyl, cyclohexyl methyl, adamantyl methyl or two ring (2,2,1) heptyl methyl, be more preferably neo-pentyl.

The example of aromatic sulfonic acid ester derivative is as follows shown in the general formula (1-a):

Other example of aromatic sulfonic acid ester derivative shown in the general formula (1-a) comprises that the chlorine atom that replaces in the above-claimed cpd with bromine atoms or iodine atom obtains compound, usefulness-SO ₂-replace in the above-claimed cpd-CO-obtains compound and replaces chlorine atom in the above-claimed cpd, and usefulness-SO with bromine atoms or iodine atom ₂-replace in the above-claimed cpd-compound that CO-obtains.

R in the general formula (1-a) ^bBase is from primary alconol.β carbon is preferably tertiary carbon or quaternary carbon, and this is because of its excellent in stability in polymerization procedure, can be because of forming sulfonic acid by de-ester reaction and suppressing polyreaction or cause crosslinked.And preferably these ester groups are from primary alconol, and the β position is a quaternary carbon.

The method that is used for compound shown in the synthesis type (a)

The sulfonation reaction of step (1) compound (I) (for example, using the method for acetylsulfuric acid and sodium hydroxide):

For example, under 60 ℃, with compound (I) 2,1 of 5-dichloro benzophenone, 1 of the acetylsulfuric acid salt of 2-dichloromethane solution and 5 moles of multiples, 2-methylene dichloride reaction 3-5 hour.After the reaction, finish reaction, and pour 3 moles of NaOH aqueous solution doubly into the 1-propyl alcohol.Concentrate gained solution, make 2,5-dichloro benzophenone-3 '-sodium sulfate fine powder.

The chlorination of step (2) compound (II) (for example, using the phosphinylidyne muriate):

For example, will be as 2 of compound (II), 5-dichloro benzophenone-3 '-sodium sulfate is dissolved in 2,5-dichloro benzophenone-3 '-sodium sulfate meter is about the doubly solvent (mixed solvent of (weight/volume) of 3-4, tetramethylene sulfone/acetyl nitrile /=H/b (volume ratio)) in, be heated to 70 ℃, and 10 ℃ down and phosphoryl chloride reacted about 5 hours.After the reaction, dilute described reactant, deposit described product with a large amount of cold water.After the filtration,, make the crystallization 2 of purifying, 5-dichloro benzophenone-3 '-sulfuric acid muriate with the described product of toluene recrystallization.

When using 5-10 mole chlorsulfonic acid doubly to replace the acetylsulfuric acid that uses in the step (1), just carry out the muriatic conversion of sulfonation so at once.

The esterification of step (3) compound (III) (for example, using the method for isopropylcarbinol):

For example, will be as 2 of compound (III), 5-dichloro benzophenone-3 '-sulfuric acid muriate is added drop-wise to 2, and 5-dichloro benzophenone-3 '-sulfuric acid muriate is counted in the mixing solutions of equivalent or more (be generally 1-3 mole doubly) refrigerative isopropylcarbinol and pyridine and reacted.Described being reflected under the highest 20 ℃ carried out.According to the scale of described reaction, the described reaction times was about 10 minutes-5 hours.Described reaction mixture is handled with dilute hydrochloric acid, and washes with water, uses the ethyl acetate extraction target product then.Concentrate described extract and separation, carry out recrystallization with methyl alcohol then, make aromatic sulfonic acid ester derivative (compound IV).

Compound shown in the type (b)

Compound shown in the type (b) is the compound shown in the following general formula (1-b).

In general formula (1-b), X, A, B, Ar and m have and the identical meaning of general formula (1).

In the aromatic sulfonic acid ester derivative shown in the general formula (1-b), B is preferably the divalence electron-donating group, has-SO ₃R ^bSubstituent Ar aryl is preferably has dinuclear or more multinuclear aryl, and R ^bBe preferably the alkyl of 3-20 carbon atom.

The preferred example of described multinuclear aryl comprises naphthyl, anthryl and phenanthryl, preferably naphthyl.

In described multinuclear aryl or have one or two or an a plurality of substituting group-SO ₃R ^bWhen there being two or more substituting groups, can be identical or different between the described substituting group.In the present invention, described compound preferably has two substituting group-SO of existence in the described polycyclic ring ₃R ^bStructure.

R ^bBe preferably sec.-propyl, normal-butyl, neo-pentyl, tetrahydrofurfuryl, cyclopentyl, cyclohexyl, cyclohexyl methyl, adamantyl methyl or two ring (2,2,1) heptyl methyl, and be preferably neo-pentyl.

M is preferably the integer between the 0-3.

The described aromatic sulfonic acid ester derivative of general formula (1-b) example is as follows:

Other example of the described aromatic sulfonic acid ester derivative of general formula (1-b) comprises compound, the usefulness-SO that replaces the chlorine atom acquisition in the above-claimed cpd with bromine atoms or iodine atom ₂-replace in the above-claimed cpd-compound that CO-obtains and replace chlorine atom in the above-claimed cpd, and usefulness-SO with bromine atoms or iodine atom ₂-replace in the above-claimed cpd-compound that CO-obtains.

R in the general formula (1-b) ^bBase is from primary alconol.β carbon is preferably tertiary carbon or quaternary carbon, and this is because of its excellent in stability in polymerization procedure, can be because of forming sulfonic acid by de-ester reaction and suppressing polyreaction or cause crosslinked.And preferably these ester groups are from primary alconol, and the β position is a quaternary carbon.

The method that is used for compound shown in the synthesis type (b)

For example, the compound shown in by the following method can synthesis type (b), compound shown in the general formula (1-b) for example, in the formula, Ar has substituting group-SO ₃R ^bNaphthyl, m is 1, promptly by the compound shown in the following general formula (1-b-1).

In the formula, A, B have and the identical meaning of general formula (1-b) with X, r and the s integer between the 0-4 of respectively doing for oneself, and satisfy r ÷ s 〉=1.

Step (1) etherification reaction:

In order to illustrate, in the presence of salt of wormwood, yellow soda ash etc., at aprotic polar solvent such as methyl-sulphoxide, N, carry out as 2 of compound (I) in N '-N,N-DIMETHYLACETAMIDE, the N-Methyl pyrrolidone etc., 5-two chloro-4 '-fluorine benzophenone and naphthols vitriolic nucleophilic substitution reaction prepare naphthalene sulfonic acid derivant thus.The example of naphthene sulfonic acid comprises beta naphthal-3,6-disulfonic acid, beta naphthal-6,8-disulfonic acid, 1-naphthols-3,6-disulfonic acid, beta naphthal-6-sulfonic acid, Neville acid and beta naphthal-7-sulfonic acid.Wherein, preferred beta naphthal-6,8-disulfonic acid.

The conversion of step (2) SULPHURYL CHLORIDE

In organic solvent such as acetonitrile, will convert it into SULPHURYL CHLORIDE as the naphthalene sulfonic acid derivant and the reactions such as phosphoryl chloride or thionyl chloride of compound (II).

Step (3) esterification

In organic solvent such as pyridine etc., will prepare aromatic sulfonic acid ester derivative (compound IV) as the SULPHURYL CHLORIDE and the alcohol reaction of compound (III).

Compound shown in the type (c)

Described type of compounds (c) is by the compound shown in the following general formula (1-c).

In formula (1-c), suppose m+n 〉=1, X, A, B, Ar, R ^a, m, n have and the identical meaning of general formula (1) with k.When n=0, Ar is a phenyl.

The example of the aromatic sulfonic acid ester derivative shown in the general formula of the present invention (1-c) comprises following compound.

Other example of aromatic sulfonic acid ester derivative shown in the general formula (1-c) comprises compound, the usefulness-SO that replaces the chlorine atom acquisition in the above-claimed cpd with bromine atoms or iodine atom ₂-replace in the above-claimed cpd-compound that CO-obtains and replace chlorine atom in the above-claimed cpd, and usefulness-SO with bromine atoms or iodine atom ₂-replace in the above-claimed cpd-compound that CO-obtains.

R shown in the general formula (1-c) ^bBase is from primary alconol.β carbon is preferably tertiary carbon or quaternary carbon, and this is because of its excellent in stability in polymerization procedure, can be because of forming sulfonic acid by de-ester reaction and suppressing polyreaction or cause crosslinked.And preferably these ester groups are from primary alconol, and the β position is a quaternary carbon.

The method of compound shown in the synthesis type (c)

By the compound of following method shown in can synthesis type (c).

Step (1) sulfonation

In order to illustrate, at room temperature, reaction makes its sulfonated products as the 4-phenoxy phenyl of compound (I) 2 hours in the vitriol oil.Use 4-phenylphenol or 4-(4-phenoxy group) phenoxy phenyl, can make corresponding sulfonated products by above-mentioned identical method.

And, can use the mixture of sulphonating agent such as anhydrous sulphonic acids, oleum, chlorsulfonic acid etc. or these sour He dioxs, acetate etc. to replace the vitriol oil to carry out sulfonation reaction.Position or the quantity that can regulate and control to introduce sulfonic acid by the sulphonating agent that uses or temperature of reaction.When separating described sulfonated products, it can be the form that does not contain sulfonic acid, and perhaps it can be neutralized into sulfonate such as sylvite, sodium salt etc. with alkali aqueous solution.

Step (2) etherificate

In order to illustrate, in the presence of salt of wormwood, carry out 5-two chloro-4 '-fluorine benzophenone and as the nucleophilic substitution reaction of the dithionate of the 4-phenoxy phenyl of compound (II) as 2 of compound (III).Aprotic polar solvent such as N,N-dimethylacetamide, methyl-sulphoxide, N-Methyl pyrrolidone, tetramethylene sulfone etc. can be used as solvent.And described reaction can be carried out smoothly by removing from the water that uses the reaction can cause the system with water azeotropic solvent (as toluene etc.) to begin to produce.Described temperature of reaction is preferably 100 ℃ of boiling points to described solvent.Using 2, during 5-two chloro-4 '-fluorine benzophenone, the fluorin radical that selective reaction specific activity cl radical is higher carries out etherificate thus.

The chlorination of step (3) sulfonic acid:

In order to illustrate, in inert solvent such as acetonitrile etc., will by above-mentioned reaction make as 2 of compound (IV), 5-two chloro-4 '-(4-phenoxy group) phenoxy group benzophenone disulfonic acid sylvite and reactions such as phosphoryl chloride or thionyl chloride change into disulfonic acid chloride with sulfonate (sylvite).

Step (4) esterification:

In order to illustrate, will be in basic solvent such as pyrimidine etc. as 2 of compound (V), 5-two chloro-4 '-(4-phenoxy group) phenoxy group benzophenone disulfonic acid chloride and various alcohol reaction with 4 or a plurality of carbon atoms make aromatic sulfonic acid ester derivative (compound VI).

(having sulfonic polyarylene)

Only by at least a at least a monomer that is selected from aromatic sulfonic acid ester derivative shown in the general formula (1) of polymerization, perhaps copolymerization is selected from least a monomer and other aromatic monomer in the described aromatic sulfonic acid ester derivative of general formula (1), be preferably at least a monomer that is selected from compound shown in the following general formula (A) and prepare polyarylene, the hydrolysis by polyarylene afterwards prepares the present invention and has sulfonic polyarylene.

In the general formula (A), R ' and R ' ' be in the same manner or differently beyond the defluorination halogen atom or-OSO ₂The compound that Z represents, wherein, Z is alkyl, fluorine substituted alkyl or aryl.The exemplary alkyl of being represented by Z is methyl and ethyl, and the example of fluorine substituted alkyl is a trifluoromethyl, and exemplary aryl is phenyl and p-methylphenyl.

R ¹-R ⁸Can be identical or different, respectively doing for oneself be selected from least a atom or group in hydrogen, fluorine atom, alkyl, fluorine substituted alkyl, allyl group and the aryl.

Exemplary alkyl is methyl, ethyl, propyl group, butyl, amyl group and hexyl, preferable methyl and ethyl.

Exemplary fluorine substituted alkyl is trifluoromethyl, perfluor ethyl, perfluoro propyl, perfluoro butyl, perfluor amyl group and perfluoro hexyl, preferred trifluoromethyl and pentafluoroethyl group.

Exemplary allyl group is a propenyl.

Exemplary aryl is phenyl and pentafluorophenyl group.

W represents the divalence electron-withdrawing group, and the example of described electron-withdrawing group comprises above-mentioned identical group.

T is a divalent organic group, and can be electron-withdrawing group or electron-donating group.The example of described electron-withdrawing group and electron-donating group is with above-mentioned identical.

P is 0 or positive integer, and maximum value is generally 100, is preferably 80.

When P=0, examples of compounds shown in the general formula (A) comprises 4,4 '-dichloro benzophenone, 4,4 '-dichloro-benzoyl aniline, two (chlorophenyl) methylene fluoride, 2, replaces the chlorine atom in these compounds and compound that the compound that makes and replace in the 4-position makes at least one halogen atom of 3-position replacement with bromine atoms or iodine atom at 2-two (4-chlorophenyl) HFC-236fa, 4-chlorinated benzene formic acid-4-chlorophenyl, two (4-chlorophenyl) sulfoxide, two (4-chlorophenyl) sulfone.

When P=1; the examples of compounds of general formula (A) expression comprises 4; 4 '-two (4-chlorinated benzene formyl) diphenyl ether; 4; 4 '-two (4-chlorinated benzene formamido group) diphenyl ether; 4; 4 '-two (4-chlorophenyl alkylsulfonyl) diphenyl ether; 4; 4 '-two (4-chlorophenyl) diphenyl ether dicarboxylic ester; 4; 4 '-two [(4-chlorophenyls)-1,1,1; 3; 3,3-hexafluoro propyl group] diphenyl ether; 4,4 '-two [(4-chlorophenyls)-1; 1; 1,3,3; 3-hexafluoro propyl group] diphenyl ether; 4,4 '-two [(4-chlorophenyl)-tetrafluoro ethyl] diphenyl ether; the chlorine atom that replaces in the above-claimed cpd with bromine atoms or iodine atom obtains compound; the compound that at least one halogen atom that replacement replaces to the 3-position in the 4-position and the compound that makes and replace in phenyl ether 4-position makes at least one halogen atom of 3-position replacement.

Other example of compound comprises 2 shown in the general formula (A), 2-two [4-(4-(4-chlorinated benzene formyl) phenoxy group) phenyl], 1,1,1,3,3,3-HFC-236fa, two [4-(4-(4-chlorinated benzene formyl) phenoxy group) phenyl] sulfone and by the compound shown in the following general formula.

Compound shown in the general formula (A) can synthesize by for example following method.

At first, for the bis-phenol that will be connected with electron-withdrawing group becomes corresponding bis-phenol an alkali metal salt, toward having the polar solvent of high-k such as N-N-methyl-2-2-pyrrolidone N-, N, add basic metal such as lithium, sodium, potassium etc. in N-N,N-DIMETHYLACETAMIDE, tetramethylene sulfone, sulfobenzide, the dimethyl sulfoxide (DMSO) etc., hydrogenated alkali metal, basic metal hydrate, alkaline carbonate etc.

Usually, basic metal is with the excessive response a little of Pyrogentisinic Acid's hydroxyl, and usually with 1.1-2 equivalent multiple, is preferably 1.2-1.5 equivalent multiple and uses.In this step, with water azeotropic solvent such as benzene,toluene,xylene, hexane, hexanaphthene, octane, chlorobenzene, diox, tetrahydrofuran (THF), methyl-phenoxide, phenyl ethyl ether etc. in the presence of, the aromatics dihalide compound that reaction replaces with halogen atom such as fluorine, chlorine etc., described compound is activated by electron-withdrawing group.The example of described aromatics dihalide compound is 4,4 '-difluoro benzophenone, 4,4 '-dichloro benzophenone, 4,4 '-chlorine fluorine benzophenone, two (4-chlorophenyl) sulfone, two (4-fluoro phenyl) sulfone, 4-fluoro phenyl-4 '-chlorophenyl sulfone, two (3-nitro-4-chlorophenyl) sulfone, 2,6-dichlorophenyl nitrile, 2,6-difluorophenyl nitrile, phenyl-hexafluoride, decafluorobiphenyl, 2,5-difluoro benzophenone, 1,3-two (4-chlorinated benzene formyl) benzene etc.With regard to reactive behavior, preferably use fluorine cpd.But, with regard to following aromatics coupled reaction, must arrange nucleophilic aromatic substitution reaction, making described end is the chlorine atom.With every mole of bis-phenol 2-4 mole doubly, be preferably 2.2-2.8 mole amount doubly and use described active aromatics dihalide.Before described nucleophilic aromatic substitution reaction, described bis-phenol can be pre-formed an alkali metal salt of bis-phenol.Described temperature of reaction is 60-300 ℃, is preferably 80-250 ℃.The described reaction times is 15 minutes-100 hours, is preferably 1-24 hour.

Described most preferred method comprises the chlorine fluorine compound of use as active aromatics dihalide, the end of described compound has the different halogen atom of reactive behavior separately, this is because fluorine atom preferentially causes the nucleophilic substitution reaction with phenates, makes it be suitable for obtaining described compound with directed activation chlorine end group.

In general formula, W is described identical with general formula (A).

And, as described in JP-A-2 (1990)-159, existing to be used for the synthetic method that comprises the plasticization compound of directed electron-withdrawing group and electron-donating group, described method is undertaken by comprehensive nucleophilic substitution reaction and electrophilic substitution reaction.

Particularly, with electron-withdrawing group activatory aromatics dihalide, for example (4-chlorophenyl) sulfone and phenol carry out nucleophilic substitution reaction and prepare the hexichol oxy substituents.Afterwards, this substituting group and chlorination 4-chloro-benzoic acid carry out the Friedel-CRafts reaction, make target compound.Above-claimed cpd can be applicable to used herein through electron-withdrawing group activatory aromatics dihalide.Though, can replace described oxybenzene compound, from thermotolerance and flexural property, preferred described unsubstituted oxybenzene compound.Preferred described an alkali metal salt carries out the phenol substitution reaction, and the suitable example of alkali metal compound used herein comprises above-mentioned compound.Described alkali metal compound uses with the amount of per 1 moles of phenol 1.2-2 mole multiple.In described reaction, can use above-mentioned polar solvent or and water azeotropic solvent.The hexichol oxycompound is at the Friedel-CRafts reacting movable agent, for example Lewis acid as aluminum chloride, boron tribromide, zinc chloride etc. exist time and as described in as the chlorination chloro benzoic acid of acylating reagent.Described chlorination chlorinated benzene formic acid with every mole of hexichol oxycompound 2-4 mole doubly is preferably 2.2-3 mole amount doubly and uses.Described Friedel-CRafts reacting movable agent uses as the benzoic 1.1-2 equivalent of the chloro multiple that uses as acylating reagent with per 1 mole of activation muriate.The described reaction times is 15 minutes-10 hours, the described reaction times is-and 20-80 ℃.Solvent used herein comprises chlorobenzene, oil of mirbane etc., and reaction does not have activity to Friedel-CRafts for they.

And, the compound shown in the general formula (A) comprise by chemical combination bis-phenol and at least a being selected from＞C=O ,-SO ₂-and＞C (CF ₃) ₂Electron withdrawing group W and the compound that makes, described bis-phenol provides the ether oxygen as electron-donating group T, in the general formula (A), P is 2 or bigger.Particularly, at polar solvent such as N-N-methyl-2-2-pyrrolidone N-, N, N-N,N-DIMETHYLACETAMIDE, tetramethylene sulfone etc. exist down, the an alkali metal salt that makes bis-phenol is as 2,2-two (4-hydroxy phenyl)-1,1,1,3,3,3-HFC-236fa, 2,2-two (4-hydroxy phenyl) acetone, 2,2-two (4-hydroxy phenyl) sulfones etc. and excessive active aromatic halide are as 4, and 4-benzophenone of dichloro, two (4-chlorophenyl) sulfone carries out substitution reaction, prepares described compound with the polymerization of above-mentioned described monomer synthetic method afterwards.

The example of these compounds comprises the compound shown in the following general formula.

In following formula, q is 2 or bigger integer, is preferably 2-100.

Polyarylene of the present invention comprises the repeated structural unit from aromatic monomer, and it comprises the repeated structural unit shown in the following general formula (1 ') at least.

In general formula (1 '), A, B, R ^aWith Ar be with general formula (1) in the identical group of group, and m, n are also described identical with general formula (1) with k.

Except general formula (1 '), constitute the repeated structural unit of polyarylene of the present invention, for example, shown in general formula (A ').The repeated structural unit of the formation polyarylene of the present invention except general formula (1 ') is by general formula (A ') expression.

In general formula (A '), R ¹-R ⁸, W and T be with general formula (A) in identical atom or the group of group, P also be with general formula (A) in identical numeral.

The content ratio of the repeated structural unit shown in the general formula (1 ') that comprises in the polyarylene of the present invention is not particularly limited, and is preferably 0.5-100 mole %, is more preferably 10-99.999 mole %.And the content ratio of repeated structural unit is preferably 0-99.5 mole % shown in the general formula that comprises in the polyarylene of the present invention (A '), is more preferably 0.001-90 mole %.

(synthesizing of polyarylene)

By at least a monomer that is selected from by the aromatic sulfonic acid ester derivative shown in the general formula (1) of reaction in the presence of catalyzer, at least a monomer and the 0-99.5 mole % that is selected from the aromatic sulfonic acid ester derivative shown in the general formula (1) that perhaps make 0.5-100 mole % in the presence of catalyzer, is more preferably 10-99.999 mole %, other aromatic monomer that is preferably 0.001-90 mole % are preferably and at least aly are selected from the compound shown in the general formula (A) and prepare polyarylene of the present invention.Used catalyzer is the catalyst system that comprises transistion metal compound in the reaction.Described catalyst system comprises (1) transition metal salt and part with compound (hereinafter referred to as " part component ") or have transition metal complex (comprising mantoquita) and (2) reductive agent and the optional salt that is used to improve rate of polymerization of coordination valence part.

The example of described transition metal salt comprises nickel compound such as nickelous chloride, nickelous bromide, nickelous iodide and acetopyruvic acid nickel, palladium compound such as Palladous chloride, palladium bromide and palladium iodide, iron cpd such as iron(ic) chloride, iron bromide and ferric iodide and cobalt compound such as cobalt chloride, cobaltous bromide and cobaltous iodide.Wherein, preferred nickelous chloride and nickelous bromide.

The example of described part component comprises triphenylphosphine, 2,2 '-two pyridines, 1,5-cyclooctadiene, 1,3-two (diphenylphosphino) propane etc.Wherein, triphenylphosphine and 2,2 '-two pyridines.The compound that more than is used for the part component can use separately or both or many persons mix use.

And, the transition metal complex of described coordination valence part comprises that nickelous chloride closes two (triphenylphosphines), nickelous bromide and closes two (triphenylphosphines), nickelous iodide and close that two (triphenylphosphines), nickel oxide close two (triphenyl is seen), nickelous chloride closes 2,2 '-two pyridines, nickelous bromide close 2,2 '-two pyridines, nickelous iodide close 2,2 '-two pyridines, nickel oxide close 2,2 '-two pyridines, two (1, the 5-cyclooctadiene) nickel, four (triphenylphosphine) nickel, four (triphenyl phosphorous acid) nickel, tetrakis triphenylphosphine palladium etc.Wherein, preferred nickelous chloride closes two (triphenylphosphines) and nickelous chloride closes 2,2 '-two pyridines.

The reductive agent that uses in above-mentioned catalyst system comprises for example iron, zinc, manganese, aluminium, magnesium, sodium, calcium etc.Wherein, preferred zinc, magnesium and manganese.These reductive agents activate by described reductive agent contact acid such as organic acid are waited further.

The salt that uses in the above-mentioned catalyst system comprises sodium compound such as Sodium Fluoride, sodium-chlor, Sodium Bromide, sodium iodide and sodium sulfate, potassium compound such as Potassium monofluoride, Repone K, Potassium Bromide, potassiumiodide and vitriolate of tartar, and ammonium compound is as fluoridizing tetraethyl ammonium, etamon chloride, tetraethylammonium bromide, iodate tetraethyl ammonium and sulfuric acid tetraethyl ammonium.Wherein, preferred Sodium Bromide, sodium iodide, Potassium Bromide, tetraethylammonium bromide and iodate tetraethyl ammonium.

As for the ratio of used each component, in 1 mole of described monomeric total amount, described transition metal salt or transition metal complex consumption are the 0.0001-10 mole, are preferably the 0.01-0.5 mole.When its amount was lower than 0.0001 mole, described polyreaction can not fully be carried out sometimes, and on the other hand, when its amount surpassed 10 moles, its molecular weight reduced sometimes.

In described catalyst system, when using described transition metal salt and part component, in 1 mole of transition metal salt, the consumption of described part component is generally the 0.1-100 mole, is preferably the 1-10 mole.When its amount was lower than 0.1 mole, described catalyst activity was also insufficient sometimes, and on the other hand, when its amount was lower than 100 moles, its molecular weight reduced sometimes.

In 1 mole of described monomeric total amount, the amount of used reductive agent is generally the 0.1-100 mole, is preferably the 1-10 mole.When its amount was lower than 0.1 mole, described polyreaction can not fully be reacted sometimes, and on the other hand, when it surpassed 100 moles, the purifying of resulting polymers was just too difficult sometimes.

In addition, when using salt, in 1 mole of described monomeric total amount, its amount is generally the 0.001-100 mole, is preferably the 0.01-1 mole.When its amount was lower than 0.001 mole, the effect that improves polymerization rate was just insufficient sometimes.On the other hand, when its amount surpassed 100 moles, the purifying of resulting polymers was just too difficult sometimes.

Polymerization solvent used herein comprises tetrahydrofuran (THF), hexanaphthene, dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, v-butyl lactone (butylolactone), tetramethylene sulfone, v-butyl lactan, methylimidazole ketone, 4-methyl urea etc.Wherein, preferred tetrahydrofuran (THF), N, dinethylformamide, N,N-dimethylacetamide and N-N-methyl-2-2-pyrrolidone N-.These polymer solvents are suitable thorough drying before using.

The whole monomeric concentration that comprises in polymer solvent is generally 1-90 weight %, is preferably 5-40 weight %.

And the polymerization temperature in polyreaction is generally 0-200 ℃, is preferably 50-120 ℃.Described polymerization time is generally 0.5-100 hour, is preferably 1-40 hour.

By this way, at least a monomer that is selected from by the aromatic sulfonic acid ester derivative of general formula (1) expression of (copolymerization) polymerization, perhaps at least a monomer and at least a monomer that is selected from the compound of general formula (A) expression that is selected from the aromatic sulfonic acid ester derivative of general formula (1) expression of copolymerization makes the polymeric solution that comprises polyarylene.

The molecular weight of the polyarylene that makes thus, i.e. weight-average molecular weight with regard to polystyrene, (GPC) is measured as 10000-1000000 by gel permeation chromatography, is preferably 20000-800000.

(having sulfonic polyarylene)

By the hydrolysis reaction of above-mentioned polyarylene, with the sulfonate ester group (SO in the repeated structural unit shown in the general formula (1 ') ₃R ^a,-SO ₃R ^b) change into sulfonic group (SO ₃H), prepare the present invention and have sulfonic polyarylene.

Exemplary hydrolysis reaction package is drawn together:

(1) above-mentioned polyarylene is introduced in the excessive water or alcohol, stirred then 5 minutes or above method, described water and each self-contained a spot of hydrochloric acid of alcohol.

(2) under about 80-120 ℃ temperature, above-mentioned polyarylene 5-10 hour method of reaction in trifluoroacetic acid,

(3) under about 80-150 ℃ temperature, reaction is above-mentioned polyarylene 3-10 hour in solution, and adds the method for hydrochloric acid afterwards, with 1 mole of contained in the polyarylene described sulfonic group (SO ₃R ^a,-SO ₃R ^b) meter, described solution comprises the lithiumbromide of 1-3 mole multiple, and described solution for example is N-Methyl pyrrolidone solution.

The sulfonic polyarylene that has that makes thus has 0.5-3meq/g, is preferably the sulfonic acid of 0.8-2.8meq/g.When its amount is lower than 0.5meq/g, can not increase its proton conductive performance, on the other hand, when its amount surpasses 3meq/g, its wetting ability improves, and the gained polyarylene is water-soluble, even perhaps water insoluble, it can be dissolved in hot water, and, even water insoluble, but its durability degree can reduce.

By changing the ratio of described aromatic sulfonic acid ester derivative (1) and compound (A), and the kind that changes monomer and composition thereof again can easily be controlled described sulfonic amount.

From by infrared absorption spectrum at 1230-1250cm ^-1The place the C-O-C absorption value or at 1640-1660cm ^-1The C=O absorption value at place can confirm to have the structure of the polyarylene of sulfonic acid, and, can also from NMR (Nuclear Magnetic Resonance) spectrum ( ¹H-NMR) determine at the peak of 6.8-8.0ppm place aromatics proton.

In the present invention, preferred polyarylene contained 90% or above sulfonic group (SO ₃R ^a,-SO ₃R ^b) change into sulfonic group (SO ₃H).

(copolymer solid electrolyte)

Copolymer solid electrolyte of the present invention comprises and has above-mentioned sulfonic polyarylene.

Copolymer solid electrolyte of the present invention is applicable to for example galvanic cell ionogen, secondary cell electrolysis matter, fuel cell proton conductive membrane, display element, various transmitter, signal transmission medium, solid capacitor, ion-exchange membrane etc.

(proton conductive membrane)

Proton conductive membrane of the present invention comprises and has sulfonic polyarylene.Prepare the described proton conductive membrane from having sulfonic polyarylene, have the sulfonic polyarylene, also can use mineral acid such as sulfuric acid, phosphoric acid etc. simultaneously, comprise the organic acid of carboxylic acid and suitable quantity of water except described.

In the present invention, described have sulfonic polyarylene and be dissolved in the solvent, and preparation solution by in the casting impouring substrate, and is molded as film by film forming casting process with the solution of gained, and prepares described proton conductive membrane thus.In this case, described substrate is not particularly limited, as long as it can be used for common solution casting method.For example, use plastics or metal base, the substrate that should use thermoplastic resin to make is as polyethylene terephthalate (PET) film.

The described solvent that can dissolving has a sulfonic polyarylene comprises aprotic polar solvent such as N-N-methyl-2-2-pyrrolidone N-, N, dinethylformamide, ν-butyl lactone, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), dimethyl urea, methylimidazole ketone etc., from solubleness and soltion viscosity, especially preferred N-N-methyl-2-2-pyrrolidone N-(hereinafter referred to as " NMP ").Described aprotic polar solvent can use separately or both or above mixing are used.

As for dissolving solvent, can use the mixture of above-mentioned aprotic polar solvent and alcohol with sulfonic polyarylene.The example of described alcohol comprises methyl alcohol, ethanol, propyl alcohol, Virahol, sec-butyl alcohol, tertiary butyl alcohol etc., and especially preferred is methyl alcohol, and this is because have the effect that reduces described soltion viscosity in the compositing range of wide region.Described alcohol can use separately or both or above mixing are used.

Though soltion viscosity depends on molecular weight or the polymer concentration with sulfonic polyarylene, soltion viscosity is generally 2000-100000mPas, is preferably 3000-50000mPas.When soltion viscosity was lower than 2000mPas, the retentivity of described solution in film formation process was just poor, flows down from substrate sometimes.On the other hand, when it surpassed 100000mPas, viscosity was too high, therefore can not extrude from the mold die orifice, and be difficult to sometimes form film by casting.

When using high boiling solvent as casting solvent, the film that makes in the above described manner has a large amount of residual solvents sometimes, but when the gained green film was immersed in the water, solvent contained in the described green film can be replaced by water, can reduce solvent residual in the gained film like this.

The Application Example that described green film is immersed in the method in the water can be that sheet is immersed in the discontinuous method in the water and will (for example obtaining substrate film usually; what PET) go up to form is membranaceous laminated film, perhaps isolating film immersion air-dry then continuation method water from substrate.

The preferred discontinuous method that uses, this is the film after the described processing to be installed in the processing in the frame because it can suppress and the fold that forms at described film surface.

Described green film should be not less than 10 weight parts with the green film of per 1 weight part, and the contact ratio that is preferably 30 weight parts is immersed in the water.Preferably keep its contact ratio as wide as possible, to reduce residual quantity of solvent in the gained proton conductive membrane.And, in order to be reduced in quantity of solvent residual in the gained proton conductive membrane effectively, can change water used in dipping, perhaps the concentration of organic solvent in the water is remained under the fixed concentration or by overflow and reduce.In order to suppress the horizontal distribution of residual organic solvent in the described proton conductive membrane effectively, can wait by stirring to make in the water concentration of organic solvent even.

The dried thick 10-100 micron that is generally of described proton conductive membrane by the preparation of this method is preferably the 20-80 micron.

In addition, in the present invention, under the condition that is not hydrolyzed, polyarylene is molded as film, is hydrolyzed with above-mentioned identical method afterwards, and also can prepare the described proton conductive membrane that comprises thus with sulfonic polyarylene by aforesaid method.

Aromatic sulfonic acid ester derivative of the present invention and polyarylene can be used for above-mentioned polyarylene with sulfonic acid and preparation method thereof.

Embodiment

The following non-limiting example of hereinafter with reference describes the present invention in detail.

In an embodiment, carry out the measurement of sulfonic acid base unit weight, proton conductive and thermolysis starting temperature with the following methods, and tensile strength performance, hot water resistance and to the evaluation of the tolerance of Fenton reagent.

Measure sulfonic amount

Water thorough washing gained has sulfonic polyarylene, up to washing water neutrality, removes residual free acid, and carries out drying.The products therefrom of weighing specified amount, and be dissolved in the THF/ water mixed solvent, and use phenolphthalein to carry out titration as indicator and NaOH standardized solution, measure the amount of sulfonic acid by the point of neutralization.

Measure proton conductive

By (φ=0.5mm) is fixed on the surface of band shape cutting film that width is 5mm, and sample is remained in the device of steady temperature and constant humidity, and measures the resistance that exchange current is determined in exchange current impedance between the described platinum line with the platinum line.That is be impedance under the 10KHz, measuring at exchange current under the condition of the following stated.Use the device of chemical impedance measuring system (by NF circuit design block Co., Ltd. makes), and use the JW241 that makes by Yamato Scientific Co.Ltd. device as steady temperature and constant humidity as measuring resistance.Fix 5 platinum lines with the spacing of 5mm, the distance between the described lead-in wire becomes 5-20mm, measures the resistance of described exchange current.The resistivity of described film is calculated by the distance of described lead-in wire and the gradient of resistance, and the impedance of described exchange current is calculated by the inverse of resistivity, and described proton conductive is calculated by this impedance.

Resistivity R (gradient between (cm) * film thickness (cm) * resistance wire of Ω/cm)=0.5 (Ω/cm)

Tensile strength performance

Prepare the banded cutting of one 3mm * 65mm film sample, use tensile testing machine to measure Young's modulus, breaking tenacity and extensibility.

The hot water tolerance test

Film is cut into 2.0cm * 3.0cm rectangle and weighs, prepare the test testing plate.This film places the polycarbonate bottles of 250ml, the about 100ml distilled water of past wherein adding, and applying pressure pot trier is (by HIR ^AThe PC-242HS that YAMA MFS CORP makes) heated 24 hours down at 120 ℃.Finish after the described test, from hot water, take out each film, and the water that exists on the wipe surfaces gently with KIMWIPE (trade(brand)name).Weighing contains the film weight of water, determines water-content.And, measure the yardstick of described film, determine the degree of exapnsion.In addition, used the dry this film of Vacuumdrier 5 hours, thus with the water evaporate to dryness, then, the film of preparation is determined residual weight after the weighing hot water test.

The test of Fenton reagent tolerance

Film is cut into 3.0cm * 4.0cm rectangle and weigh, prepare the test testing plate.This thin film dipped in the distilled water of 200ml 48 hours, contained residual solvent in the wash-out film thus.In this step, distilled water is changed twice.After water retting, described film is stacked with strainer, extracts the water that exists on the described surface thus, then with described film air dried overnight with weigh.

With commercially available 30% superoxol of distilled water diluting, the superoxol of preparation 3%.In described solution, add the ferrous sulfate heptahydrate, and dissolving, making Fe (II) ion is 20ppm, prepares Fenton reagent thus.In this solution impouring of 200ml 250ml polyester bottles, use heating in water bath and remain on 45 ℃.The temperature of determining described solution is added to each film in the described bottle, and heated 26 hours after 45 ℃.After 26 hours, from solution, take out solid and air dried overnight.The described solid weight of weighing, the gravimetry residual value.

Heat decomposition temperature

The decomposition temperature with sulfonic polyarylene (under nitrogen atmosphere, 20 ℃/minute temperature rising speed) that to measure with TGA (thermogravimetric analysis) is as heat decomposition temperature.

Embodiment 1

(1) preparation 4-[4-(2, the 5-dichloro-benzoyl) phenoxy group] sodium salt (A-SO of Phenylsulfonic acid ₃Na)

In the three-necked flask that agitator and prolong are housed, add 2,5-two chloro-4 '-phenoxy group benzophenone (A, 137.3g 400mmol), add 500ml1 afterwards, and the 2-ethylene dichloride (1,2-DCE) also dissolving.In addition, under agitation in described solution, add by 56ml concentrated vitriol, 152ml diacetyl oxide and 400ml1, the freshly prepd 2M acetylsulfuric acid of 2-DCE, and in 60 ℃ oil bath, reacted 3 hours.After fixed time, come stopped reaction by adding the 30ml1-propyl alcohol.Afterwards, concentrating described reaction soln is 400ml up to volume, adds the NaOH aqueous solution (120g (3 moles)/water 400ml) then.Steam 1 in the solution by azeotropic, 2-DCE cools off the transparent pale yellow solution of gained then, obtains settling, and the settling of filter deposition.At 70 ℃ of described settlings of following vacuum-drying, make 4-[4-(2, the 5-dichloro-benzoyl) phenoxy group thus] sodium salt (A-SO of Phenylsulfonic acid ₃Na) white fine powder end.Described coarse crystallization is used to not have the following steps of purifying.As for the gained white powder, in Fig. 1, represented IR spectrum, and the expression in as 2 and 3 of described NMR spectrum.

(2) preparation 4-[4-(2, the 5-dichloro-benzoyl) phenoxy group] Phenylsulfonic acid chlorine (A-SO ₂Cl)

Toward 215g (about 400ml) A-SO ₃Add 300ml acetonitrile and 200ml tetramethylene sulfone in the coarse crystallization of Na as solvent, and add phosphinylidyne trichlorine (245.3g, 1.6 moles) again, then, react the acquisition reaction mixture down at 70 ℃.And toward wherein adding 5mlN, the N-N,N-DIMETHYLACETAMIDE 71-73 ℃ of yellow suspension that stirs gained down 40 minutes, is cooled to 3 ℃ then.Add the 1L water coolant in described suspension, its adding speed makes the temperature of described reactive system be no more than 10 ℃.Collect the gained settling, use cold water washing, and carry out recrystallization, make 153g target white crystals A-SO with 350ml toluene ₂Cl, fusing point are 130.5-131.5 ℃ (with A be 87% for the benchmark productive rate).Fig. 4 has shown IR spectrum, and Fig. 5 and 6 has shown NMR spectrum.

(3) preparation 4-[4-(2, the 5-dichloro-benzoyl) phenoxy group] Phenylsulfonic acid isobutyl ester (A-SO ₃Iso-Bu)

Under mechanical stirring, under cooling, (4.0g 55mmol) He in the 30ml pyridine drips 22.09g (50mmol) A-SO toward 2-methyl isophthalic acid-propyl alcohol in 40 minutes ₂Cl.As a result, make dense suspension, and, continuously stirring 1 hour again under 12-15 ℃.Disposable adding 30ml concentrated hydrochloric acid and 100g frozen water in the described suspension.Stir described suspension, make it become even gradually.Afterwards, filter the suspension of described homogeneous rapidly with the Buchner funnel.Reclaim white thickness settling.Described settling is dissolved in once more in the ethyl acetate of 300ml, and washs by the separating funnel water.With dried over mgso gained organic layer, and under reduced pressure, steam described solvent.After concentrating, light yellow oily liquid is dissolved in the hot hexane of 30ml, and rests in the refrigerator chamber several days, obtain the target white crystals A-SO of 16.67g ₃Iso-Bu, its fusing point are 73-74 ℃, and productive rate is 70%.Fig. 7 shows IR spectrum, and Fig. 8 and 9 has shown NMR spectrum.

Embodiment 2

Preparation 4-[4-(2, the 5-dichloro-benzoyl) phenoxy group] Phenylsulfonic acid peopentyl ester (A-SO ₃Neo-Pe)

Under mechanical stirring, under cooling, toward 2, (4.85g 55mmol) with in the 30ml pyridine drips identical A-SO to 2-dimethyl-1-propyl alcohol in 40 minutes ₂Cl (22.09g, 50mmol).As a result, make dense suspension, and under 12-15 ℃ continuously stirring 1 hour again.

Make the reaction of described suspension and 30ml concentrated hydrochloric acid and 100g frozen water, produce settling.Collect described settling by filtering,, make it then to contact with 150ml ebullient toluene with cold water washing and dry.(its great majority are A-SO by removing by filter insoluble component ₃The pyridinium salt of H), and concentrates described filtrate, preparation 40ml concentrated solution.Described concentrated solution is rested in the refrigerator chamber deposition white crystals A-SO ₃Neo-Pe (fusing point: 112.0-112.5 ℃).Its amount is 16.92g, and productive rate is 69%.Figure 10 shows IR spectrum, and Figure 11 and 12 has shown NMR spectrum.

Synthetic embodiment 1

Preparation oligopolymer (being called " BCPAF oligopolymer ")

Toward the 1L three-necked flask adding 67.3g (0.20 mole) 2 that agitator, thermometer, prolong, Dean-Stark pipe is housed and is used to introduce the Y-tube of nitrogen, 2-two (4-hydroxy phenyl)-1,1,1,3,3,3-HFC-236fa (bisphenol AF), 60.3g (0.24 mole) 4,4 '-dichloro benzophenone (4,4 '-DCBP), 71.9g (0.52 mole) salt of wormwood, 300mlN, N-N,N-DIMETHYLACETAMIDE (DMAc) and 150ml toluene react in nitrogen atmosphere under 130 ℃ of heating, stir in oil bath simultaneously.Carry out described reaction,, from system, remove by the Dean-Stark pipe up to water and the methylbenzene azeotropic that reaction produces.After reaction in about 3 hours, almost can't see the generation of water.After this, when temperature of reaction is increased to 150 ℃ gradually, remove most toluene, then 150 ℃ of following successive reactions 10 hours.After reacting 10 hours, add 10.0g (0.040 mole) 4,4 '-DCBP continues reaction 5 hours again.The gained reaction soln is left standstill cooling, remove by filter the deposition mineral compound as by product of generation then, and filtered liquid is introduced in the 4L methyl alcohol.Described sedimentation products is collected by filtering, and drying also is dissolved in the 300ml tetrahydrofuran (THF).Described solution is deposited in the 4L methyl alcohol again, makes the subject polymer (productive rate 85%) of 95g.

The weight-average molecular weight of resulting polymers is measured as 12500 by GPC (THF solvent) with regard to polystyrene.And described polymkeric substance is dissolved in THF, NMP, DMAc and the tetramethylene sulfone, and Tg is 110 ℃, and heat decomposition temperature is 498 ℃.

Resulting polymers is the oligopolymer (" BCPAF " oligopolymer hereinafter referred to as) of following general formula (I) expression.

Synthetic embodiment 2

Preparation oligopolymer (being called " BCPFL oligopolymer ")

Except using 80.6g (0.23 mole) 9,9-two (4-hydroxy phenyl) fluorine (FLBP) replaces 67.3g (0.20 mole) 2,2-two (4-hydroxy phenyl)-1,1,1,3,3,3-HFC-236fa (bisphenol AF), and replace DMAc as outside the solvent with NMP, repeat synthetic embodiment 1 described step, react and aftertreatment.As a result, obtain the subject polymer of 103g.(productive rate: 83%).

The weight-average molecular weight of resulting polymers is measured as 12300 by GPC (THF solvent) with regard to polystyrene.And described polymkeric substance is dissolved among THF, NMP and the DMI, and Tg is 175 ℃, and heat decomposition temperature is 524 ℃.

Resulting polymers is the oligopolymer (" BCPFL " oligopolymer hereinafter referred to as) of following general formula (II) expression.

The polyreaction of polyarylene

Embodiment 3

Preparation has polyarylene (the poly-AB-SO as the isobutyl-of protecting group ₃I-Bu)

Under nitrogen atmosphere, toward 15.34g (32mmol) ASO of embodiment 1 preparation ₃10.52g (1.33mmol) BCPAF oligopolymer, 0.65g (1mmol) Ni (PPH that-isobutyl-, synthetic embodiment 1 make ₃) ₂Cl ₂, 33.50g (13.33mmol) PPh ₃, 0.65g (4.83mmol) NaI and 5.45g (83.33mmol) zinc powder dirt mixture in add the dry N-Methyl pyrrolidone (NMP) of 60ml.

Under agitation condition, heat described reaction mixture (finally being heated to 74 ℃), and reacted 3 hours.In reaction process, observe the viscosity in the described reaction soln raise.Dilute described polymeric reaction solution with 250mlTHF, stirred 30 minutes, and use Celite (TM John-Manville is as filtering auxiliary) to filter.In the 1500ml methyl alcohol that described filtered liquid impouring is excessive, condense thus.By filter collecting the coagulum of gained, and air-dry, and dissolving once more in THF/NMP (200ml/30ml) is condensed and is deposited by excessive 1500ml methyl alcohol.The coagulum of Chu Liing is air-dry thus, and heat drying makes 20.54g and (gathers AB-SO with the yellow laminar polymkeric substance of the target of the sulfonic acid of isobutyl-protection then ₃I-Bu) (productive rate is 78%).

With regard to polystyrene, the number-average molecular weight that is recorded described polymkeric substance by GPC (THF solvent) is 13200, and weight-average molecular weight is 33300.Figure 13 has shown IR spectrum, and Figure 14 has shown NMR spectrum.

Embodiment 4

Preparation has polyarylene (the poly-AB-SO as the neo-pentyl of protecting group ₃Neo-Pe)

Use 39.46g (98.33mmol) ASO of embodiment 2 preparations ₃18.70g (0.167mmol) BCPAF oligopolymer, 1.96g (0.30mmol) Ni (PPH that-neo-pentyl, synthetic embodiment 1 make ₃) ₂Cl ₂, 10.49g (4.00mmol) PPH ₃, the NMP that does of 0.45g (0.30mmol) NaI, 15.69g (24.00mmol) zinc powder and 129ml, carry out described polyreaction by embodiment 3 described identical steps.After beginning polyreaction 60 minutes, observe described reaction soln medium viscosity and raise.Proceed described polyreaction 3 hours.Afterwards, described polymeric reaction solution dilutes with THF, carries out aftertreatment afterwards.The result makes the target yellow fibers shape multipolymer of 47.0g with the sulfonic acid of neo-pentyl protection.(poly-AB-SO ₃Neo-Pe) (productive rate: 92%).

With regard to polystyrene, the number-average molecular weight that is recorded described polymkeric substance by GPC (THF solvent) is 53700, and weight-average molecular weight is 187000.Figure 15 has shown IR spectrum, and Figure 16 and 17 has shown NMR spectrum.

Embodiment 5

Use the BCPFL oligopolymer of synthetic embodiment 2 preparations of 7.62g (0.62mmol) to replace the used BCPAF oligopolymer of 4.88g (0.62mmol) embodiment 4, and use the A-SO of 17.81g (44.38mmol) embodiment 2 preparations ₃Neo-Pe, 0.88g (1.35mmol) Ni (PPH ₃) ₂Cl ₂, 4.72g (18.00mmol) PPH ₃, the NMP that does of 0.20g (1.35mmol) NaI, 7.06g (108.00mmol) zinc powder and 60ml, carry out described polyreaction and aftertreatment with embodiment 4 described identical steps.

As a result, make the target yellow fibers shape multipolymer of 21.0g with the sulfonic acid of neo-pentyl protection.(poly-AB-SO ₃Neo-Pe) (productive rate: 77%).

With regard to polystyrene, the number-average molecular weight that is recorded described polymkeric substance by GPC (THF solvent) is 22100, and weight-average molecular weight is 90800.Figure 18 has shown IR spectrum.

Change into by hydrolysis and to have sulfonic polyarylene

Embodiment 6

To have polyarylene (poly-AB-SO as the isobutyl-of protecting group ₃I-Bu) change into and have sulfonic polyarylene (poly-AB-SO ₃H)

With 5.08g (with SO ₃I-Bu counts 2.7mmol) the poly-AB-SO of embodiment 3 preparation ₃I-Bu is dissolved among the 60mlNMP, and is heated to 90 ℃.The mixture of disposable adding 50ml methyl alcohol and 8ml concentrated hydrochloric acid in the described reaction soln.Under suspended state, carrying out described reaction 10 hours under the gentle reflux condition.Set water distilling apparatus, and steam excessive methyl alcohol, make jade-green clear solution thus.Described solution casting forms film on sheet glass.After film forms, will be described thin film dipped in water 3 days, air-dry and vacuum-drying, make dried thick be 50 microns film.By IR spectrum and ion exchange column quantitative analysis as can be known, described sulfonate ester group (SO ₃R) change into sulfonic group (SO quantitatively ₃H).

Figure 19 has shown IR spectrum, and Figure 20 has shown NMR spectrum.Describedly comprise the sulfonic group content (the sulfonic group content for preparing in the polyreaction is 1.47meq/g) that sulfonic polyarylene has 1.46meq/g.

Embodiment 7

The polyarylene that has as the neo-pentyl of protecting group that will be used for sulfonic acid (gathers AB-SO ₃Neo-Pe) change into and have sulfonic polyarylene (poly-AB-SO ₃H)

With 4.50g (with SO ₃Neo-Pe counts 8mmol) poly-AB-SO ₃Neo-Pe adds in the 35ml trifluoroacetic acid gradually.The gained viscous solution is heated to light reflux state.In reaction process, add the 5ml trifluoroacetic acid again.After 2 hours, polymer deposition, and continue again to stir, described reaction was carried out 4 hours altogether.After the reaction, leave standstill described reaction mixture, reduce to room temperature up to temperature.Collect described settling as aggregate by filtering.Under agitation condition, described aggregate is suspended among the 400mlTHF, and washs, and afterwards, collects described aggregation, the air-dry crude product that makes by filtering.Wash described crude product twice with water, make the powder polymer of light brown at last.

8 weight %NMP solution castings of resulting polymers are formed film on sheet glass.After film formed, the air-dry and vacuum-drying with described film made that to do thick be 40 microns film.By IR spectrum and ion exchange column quantitative analysis as can be known, described sulfonate ester group (SO ₃R) change into sulfonic group (SO quantitatively ₃H).

Figure 21 has shown IR spectrum, and Figure 22 has shown NMR spectrum.Describedly comprise the sulfonic group content (the sulfonic group content for preparing in the polyreaction is 2.0meq/g) that sulfonic polyarylene has 2.0meq/g.

It is as described below that gained has the character of sulfonic group polyarylene film.

(1) proton conductive

85℃ 95％RH：0.268S/cm

85℃ 70％RH：0.100S/cm

85℃ 30％RH：0.018S/cm

(2) tensile property

Room temperature: Young's modulus 4.4Gpa, tensile strength 153Mpa, yield strength 98Mpa, extensibility 52%

120 ℃: Young's modulus 4.4Gpa, tensile strength 131Mpa, extensibility 38%

(3) water content

95 ℃ 48 hours: 65%

After 95 ℃ flooded 500 hours down, described film was stable, does not change the equivalent of sulfonic acid.

(4) thermostability

120 ℃ 500 hours: after 120 ℃ of following thermal treatments 500 hours, do not produce insoluble component, described film is stable, does not change the equivalent of sulfonic acid.

Heat decomposition temperature: 162 ℃

Embodiment 8

Except using the poly-AB-SO of 4.90g embodiment 5 preparations ₃Neo-Pe and 40ml trifluoroacetic acid replace used poly-AB-SO among the embodiment 4 ₃Beyond the neo-Pe, repeat the step of embodiment 7, finally make the powder polymer of light brown.

Figure 23 has shown IR spectrum.Describedly comprise the monomer sulfonic group content (the sulfonic group content for preparing in the polyreaction is 2.2meq/g) that sulfonic polyarylene has 1.8meq/g.

(1) proton conductive

85℃ 95％RH：0.250S/cm

85℃ 70％RH：0.095S/cm

85℃ 30％RH：0.018S/cm

(2) tensile property

Room temperature: Young's modulus 4.6Gpa, tensile strength 136Mpa, extensibility 44%

120 ℃: Young's modulus 4.6Gpa, tensile strength 117Mpa, extensibility 30%

(3) water content

95 ℃ 48 hours: 70%

(4) thermostability

After 120 ℃ of following thermal treatments 500 hours, do not produce insoluble component, described film is stable, does not change the equivalent of sulfonic acid.

Heat decomposition temperature: 170 ℃

Embodiment 9

The polyreaction of polyarylene

In nitrogen atmosphere, compound shown in 100ml exsiccant N,N-dimethylacetamide (DMAc) the adding following general formula of 26.66g (41.7mmol) (3), 17.47g (1.56mmol) are synthesized BCPAF oligopolymer, 0.79g (1.2mmol) Ni (PPH that embodiment 1 makes ₃) ₂Cl ₂, 4.20g (16.01mmol) PPH ₃, 0.18g (1.20mmol) NaI, 6.28g (96.07mmol) zinc powder mixture in.

Under agitation condition, heat described reaction soln (finally being heated to 79 ℃), and reacted 3 hours.In reaction process, observe the rising of described reaction soln medium viscosity.Afterwards, dilute described polymeric reaction solution, after stirring 30 minutes, filter as filtering auxiliary with Celite with 425mlDMAc.With a part of filtered liquid impouring methyl alcohol and condense.Gained has the multipolymer of the sulfonate derivatives of neo-pentyl, and with regard to polystyrene, recording its number-average molecular weight by GPC (THF solvent) is 59400, and weight-average molecular weight is 178300.Figure 24 has shown IR spectrum, and Figure 25 has shown NMR spectrum.

Concentrate above-mentioned filtered liquid with vaporizer, be concentrated into 344g,, add 10.00g (0.12mol) LiBr, under nitrogen atmosphere, under 110 ℃ inside bath temperature (bathing 120 ℃ of temperature), carry out described reaction 7 hours toward wherein.After the reaction, cool off described reaction soln to room temperature, and in the impouring 4L acetone, and condense.Collect gained coagulum and air-dry by filtering.Afterwards, described coagulum is pulverized by mixing tank, and washs under agitation condition with 1500ml1N hydrochloric acid.After the filtration, with ion-exchange water washing products therefrom, making pH is 5 or bigger, finally makes polymer powder.

8 weight %NMP solution castings of resulting polymers are formed film on sheet glass.After film formed, the air-dry and vacuum-drying with described film made that to do thick be 40 microns film.By IR spectrum and ion exchange column quantitative analysis as can be known, described sulfonate ester group changes into sulfonic group quantitatively.

The described sulfonic group content that sulfonic polyarylene has 2.0meq/g (the sulfonic group content theoretical value of being determined by the monomer mole ratio for preparing in the polyreaction is 2.0meq/g) that comprises.Figure 26 has shown that gained comprises the IR spectrum of sulfonic group polyarylene, and Figure 27 has shown NMR spectrum.

(1) proton conductive

85℃ 95％RH：0.275S/cm

85℃ 70％RH：0.106S/cm

85℃ 30％RH：0.022S/cm

(4) thermostability

Embodiment 10

S-2,5-DCPPB chlorosulphonation compound sulphonate

(S-2,5-DCPPB peopentyl ester)

In above-mentioned general formula, Np is a neo-pentyl.

(1) two sulfonated compounds of synthesis of phenoxy phenol

Toward 1L three-necked flask adding 370g (0.69 mole) the 4-phenoxy phenyl that agitator, thermometer is housed and introduces the conduit of nitrogen, and in about 1 hour, drip the 740ml vitriol oil.After being added dropwise to complete, stirred described solution 3 hours down at 50 ℃.Reaction is diluted described reaction soln with 200ml water after finishing, and (KOH 1.5Kg/ water 750ml) neutralizes with KOH solution.Filter sedimentary thus solid, and wash, make the 1709g white powder with acetone.Described powder comprises the sylvite (SPPO) and the potassium hydroxide of phenoxy phenyl two sulfonated compounds.Figure 28 has shown the NMR spectrum of described powder.

(2) Synthetic 2, and 5-two chloro-4 '-(4-phenoxy group phenoxy group) benzophenone two sulfonated compounds (S-2,5-DCPPB)

Toward 1L three-necked flask adding 43.7g (0.31 mole) SPPO, the 43.14g (0.10 mole) 2 that agitator, thermometer is housed and introduces the conduit of nitrogen, 5-two chloro-4 '-fluoro benzophenone, 2.6g (8mmol) bromination tetra-n-butyl ammonium (TBAB) and 200ml dimethyl sulfoxide (DMSO), and under 160 ℃, in nitrogen atmosphere, stir.And, suitably add 30g (65mmol) SPPO and 1.0g (3mmol) TBAB, and continue reaction.After 30 hours, filter the salt of gained, and in the acetone with filtered liquid impouring 4.5L.Filter sedimentary thus solid, and with 1-1.5L washing with acetone 4-5 time.The described solid of vacuum-drying makes 81gS-2,5-DCPPB (productive rate 70%).Figure 29 has shown the NMR spectrum of described compound.

(3) synthetic S-2,5-DCPPB chlorosulphonation compound

Toward 1L three-necked flask adding 146.5g (0.22 mole) S-2 that agitator, thermometer is housed and introduces the conduit of nitrogen, 5-DCPPB and 650ml acetonitrile, and 70 ℃ of stirrings down.In 15 minutes, in described solution, drip the 220g phosphoryl chloride, stirred afterwards 5 hours.After reaction is finished, in described reaction soln, drip the 1.3Kg frozen water, and use the 2.5L dilution with toluene.With the described organic phase of anhydrous magnesium sulfate drying.(launch solvent: toluene) remove after the described residual inorganic phase,, make 71g target compound (productive rate is 52%) with the silica gel chromatogram with the described residue of toluene/hexane recrystallization.Figure 30 has shown the NMR spectrum of described compound.

(4) synthetic S-2, the 5-DCPPB peopentyl ester

Toward 1L three-necked flask adding 59.5g (94mmol) S-2 that agitator, thermometer is housed and introduces the conduit of nitrogen, 5-DCPPB chlorosulphonation compound and 400ml pyridinium salt, and in frozen water, cool off.In described solution, add 20.5g (233mmol) neopentyl alcohol and stirring, afterwards, remove described ice-water bath, at room temperature stirred described solution 5 hours.Remove by filter sedimentary thus pyridine, and extract described residue with toluene/ethyl acetate (600ml/600ml).The solution (concentrated hydrochloric acid 300ml/ water 300ml) that washs described extraction with aqueous hydrochloric acid several times, then several times with 5% sodium bicarbonate aqueous solution and saturated sodium-chloride water solution washing.Steam described solvent, (launch solvent: toluene) separate, make 36gS-2, the 5-DCPPB peopentyl ester by the silica gel chromatogram.Figure 31 has shown the IR spectrum of described ester, and Figure 32 has shown NMR spectrum.

Embodiment 11

Synthetic polyarylene

The past 500mL three-necked flask that the conduit of agitator, thermometer and introducing nitrogen is housed is weighed and is added the S-2 that 21.4g (29mmol) embodiment 10 makes, BCPAF oligopolymer, 0.59g (0.9mmol) dichloride two (triphenylphosphine) nickel, 0.13g (0.9mmol) sodium iodide, 3.15g (12mmol) triphenyl phosphorus and 4.71g (72mmol) zinc that the synthetic embodiment 1 of 5-DCPPB peopentyl ester, 9.90g (0.9mmol) makes, and vacuum-drying 2 hours.Afterwards,, and the 73ml N,N-DIMETHYLACETAMIDE that dewaters added in the flask, begin polyreaction then with exsiccant nitrogen wash described flask.

Described temperature of reaction being controlled at when not being higher than 90 ℃, continued described polyreaction 3 hours.Afterwards, dilute described polymeric reaction solution, pour into then (methyl alcohol 2.7L/ concentrated hydrochloric acid 0.3L) in methyl alcohol/concentrated hydrochloric acid solution by adding the 80ml tetrahydrofuran (THF).

Filter sedimentary thus product, and wash, carry out air-dry then with methyl alcohol.In described exsiccant polymer dissolution tetrahydrofuran (THF), and by removing by filter insoluble component, afterwards, redeposited residue in 3.5L methyl alcohol.Filter described polymkeric substance, and vacuum-drying makes 23.5g polyarylene (productive rate 80%).With regard to polystyrene, the number-average molecular weight that is recorded described polymkeric substance by GPC (THF solvent) is 61000, and weight-average molecular weight is 278000.

In general formula, NP is a neo-pentyl.

Embodiment 12

Synthesize and have sulfonic polyarylene

300mL three-necked flask toward the conduit that agitator, thermometer and introducing nitrogen are housed adds polyarylene, 6.34g (73mmol) lithiumbromide that 23.5g embodiment 11 makes, and stirs 7 hours down at 120 ℃.The reaction soln of gained is poured in the acetone, and polymkeric substance condenses.Handling gained solid polymer twice with distilled water/concentrated hydrochloric acid solution (3.0L/0.37L), is neutral with distilled water wash up to pH then.Dry described solid polymer is 12 hours under 70 ℃, makes shown in the following general formula of 19.9g to have sulfonic polyarylene.

With regard to polystyrene, the number-average molecular weight that is recorded described polymkeric substance by GPC (THF solvent) is 78000, and weight-average molecular weight is 230000.Described have sulfonic polyarylene and have the 2.19meq/g loading capacity.Use N-Methyl pyrrolidone, making thickness by pouring procedure is 40 microns film.

Performance evaluation

To the film of gained, estimate its character.In table 1, listed the result.

Table 1

Assessment item	Unit
Assessment item	Unit		Proton conductive (85 ℃, 90%RH)	S/cm	0.25
Young's modulus	Gpa	3.5	Proton conductive (85 ℃, 90%RH)	S/cm	0.25
Young's modulus	Gpa	3.5	Breaking tenacity	Mpa	84
Extensibility	％	46	Breaking tenacity	Mpa	84
Extensibility	％	46	Tolerance (120 ℃, 100 hours) to hot water	The weight conservation rate, %	100
Tolerance (3%H2O to Fenton reagent ₂, 20ppmFe2+, 45 ℃, 20 hours)	The weight conservation rate, %	100	Tolerance (120 ℃, 100 hours) to hot water	The weight conservation rate, %	100
	The weight conservation rate, %	100	Thermolysis begins temperature	℃	240

Effect of the present invention

It is safe that the present invention has sulfonic poly (arylene ether) and preparation method thereof, and load is low in polymer recovery, and this is because have in the sulfonic poly (arylene ether) in that poly (arylene ether) is changed into, and does not use sulfonating agent. And sulfonic amount and the introducing position thereof of introducing in the polymer are controlled easily.

Aromatic sulfonic acid ester derivative of the present invention and poly (arylene ether) are used for above-mentioned poly (arylene ether) with sulfonic acid and preparation method thereof.

Proton conducting film of the present invention has good electric conductivity.

Claims

1. a polyarylene comprises the repeated structural unit from aromatic substance, and comprises the repeated structural unit by general formula (1 ') expression at least:

In the formula, A is-CO-,-C (CF ₃) ₂-or-SO ₂-, B is-O-R ^aBe the alkyl of 1-20 carbon atom, Ar has by-SO ₃R ^bThe substituent aryl of expression ,-SO ₃R ^bIn, R ^bBe the alkyl of 1-20 carbon atom, m is the integer between the 0-10, and n is the integer between the 0-10, and k is the integer of 1-4.

2. polyarylene as claimed in claim 1 is characterized in that, described polyarylene comprises repeated structural unit shown in the repeated structural unit shown in the 0.5-100 mole % general formula (1 ') and the 0-99.5 mole % general formula (A ');

3. preparation has the method for sulfonic polyarylene, and said method comprising the steps of: the coupling polymerization comprises the aromatic substance of the aromatic sulfonic acid ester derivative shown in the general formula (1), preparation polyarylene, and the described polyarylene of hydrolysis:

In the formula, X is the halogen atom that is selected from beyond the defluorination, A is-CO-,-C (CF ₃) ₂-or-SO ₂-, B is-0-R ^aBe the alkyl of 1-20 carbon atom, Ar has by-SO ₃R ^bThe substituent aryl of expression ,-SO ₃R ^bIn, R ^bBe the alkyl of 1-20 carbon atom, m is the integer between the 0-10, and n is the integer between the 0-10, and k is the integer of 1-4.

4. copolymer solid electrolyte, described ionogen comprise by what the described method of claim 3 made and have a sulfonic polyarylene.

5. fuel cell proton conductive membrane, described film comprises the described copolymer solid electrolyte of claim 4.