CN1250610C - Sulfonated benzoxaazole or sulfonated polybenzoxaazole and preparation thereof - Google Patents
Sulfonated benzoxaazole or sulfonated polybenzoxaazole and preparation thereof Download PDFInfo
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Abstract
The present invention provides sulfonated polybenzoxazole or sulfonated polybenzothiazole and a preparation method thereof. 3, 3'-disulfonyl (sulfonate)-4, 4'-dicarboxyl diphenyl sulphone or a derivative thereof is used as a sulfonated monomer reacting with aromatic dicarboxylic acid or aromatic heterocyclic dicarboxylic acid or a derivative thereof and dihydroxyl aromatic diamine or dimercapto aromatic diamine or hydrochloride thereof in polyphosphoric acid in a solution polycondensation mode, and the high thermal stability sulfonated polybenzoxazole or the high thermal stability sulfonated polybenzothiazole controllable in the sulphonation degree can be obtained. The sulfonated polybenzoxazole or the sulfonated polybenzothiazole which can be used as membrane materials, such as electrodialysis membranes, ultrafiltration membranes, ion exchange membranes or proton exchange membranes, etc., has broad application prospects.
Description
Technical field: the present invention relates to a kind of functional high molecule material and preparation method thereof, particularly a kind of sulfonated polyphenyl Bing oxazole or sulfonated polyphenyl and thiazole and preparation method thereof.
Background technology: Proton Exchange Membrane Fuel Cells (PEMFC) has obtained to develop rapidly at recent two decades.As one of three big critical materials of PEMFC, the development of novel proton exchange membranes material has been subjected to investigator's great attention.At present, though sulfonic acid type full fluorin proton exchange film such as the commercialization of Nafion mould material because cost an arm and a leg, proton conductivity reduces and the high deficiency of methanol permeability has limited it and uses more widely under high temperature or low humidity condition.Therefore, in the research and development process of novel proton exchange membranes material, more concern is placed on sulfonation special engineering plastics aspect, as sulfonated polyether sulfone, sulfonated poly thioether sulfone, sulfonated polyether ketone, sulfonated polyether-ether-ketone and sulfonated polyimide etc.Polybenzimidazole is the special engineering plastics of a class excellent combination property, has excellent thermostability, chemical stability and dimensional stability.People such as Wainright reported first in 1994 phosphate-doped polybenzimidazole can be used for the discovery of proton exchange membrane.After this, the research of acid or alkali doping polybenzimidazole and sulfonated polyphenyl and imidazoles has caused investigator's great interest and since this class film have excellent physical chemistry and an electric property, they have broad application prospects in the PEMFC field.
Similar with polybenzimidazole, polybenzoxazole also is the special engineering plastics of a class excellent combination property, it is invented by United States Air Force kinetics development research personnel the earliest, the basic patent that is at first had polybenzoxazole by institute of Stanford Univ USA is obtained its whole world enforcement right by Dow chemical company and is carried out industrialized developing.Up in October, 1998, polybenzoxazole fibers just spins commercialization (commodity are called Zylon) by Japan.Up to now, less about the sulfonation modifying report of polybenzoxazole.Before surplus in the of ten year, Dow chemical company (US5216114,1993) has applied for that the Direct Sulfonation polybenzoxazole is to improve the patent of it and matrix resin adhesiveproperties.Recently, institute of Stanford Univ USA has applied for the patent (US6176984,2001) based on the high temperature polymer electrolyte of sulfonated polyphenyl Bing oxazole.People (the JP2002206026 such as Yoshimitsu Sakaguchi of company spin in Japan Japan; Polymer Materials:Science﹠amp; Engineering 2001,84,899) with 5-sodium sulfonate m-phthalic acid and another kind of business-like 2-sodium sulfonate terephthalic acid as sulfonated monomers, with terephthalic acid and 3, the high sulfonated polyphenyl Bing oxazole of Heat stability is good and proton conductivity has been synthesized in the polycondensation of 3 '-dihydroxybiphenyl amine.
Summary of the invention: the present invention is from Molecular Structure Design and practical application angle, adopt the own synthetic sulfonation 4 of contriver, this class sulfonated monomers of 4 '-Dicarboxy diphenylsulfone or derivatives thereof, sulfonated polyphenyl Bing oxazole or the sulfonated polyphenyl and the thiazole of the Heat stability is good that synthetic sulfonation degree is controlled, their repeated structural unit is as follows:
(x+z)/y=0.98-1.02 wherein, 0＜x/ (x+z)≤100%, 0≤z/ (x+z)＜100%, 4＜m＜2000;
R
1Be hydrogen, lithium, sodium, potassium, caesium, magnesium, calcium, barium, lead or iron;
R
2Be oxygen or sulphur;
Ar
1Structure is as follows:
Or
R
2Can be 6,6 ' position or 5,5 ' position, can be :-, O, S, SO
2, CH
2, C (CH
3)
2, C (CF
3)
2, or
Wherein can include a kind of or two or more corresponding Ar respectively in the repeated structural unit of sulfonated polyphenyl Bing oxazole or sulfonated polyphenyl and thiazole
1Structure;
Ar
2Structure is as follows:
1,4, prosposition, 2,6 or 2,7;
Or
2,2 ', 3,3 ' or 4,4 ', wherein: Y=-, O, S, SO
2, CO, CH
2, C (CH
3)
2Or C (CF
3)
2
Wherein can include a kind of or two or more Ar respectively in the repeated structural unit of sulfonated polyphenyl Bing oxazole or sulfonated polyphenyl and thiazole
2Structure.
The method that the present invention prepares sulfonated polyphenyl Bing oxazole or sulfonated polyphenyl and thiazole is a solution polycondensation, and concrete preparation process is as follows:
(1) reinforced mix stages, at first at 50-200 ℃ the polyphosphoric acid solvent is carried out deoxidation with rare gas element such as nitrogen or argon gas, then with dihydroxyl aromatic diamines or its hydrochloride of dimercapto aromatic diamines and sulfonated monomers and aromatics or fragrant heterocyclic di-carboxylic acid, dicarboxylic esters or binary acyl chlorides add in this solvent together and stir evenly, the mole number of above-mentioned dihydroxyl aromatic diamines or dimercapto aromatic diamines or its hydrochloride and sulfonated monomers and aromatics or fragrant heterocyclic di-carboxylic acid, the ratio of the mole number sum of dicarboxylic esters or binary acyl chlorides is between 0.98-1.02, preferably this ratio is 1, just can obtain high-molecular weight sulfonated polyphenyl Bing oxazole or sulfonated polyphenyl and thiazole; Monomer mass content is between 0.2-30% in this solution polymerization system;
(2) the temperature reaction stage, adopt progressively temperature-raising method, carry out polycondensation at 50-250 ℃, the reaction times is 4-400 hour, and wherein the temperature interval value is controlled at 5-60 ℃, and at each temperature spot, duration of the reaction is between 0.1-100 hour;
(3) discharging post-processing stages, after polyreaction finishes, with reaction mass directly or with pouring in the precipitation agent after the thinner dilution, repetitive scrubbing is to remove solvent remaining in the product then, or with washing with water to neutrality behind the solvent remaining in alkali or the weakly alkaline inorganic salt neutralized reaction product, final drying get final product sulfonated polyphenyl Bing oxazole or sulfonated polyphenyl and thiazole.
Synthetic sulfonated polyphenyl Bing oxazole of the present invention or sulfonated polyphenyl and the used sulfonated monomers of thiazole have following molecular structure:
Wherein, R
1Be hydrogen, lithium, sodium, potassium, caesium, magnesium, calcium, barium, lead or iron, preferred R
1Be hydrogen, lithium, sodium or potassium; R
4And R
5Can be identical, also can be different, R
4And R
5Can be hydroxyl, chlorine, phenoxy group or contain the straight chain or the branched alkoxyl group of 1 to 20 carbon atom, preferred R
4And R
5Be hydroxyl, chlorine or phenoxy group.
The present invention synthesizes the used sulfonated monomers of sulfonated polyphenyl Bing oxazole or sulfonated polyphenyl and thiazole as 3,3 '-disulfonic acid base-4, and the preparation method of 4 '-Dicarboxy diphenylsulfone is as follows:
Fs: sulfonation stage, 4,4 '-dialkyl group sulfobenzide contacts with sulphonating agent, sulphonating agent is the vitriol oil, oleum, sulphur trioxide, chlorsulfonic acid and composition thereof, preferred sulphonating agent is an oleum, for every mole 4,4 '-dialkyl group sulfobenzide, used oleum contains the free sulphur trioxide of 2-100mol, preferred oleum contains the free sulphur trioxide of 3-12mol, and carries out sulfonation reaction under 0-200 ℃, and temperature of reaction is preferably at 70-150 ℃, reaction times is 1-12 hour, is preferably 6-10 hour;
Subordinate phase: saltout or neutralization stage, under ice-water bath or normal temperature, while stirring reaction product is slowly poured in the saturated aqueous solution such as the inorganic salt of sodium-chlor, the 0.1-300 of used oleum volume doubly when the volume of the saturated aqueous solution of these inorganic salt was sulfonation, be preferably 1-10 doubly, after leaving standstill for some time, be that the adularescent product is separated out, filter, use then such as the saturated aqueous solution of the alkali of sodium hydroxide or such as the saturated aqueous solution neutralization of the inorganic salt of yellow soda ash, crystallization is filtered to remove vitriol;
Phase III: product purification stage, add dehydrated alcohol or methyl alcohol in the filtrate after removing by filter vitriol with precipitation or crystallization, filter, filtration cakes torrefaction, can get white 4 of two the sulfonate structures that contain, the pure product of 4 '-dialkyl group sulfobenzide, this product is behind acidifying, filtration and filtration cakes torrefaction, can contain 4 of two sulfonic acid structures, 4 '-dialkyl group sulfobenzide white mass.
Quadravalence section: oxidation stage, contain 4 of two sulfonic acid structures, 4 '-dialkyl group sulfobenzide contacts with oxygenant, and oxygenant is potassium permanganate, potassium bichromate, nitric acid and oxygen, preferably use potassium permanganate and dioxygen oxidation, for the above-mentioned sulfonated products of mole, the consumption of potassium permanganate is the 4-16 mole, and the consumption of preferred potassium permanganate is the 4-6 mole, under room temperature to 170 ℃, carry out oxidizing reaction, temperature of reaction is preferably at 60-100 ℃, and the reaction times is 1-15 hour, is preferably 4-10 hour;
Five-stage: the product purification stage, with the reaction mixture filtered while hot, and with small amount of thermal water washing filter residue.Merging filtrate and washing lotion are cooled off in cooling bath, are that 10% to 36.5% hcl acidifying to congo-red test paper becomes blue with concentration then, get white needle-like crystals, the a small amount of cold water washing of suction filtration, filter cake is drained drying, get 3,3 '-disulfonic acid base-4,4 '-Dicarboxy diphenylsulfone.
Synthetic sulfonated polyphenyl Bing oxazole of the present invention or sulfonated polyphenyl and the employed dihydroxyl aromatic diamines of thiazole or dimercapto aromatic diamine monomers have 2,5-dihydroxyl Ursol D, 4,6-dihydroxyl mphenylenediamine, 3,5-diamino-2,6-pyridine diphenol, 3,3 '-dihydroxybiphenyl amine, 3,3 '-diamino-4,4 '-dihydroxybiphenyl, two [4-amino-3-hydroxy base] ether, two [3-amino-4-hydroxy phenyl] ether, two [4-amino-3-hydroxy base] sulfone, two [3-amino-4-hydroxy phenyl] sulfone, 2, two [the 4-amino-3-hydroxy base] propane of 2-, 2, two [the 3-amino-4-hydroxy phenyl] propane of 2-, 2, two [the 4-amino-3-hydroxy base] HFC-236fa of 2-, 2, two [the 3-amino-4-hydroxy phenyl] HFC-236fa of 2-, two [4-amino-3-hydroxy base] methane, two [3-amino-4-hydroxy phenyl] methane, two [4-amino-3-hydroxy base] sulphur, two [3-amino-4-hydroxy phenyl] sulphur, 1, two [the 4-amino-3-hydroxy oxygen base] benzene of 4-, 1, two [the 3-amino-4-hydroxy phenoxy group] benzene of 4-, 2,5-dimercapto Ursol D, 3,6-dimethyl-2,5-dimercapto Ursol D, 4,6-dimercapto mphenylenediamine, 4,4 '-dimercapto-3,3 '-p-diaminodiphenyl, two [4-amino-3-sulfydryl phenyl] ether, two [3-amino-4-sulfydryl phenyl] ether, two [3-amino-4-sulfydryl phenyl penylene] ether, 3,6-diamino-2,5-pyridine dithiol, 1,5-diamino-2,6-naphthyl disulfide phenol, two [4-amino-3-sulfydryl phenyl] sulfone, two [3-amino-4-sulfydryl phenyl] sulfone, 2, two [4-amino-3-sulfydryl phenyl] HFC-236fa of 2-, 2, two [3-amino-4-sulfydryl phenyl] HFC-236fa of 2-, 2, two [3-amino-4-sulfydryl phenyl penylene] HFC-236fa of 2-, 2, two [3-amino-4-sulfydryl phenyl penylene] propane of 2-, 2, two [3-amino-4-sulfydryl phenyl penylene] sulfones of 2-, 2, two [3-amino-4-sulfydryl phenyl penylene] methane of 2-, two [4-amino-3-sulfydryl phenyl] methane, two [4-amino-3-sulfydryl phenyl] thioether, two [3-amino-4-sulfydryl phenyl] thioether, two [4-amino-3-sulfydryl phenoxy group] benzene or two [3-amino-4-sulfydryl phenoxy group] benzene.
The synthetic sulfonated polyphenyl Bing oxazole of the present invention or sulfonated polyphenyl and used aromatics or the fragrant heterocyclic di-carboxylic acid of thiazole, dicarboxylic esters or binary acyl chlorides monomer have terephthalic acid, m-phthalic acid, phthalic acid, to phenylene-diacetic acid, between phenylene-diacetic acid, phthalic acid, 1, the 4-naphthalic acid, 2, the 3-naphthalic acid, 2, the 6-naphthalic acid, 2, the 7-naphthalic acid, 2,2 '-biphenyl dicarboxylic acid, 3,3 '-biphenyl dicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid, 4,4 '-Dicarboxy diphenylsulfone, 4,4 '-dicarboxyl phenyl ether, 4,4 '-dicarboxyl diphenyl sulfide, 4,4 '-dicarboxyl benzophenone, 2,2 '-two (4-carboxyl phenyl) propane, 2,2 '-two (4-carboxyl phenyl) HFC-236fa, 2,5-dicarboxyl pyridine or 2,6-dicarboxyl quinoline, diphenylisophthalate, terephthaldehyde's diphenyl phthalate, 2,6-naphthalene dimethyl chloride, 4,4 '-biphenyl dimethyl chloride, m-phthaloyl chloride or p-phthaloyl chloride.
The mass content of Vanadium Pentoxide in FLAKES is between 83%-89% in the polyphosphoric acid that the present invention uses.
The thinner that the present invention uses has phosphoric acid, polyphosphoric acid, methylsulfonic acid or the vitriol oil, and its quality consumption is add 0.1-200 times of polyphosphoric acid.
The precipitation agent that the present invention uses comprises water, methyl alcohol, ethanol, tetrahydrofuran (THF) or ether.
The structure of synthetic sodium sulfonate type sulfonated polyphenyl Bing oxazole of the present invention is confirmed through Infrared spectroscopy, and its thermal stability is characterized by thermogravimetry (TGA).
Synthetic sulfonated polyphenyl of the present invention and oxazole or sulfonated polyphenyl and thiazole have that sulfonation degree is controlled, the thermostability advantages of higher, aspect the mould materials such as electrodialytic membranes, ultra-filtration membrane, ion-exchange membrane or proton exchange membrane wide application prospect are being arranged.
Description of drawings: the infrared spectrogram of Fig. 1 sulfonated polyphenyl Bing oxazole
The hot weightless picture of Fig. 2 sulfonated polyphenyl Bing oxazole
Embodiment: the following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1 (preparation of sulfonated monomers): under ice-water bath, with 5 gram (0.0202mol) 4, whipping appts is equipped with in the adding of 4 '-diphenylsulfone dimethyl, in the reactor that fills the 30ml10% oleum of reflux condensing tube, violent stirring reaction at normal temperatures is after 1 hour, slowly be warming up to 90 ℃, and insulated and stirred was reacted 6 hours under this temperature, reaction solution is pale brown look, after the question response liquid cooling but, under ice-water bath, while stirring it is slowly poured in the beaker of the saturated aqueous solution that fills 120ml sodium-chlor, stir moments later, left standstill 2 hours, filter white filter cake, this white filter cake with in yellow soda ash saturated aqueous solution and after, crystallization removes by filter sodium sulfate, and adding and the isopyknic dehydrated alcohol of filtrate are with precipitation or crystallization in the filtrate, filter, filter cake can get 3 of 7.76 gram whites, 3 '-sodium disulfonate-4 80 ℃ of following vacuum-dryings 24 hours, the pure product of 4 '-diphenylsulfone dimethyl, yield is about 75%.
Accurately take by weighing 6 gram (0.0133mol) 3,3 '-sodium disulfonate-4,4 '-diphenylsulfone dimethyl add in the 250mL round-bottomed flask, add 49ml water again, load onto prolong, on the electromagnetism heating stirrer, be heated to little boiling, under agitation with sand-bath, from the prolong total amount that adds suitable for reading in batches is 10 gram potassium permanganate, add next batch again after question response is mild, the potassium permanganate of using less water (about 1ml) will stick on the prolong inwall at last pours in the bottle, continues back flow reaction after 1 hour, with the reaction mixture filtered while hot, and with small amount of thermal water washing filter residue, merging filtrate and washing lotion are cooled off in cooling bath, become blue with 25% hcl acidifying to congo-red test paper then, white needle-like crystals is separated out, a small amount of cold water washing of suction filtration, filter cake, drain, dry, get 5.5 grams 3,3 '-disulfonic acid base-4,4 '-Dicarboxy diphenylsulfone, productive rate about 82%.
Embodiment 2 (preparation of sulfonated polyphenyl Bing oxazole): agitator is being housed and nitrogen goes out; the polyphosphoric acid solvent that adds 25 grams 84% in three mouthfuls of round-bottomed flasks of 100ml of inlet; again this round-bottomed flask is immersed in the oil bath; heating medium oil is heated to 100 ℃ and continue to stir 5 hours to remove the air in the round-bottomed flask under nitrogen protection; then in round-bottomed flask, add 1.0000 grams 4; 6-diaminobenzene diphenol hydrochloride (4.693mmol); 0.8625 restrain 4; 4 '-Dicarboxy diphenylsulfone (2.816mmol) and 0.8755 gram 3; 3 '-disulfonic acid base-4; 4 '-Dicarboxy diphenylsulfone (1.877mmol); then under nitrogen protection and agitation condition; in 100 ℃ of reactions 6 hours; 150 ℃ were reacted 7 hours; 190 ℃ of reactions are after 8 hours; the gained viscous solution slowly poured in 1.5 liters of deionized waters precipitate; obtain pale brown vitta shaped polymer; after being washed till slightly acidic with deionized water; use the aqueous solution soaking of yellow soda ash again; be washed to neutrality at last; in vacuum drying oven in 100 ℃ of vacuum-dryings 36 hours; can get 2.1224 gram sulfonation degree is 40% sodium sulfonate type sulfonated polyphenyl Bing oxazole; yield is about 99.1%; the structure of product is confirmed through Infrared spectroscopy, and its thermal stability is characterized by TGA.
Adopt pellet technique, the structure of p-sulfonic acid sodium type sulfonated polyphenyl Bing oxazole has been carried out examination of infrared spectrum, and its infrared spectrogram is seen Fig. 1, therefrom can observe the following characteristics absorption band:
3093.1cm
-1Fragrance-C-H stretching vibration absorption band;
1627.6cm
-1In the five-membered ring-C=N-stretching vibration absorption band;
1241.0,1207.1 ,-SO
3O=S=O stretching vibration absorption band among the Na;
1115.8，1011.2cm
-1
1049.2cm
-1In the five-membered ring=C-O-C stretching vibration absorption band;
694.5cm
-1-S-O stretching vibration absorption band.
This sulfonation degree is that the thermal stability of 40% sodium sulfonate type polybenzoxazole adopts TGA 2050 thermogravimetric analyzers to characterize, temperature rise rate is 20 ℃/min, nitrogen atmosphere, before beginning test in 200 ℃ of constant temperature 10min postcooling to 90 ℃, be warming up to about 900 ℃ again and test, the results are shown in Figure 2.As can be seen from Figure 2, this product has excellent thermal stability, and the temperature of its weightlessness 5% and 10% o'clock correspondence is respectively 501.5 ℃ and 524.1 ℃, and its maximum weight loss rate temperature is 545.2 ℃.
Embodiment 3 (preparation of sulfonated polyphenyl Bing oxazole): agitator is being housed and nitrogen goes out; add 25 grams, 84% polyphosphoric acid solvent in three mouthfuls of round-bottomed flasks of 100ml of inlet; again this round-bottomed flask is immersed in the oil bath; heating medium oil is heated to 100 ℃ and continue to stir 5 hours to remove the air in the round-bottomed flask under nitrogen protection; then in round-bottomed flask, add 1.0000 grams 4; 6-diaminophenol hydrochloride (4.693mmol); 0.6061 restrain 4; 4 '-dicarboxyl phenyl ether (2.347mmol) and 1.0945 grams 3; 3 '-disulfonic acid base-4; 4 '-Dicarboxy diphenylsulfone (2.347mmol); then under nitrogen protection and agitation condition; in 100 ℃ of reactions 6 hours; 150 ℃ were reacted 7 hours; 190 ℃ of reactions are after 8 hours; the gained viscous solution slowly poured in 1.5 liters of deionized waters precipitate; obtain pale brown vitta shaped polymer; after being washed till slightly acidic with deionized water; use the aqueous solution soaking of yellow soda ash again; be washed to neutrality at last; in vacuum drying oven in 100 ℃ of vacuum-dryings 36 hours; can get 2.1111 gram sulfonation degree is 50% sodium sulfonate type sulfonated polyphenyl Bing oxazole; yield is about 99.2%; the structure of product is confirmed through Infrared spectroscopy, and its thermal stability TGA characterizes.
Can also observe the characteristic absorption band of sodium sulfonate in the infrared spectrogram of this sodium sulfonate type sulfonated polyphenyl Bing oxazole.
This sulfonation degree is that the thermal stability of 50% sodium sulfonate type polybenzoxazole adopts TGA 2050 thermogravimetric analyzers to characterize, testing method is with embodiment 1, the temperature of its weightlessness 5% and 10% o'clock correspondence is respectively 491.7 ℃ and 529.5 ℃, and its maximum weight loss rate temperature is 539.3 ℃.
Embodiment 4 (preparation of sulfonated polyphenyl Bing oxazole): agitator is being housed and nitrogen goes out; add 25 grams, 84% polyphosphoric acid solvent in three mouthfuls of round-bottomed flasks of 100ml of inlet; again this round-bottomed flask is immersed in the oil bath; heating medium oil is heated to 100 ℃ and continue to stir 5 hours to remove the air in the round-bottomed flask under nitrogen protection; then in round-bottomed flask, add 1.0000 grams 4; 6-diaminophenol hydrochloride (4.693mmol); 1.4727 two (phenylformic acid) HFC-236fa (3.7544mmol) of gram and 0.4378 gram 3; 3 '-disulfonic acid base-4; 4 '-Dicarboxy diphenylsulfone (0.9386mmol); then under nitrogen protection and agitation condition; in 100 ℃ of reactions 6 hours; 150 ℃ were reacted 7 hours; 190 ℃ of reactions are after 8 hours; the gained viscous solution slowly poured in 1.5 liters of deionized waters precipitate; obtain pale brown vitta shaped polymer; after being washed till slightly acidic with deionized water; use the aqueous solution soaking of yellow soda ash again; be washed to neutrality at last; in vacuum drying oven in 100 ℃ of vacuum-dryings 36 hours; can get 2.2573 gram sulfonation degree is 20% sodium sulfonate type sulfonated polyphenyl Bing oxazole; yield is about 99.3%; the structure of product is confirmed through Infrared spectroscopy, and its thermal stability TGA characterizes.
Can also observe the characteristic absorption band of sodium sulfonate in the infrared spectrogram of this sodium sulfonate type sulfonated polyphenyl Bing oxazole.
This sulfonation degree is that the thermal stability of 20% sodium sulfonate type polybenzoxazole also adopts TGA 2050 thermogravimetric analyzers to characterize, and testing method is with embodiment 1, its weightless 5% and the temperature of 10% o'clock correspondence be respectively 485.7 ℃ and 525.2 ℃.
Claims (8)
1. a sulfonated polyphenyl and oxazole or sulfonated polyphenyl and thiazole is characterized in that having following repeated structural unit:
(x+z)/y=0.98-1.02 wherein, 0＜x/ (x+z)≤100%, 0≤z/ (x+z)＜100%, 4＜m＜2000;
R
1Be hydrogen, lithium, sodium, potassium, caesium, magnesium, calcium, barium, lead or iron;
R
2Be oxygen or sulphur;
Ar
1Structure is as follows:
Or
R
2Can be 6,6 ' position or 5,5 ' position, can be:
-，O，S，SO
2，CH
2，C(CH
3)
2，C(CF
3)
2，
Or
Wherein can include a kind of or two or more corresponding Ar respectively in the repeated structural unit of sulfonated polyphenyl Bing oxazole or sulfonated polyphenyl and thiazole
1Structure;
Ar
2Structure is as follows:
Wherein can include a kind of or two or more Ar respectively in the repeated structural unit of sulfonated polyphenyl Bing oxazole or sulfonated polyphenyl and thiazole
2Structure.
2. the preparation method of a sulfonated polyphenyl and oxazole or sulfonated polyphenyl and thiazole is characterized in that adopting the method for solution polycondensation, and concrete preparation process is as follows:
(1) reinforced mix stages: at first at 50-200 ℃ the polyphosphoric acid solvent is carried out deoxidation with nitrogen or argon gas, then with dihydroxyl aromatic diamines or dimercapto aromatic diamines or its hydrochloride and sulfonated monomers and aromatics or fragrant heterocyclic di-carboxylic acid, dicarboxylic esters or binary acyl chlorides add in this solvent together and stir evenly, the mole number of above-mentioned dihydroxyl aromatic diamines or dimercapto aromatic diamines or its hydrochloride and sulfonated monomers and aromatics or fragrant heterocyclic di-carboxylic acid, the ratio of the mole number sum of dicarboxylic esters or binary acyl chlorides is between 0.98-1.02, and monomer mass content is between 0.2-30% in this solution polymerization system;
(2) the temperature reaction stage: adopt progressively temperature-raising method, carry out polycondensation at 100-250 ℃, the reaction times is 15-40 hour, and wherein the temperature interval value is controlled at 40-60 ℃, and at each temperature spot, duration of the reaction is between 5-10 hour;
(3) discharging post-processing stages: after polyreaction finishes, with reaction mass directly or with pouring in the precipitation agent after the thinner dilution, repetitive scrubbing is to remove solvent remaining in the product then, or with washing with water to neutrality behind the solvent remaining in alkali or the weakly alkaline inorganic salt neutralized reaction product, final drying get final product sulfonated polyphenyl Bing oxazole or sulfonated polyphenyl and thiazole.
3. the preparation method of sulfonated polyphenyl Bing oxazole according to claim 2 or sulfonated polyphenyl and thiazole is characterized in that employed sulfonated monomers has following molecular structure:
Wherein, R
1Be hydrogen, lithium, sodium, potassium, caesium, magnesium, calcium, barium, lead or iron; R
4And R
5Can be identical, also can be different, R
4And R
5Comprise hydroxyl, chlorine, phenoxy group or contain the straight chain or the branched alkoxyl group of 1 to 20 carbon atom.
4. the preparation method of sulfonated polyphenyl Bing oxazole according to claim 2 or sulfonated polyphenyl and thiazole, it is characterized in that employed dihydroxyl aromatic diamines or dimercapto aromatic diamine monomers are selected from 2,5-dihydroxyl Ursol D, 4,6-dihydroxyl mphenylenediamine, 3,5-diamino-2,6-pyridine diphenol, 3,3 '-dihydroxybiphenyl amine, 3,3 '-diamino-4,4 '-dihydroxybiphenyl, two [4-amino-3-hydroxy base] ether, two [3-amino-4-hydroxy phenyl] ether, two [4-amino-3-hydroxy base] sulfone, two [3-amino-4-hydroxy phenyl] sulfone, 2, two [the 4-amino-3-hydroxy base] propane of 2-, 2, two [the 3-amino-4-hydroxy phenyl] propane of 2-, 2, two [the 4-amino-3-hydroxy base] HFC-236fa of 2-, 2, two [the 3-amino-4-hydroxy phenyl] HFC-236fa of 2-, two [4-amino-3-hydroxy base] methane, two [3-amino-4-hydroxy phenyl] methane, two [4-amino-3-hydroxy base] sulphur, two [3-amino-4-hydroxy phenyl] sulphur, 1, two [the 4-amino-3-hydroxy oxygen base] benzene of 4-, 1, two [the 3-amino-4-hydroxy phenoxy group] benzene of 4-, 2,5-dimercapto Ursol D, 3,6-dimethyl-2,5-dimercapto Ursol D, 4,6-dimercapto mphenylenediamine, 4,4 '-dimercapto-3,3 '-p-diaminodiphenyl, two [4-amino-3-sulfydryl phenyl] ether, two [3-amino-4-sulfydryl phenyl] ether, two [3-amino-4-sulfydryl phenyl penylene] ether, 3,6-diamino-2,5-pyridine dithiol, 1,5-diamino-2,6-naphthyl disulfide phenol, two [4-amino-3-sulfydryl phenyl] sulfone, two [3-amino-4-sulfydryl phenyl] sulfone, 2, two [4-amino-3-sulfydryl phenyl] HFC-236fa of 2-, 2, two [3-amino-4-sulfydryl phenyl] HFC-236fa of 2-, 2, two [3-amino-4-sulfydryl phenyl penylene] HFC-236fa of 2-, 2, two [3-amino-4-sulfydryl phenyl penylene] propane of 2-, 2, two [3-amino-4-sulfydryl phenyl penylene] sulfones of 2-, 2, two [3-amino-4-sulfydryl phenyl penylene] methane of 2-, two [4-amino-3-sulfydryl phenyl] methane, two [4-amino-3-sulfydryl phenyl] thioether, two [3-amino-4-sulfydryl phenyl] thioether, two [4-amino-3-sulfydryl phenoxy group] benzene or two [3-amino-4-sulfydryl phenoxy group] benzene.
5. the preparation method of sulfonated polyphenyl Bing oxazole according to claim 2 or sulfonated polyphenyl and thiazole, it is characterized in that employed aromatics or fragrant heterocyclic di-carboxylic acid, dicarboxylic esters or binary acyl chlorides monomer are selected from terephthalic acid, m-phthalic acid, phthalic acid, to phenylene-diacetic acid, between phenylene-diacetic acid, phthalic acid, 1, the 4-naphthalic acid, 2, the 3-naphthalic acid, 2, the 6-naphthalic acid, 2, the 7-naphthalic acid, 2,2 '-biphenyl dicarboxylic acid, 3,3 '-biphenyl dicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid, 4,4 '-Dicarboxy diphenylsulfone, 4,4 '-dicarboxyl phenyl ether, 4,4 '-dicarboxyl diphenyl sulfide, 4,4 '-dicarboxyl benzophenone, 2,2 '-two (4-carboxyl phenyl) propane, 2,2 '-two (4-carboxyl phenyl) HFC-236fa, 2,5-dicarboxyl pyridine or 2,6-dicarboxyl quinoline, diphenylisophthalate, terephthaldehyde's diphenyl phthalate, 2,6-naphthalene dimethyl chloride, 4,4 '-biphenyl dimethyl chloride, m-phthaloyl chloride or p-phthaloyl chloride.
6. the preparation method of sulfonated polyphenyl Bing oxazole according to claim 2 or sulfonated polyphenyl and thiazole, the content that it is characterized in that Vanadium Pentoxide in FLAKES in the polyphosphoric acid is between 83-89wt%.
7. the preparation method of sulfonated polyphenyl Bing oxazole according to claim 2 or sulfonated polyphenyl and thiazole is characterized in that thinner has phosphoric acid, polyphosphoric acid, methylsulfonic acid or the vitriol oil; Its quality consumption is the 0.1-200 times of add polyphosphoric acid.
8. the preparation method of sulfonated polyphenyl Bing oxazole according to claim 2 or sulfonated polyphenyl and thiazole is characterized in that precipitation agent is selected from water, methyl alcohol, ethanol, tetrahydrofuran (THF) or ether.
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| CN1317058C (en) * | 2005-06-16 | 2007-05-23 | 上海交通大学 | Sulfonated polyether sulphone block sulfonated polybutadiene proton exchange film and preparing method |
| CN105524268B (en) * | 2016-02-18 | 2017-09-15 | 中国工程物理研究院化工材料研究所 | Sulfonated polyether ketone copolymers of the group containing benzothiazole and preparation method thereof |
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| CN109880095B (en) * | 2019-02-18 | 2021-07-06 | 江苏冰城氢能科技有限公司 | High-temperature-resistant sulfonated polybenzothiazole imide proton exchange membrane and preparation method thereof |
| CN111234226B (en) * | 2020-03-20 | 2022-05-27 | 宁夏清研高分子新材料有限公司 | Sulfonated polyarylethersulfone and preparation method thereof |
| CN114015336A (en) * | 2021-11-12 | 2022-02-08 | 中山市诺必佳光学材料有限公司 | Scratch-resistant and wear-resistant folding-resistant explosion-proof water-based plastic replacement oil and preparation method thereof |
| CN114975999B (en) * | 2022-06-28 | 2023-11-28 | 河南工业大学 | Sulfonated polybenzothiazole-based cathode material for sodium ion battery and preparation method thereof |
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