CN1250609C - Benzimidazole with sulfonate as side group and benzoxaazole copolymer and its preparation - Google Patents
Benzimidazole with sulfonate as side group and benzoxaazole copolymer and its preparation Download PDFInfo
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- CN1250609C CN1250609C CN 200410024690 CN200410024690A CN1250609C CN 1250609 C CN1250609 C CN 1250609C CN 200410024690 CN200410024690 CN 200410024690 CN 200410024690 A CN200410024690 A CN 200410024690A CN 1250609 C CN1250609 C CN 1250609C
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Abstract
The present invention provides a sulfonic acid (salt) side group containing copolymer of benzimidazole and benzoxazole and a preparation method thereof. 3, 3'-disulfonyl (salt)-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, aromatic tetra-amine and dihydroxyl aromatic diamine or hydrochloride thereof in a solution polycondensation mode in polyphosphoric acid, and the sulfonic acid (salt) side group containing copolymer of benzimidazole and benzoxazole, which has high thermal stability, can be obtained. The copolymer 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, the benzoglyoxaline of particularly a kind of band sulfonic acid (salt) side group and benzoxazole multipolymer 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 research of novel proton exchange membranes material has been subjected to 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.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 ketone, sulfonated polyether-ether-ketone, sulfonated polyether sulfone, sulfonated poly thioether sulfone and sulfonated polyimide etc.
Polybenzimidazole has excellent thermostability, chemical stability and dimensional stability, is the special engineering plastics of a class excellent combination property, after last century, be developed the sixties, has been used as the matrix resin of fiber, tackiness agent, porous plastics etc.1994, people's reported first such as Wainright phosphate-doped polybenzimidazole can be used for the discovery of proton exchange membrane.After this, the research of acid or alkali doping polybenzimidazole has caused investigator's great interest.Because advantages such as the thermotolerance, chemical stability and the chemical property that have excellence of this class film and methanol permeability are low, they have broad application prospects at high temperature PEMFC and direct methanol fuel cell field.
Different with the blend complex method of above-mentioned acid or alkali doping polybenzimidazole, people such as Bae (Bae J.M.; Et al.Solid State Ionics, 2002,147,189-194; Xavier Glipa; Et al.Solid State Ionics, 1997,97,323-331.) earlier with polybenzimidazole at lithium hydride and N, the effect of N-N,N-DIMETHYLACETAMIDE generates polyanion down, again with 1, and 4-butyl sultone and 1, small molecules such as 3-N-morpholinopropanesulfonic acid lactone reaction chain are respectively received the polybenzimidazole molecular backbone chain, generate side chain and have sulfonic sulfonated polyphenyl and imidazoles.This class graft type sulfonated polyphenyl and imidazoles film all have high proton conductivity under high temperature (160 ℃) or cold condition, yet adopt this grafted method, not only the time long, and the difficult control of sulfonation degree.
The another kind of method for preparing sulfonated polyphenyl and imidazoles is to adopt sulfonated aromatic dicarboxylic acid monomer and other dicarboxylic acid monomers and fragrant quaternary amine or its hydrochloride direct condensation and make.For example: people (Polymer Materials:Science ﹠amp such as Yoshimitsu Sakaguchi; Engineering 2001,84, and 899; JP 2002-201268) with business-like 5-sodium sulfonate m-phthalic acid and 2-sodium sulfonate terephthalic acid as sulfonated monomers, with 3,3 '-diaminobenzidine and 3,3 ', 4,4 '-tetramino sulfobenzide has synthesized good and high sulfonated polyphenyl and the imidazoles of proton conductivity of some solubility properties as the tetramines aromatic monomer.People (Journal of Polymer Science:PartA:Polymer Chemistry 2002 such as Asensio J.A., 40,3703-3710) with 5-sodium sulfonate m-phthalic acid and 1,2,4,5-tetramino benzene has synthesized sulfonated polyphenyl that thermal stability is good and electrical property is high and imidazoles.
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, the benzoglyoxaline and the benzoxazole multipolymer of band sulfonic acid (salt) side group of the Heat stability is good that synthetic sulfonation degree is controlled, their repeated structural unit is as follows:
(x+z)/(y+n)=0.98-1.02 wherein, 0＜x/ (x+z)≤100%, 0≤z/ (x+z)＜100%, 0＜y/ (y+n)＜100%, 0＜n/ (y+n)＜100%, 4＜m＜2000;
R
1Be hydrogen, lithium, sodium, potassium, caesium, magnesium, calcium, barium, lead or iron;
Ar
1Structure is as follows:
Wherein can include a kind of or two or more Ar in the repeated structural unit with the benzoglyoxaline of sulfonic acid (salt) side group and benzoxazole multipolymer
1Structure, and Ar
1Two imino-s in the structure can be cis or trans;
Ar
2Structure is as follows:
The ortho position, a position or contraposition:
The ortho position, a position or contraposition;
Wherein can include a kind of or two or more Ar in the repeated structural unit with the benzoglyoxaline of sulfonic acid (salt) side group and benzoxazole multipolymer
2Structure;
Ar
3Structure is as follows:
Or
Wherein can include a kind of or two or more Ar in the repeated structural unit with the benzoglyoxaline of sulfonic acid (salt) side group and benzoxazole multipolymer
3Structure.
The present invention prepares the benzoglyoxaline of band sulfonic acid (salt) side group and the method for benzoxazole multipolymer 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 aromatic series quaternary amine and dihydroxyl 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 sum of above-mentioned aromatic series quaternary amine and dihydroxyl 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 the benzoglyoxaline and the benzoxazole multipolymer of high-molecular weight band sulfonic acid (salt) side group; 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, wash with water repeatedly then to remove solvent remaining in the product, 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 the benzoglyoxaline and the benzoxazole multipolymer of band sulfonic acid (salt) side group.
The benzoglyoxaline and the used sulfonated monomers of benzoxazole multipolymer of anamorphic zone sulfonic acid of the present invention (salt) side group 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 used sulfonated monomers of the benzoglyoxaline of anamorphic zone sulfonic acid of the present invention (salt) side group and benzoxazole multipolymer is 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.
The benzoglyoxaline of anamorphic zone sulfonic acid of the present invention (salt) side group and the employed dihydroxyl aromatic diamines of benzoxazole multipolymer (or its hydrochloride) monomer have the dihydroxyl aromatic diamine monomers to have 2,5-dihydroxyl Ursol D, 4,6-dihydroxyl mphenylenediamine, 3,5-diamino-2,6-pyridine diphenol, 1,5-diamino-2, the 6-naphthalenediol, 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 or 1 of 4-, two [the 3-amino-4-hydroxy phenoxy group] benzene of 4-.
Used aromatic series quaternary amine (or its hydrochloride) monomer of the benzoglyoxaline of anamorphic zone sulfonic acid of the present invention (salt) side group and benzoxazole multipolymer has 1,2,4,5-tetramino benzene, 1,2,5,6-tetramino naphthalene, 3,3 '-diaminobenzidine, 3,3 ', 4,4 '-tetramino sulfobenzide, 3,3 ', 4,4 '-tetramino diphenyl sulfide, 3,3 ', 4,4 '-tetramino phenyl ether, 3,3 ', 4,4 '-tetramino benzophenone, 3,3 ', 4,4 '-tetramino ditane, 2, two [4-(3, the 4-diamino phenoxy) phenyl] propane of 2-, 1,4-two [3, the 4-diamino phenoxy] benzene, 2, two [3, the 4-diamino-phenyl] propane or 2 of 2-, two [3, the 4-diamino-phenyl] HFC-236fa of 2-.
Aromatics that the benzoglyoxaline of anamorphic zone sulfonic acid of the present invention (salt) side group and benzoxazole multipolymer are used or fragrant heterocyclic di-carboxylic acid, 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 sulfonic acid type benzoglyoxaline of the present invention and benzoxazole multipolymer is confirmed through Infrared spectroscopy, and its molecular weight and thermal stability are characterized by gel chromatography (GPC) and thermogravimetry (TGA) respectively.
The benzoglyoxaline of synthetic band sulfonic acid of the present invention (salt) side group and benzoxazole multipolymer 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 sulfonic acid type benzoglyoxaline and benzoxazole multipolymer
The hot weightless picture of Fig. 2 sulfonic acid type benzoglyoxaline and benzoxazole multipolymer
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 30ml 10% 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 benzimidazole imidazoles and benzoxazole multipolymer): 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 0.7999 gram 3; 3 '-diaminobenzidine (3.7332mmol); 0.1989 restrain 4; 6-diaminobenzene diphenol hydrochloride (0.9332mmol); 0.5717 restrain 4; 4 '-Dicarboxy diphenylsulfone (1.867mmol) and 1.3060 grams 3; 3 '-disulfonic acid base-4; 4 '-Dicarboxy diphenylsulfone (2.800mmol); 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 2.5752 gram sulfonation degree is 60% sodium sulfonate type benzoglyoxaline and benzoxazole multipolymer; yield is about 99.0%; the structure of product is confirmed through Infrared spectroscopy, and its molecular weight and thermal stability are characterized by GPC and TGA respectively.
With N, dinethylformamide is made solvent, and polystyrene is a standard specimen, is 70000 in 70 ℃ of number-average molecular weights that record sodium sulfonate type benzoglyoxaline and benzoxazole multipolymer.By solution casting film forming and dilute hydrochloric acid exchange, can obtain good sulfonic acid type benzoglyoxaline of toughness and benzoxazole copolymer film, its infrared spectrogram is seen Fig. 1, therefrom can observe the following characteristics absorption band:
～3400cm
-1-N-H and-O-H stretching vibration absorption band;
3094.6cm
-1Fragrance-C-H stretching vibration absorption band;
1632.5cm
-1In the five-membered ring-C=N-stretching vibration absorption band;
1240.7,1191.2 ,-SO
3O=S=O stretching vibration absorption band among the H;
1118.7，1029.2cm
-1
1073.0cm
-1In the five-membered ring=C-O-C stretching vibration absorption band.
808.3cm
-1The absorption band of imidazolyl heterocycle;
694.5cm
-1-S-O stretching vibration absorption band.
This sulfonation degree is that the thermal stability of 60% sulfonic acid type benzoglyoxaline and benzoxazole multipolymer adopts the TGA2050 thermogravimetric analyzer 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 446.3 ℃ and 472.8 ℃, and its maximum weight loss rate temperature is 476.4 ℃.
Embodiment 3 (preparation of sulfonated benzimidazole imidazoles and benzoxazole multipolymer): 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 0.7999 gram 3; 3 '-diaminobenzidine (3.7332mmol); 0.1989 restrain 4; 6-diaminobenzene diphenol hydrochloride (0.9332mmol); 0.3101 gram m-phthalic acid (1.867mmol) and 1.3060 grams 3; 3 '-disulfonic acid base-4; 4 '-Dicarboxy diphenylsulfone (2.800mmol); 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 2.3209 gram sulfonation degree is 60% sodium sulfonate type benzoglyoxaline and benzoxazole multipolymer; yield is about 99.2%; the structure of product is confirmed through Infrared spectroscopy, and its thermal stability TGA characterizes.
With N, dinethylformamide is made solvent, and polystyrene is a standard specimen, is 53000 in 70 ℃ of number-average molecular weights that record sodium sulfonate type benzoglyoxaline and benzoxazole multipolymer.Can also observe sulfonic characteristic absorption band in the infrared spectrogram of this sulfonic acid type benzoglyoxaline and benzoxazole multipolymer.
This sulfonation degree is that the thermal stability of 60% sulfonic acid type benzoglyoxaline and benzoxazole multipolymer adopts the TGA2050 thermogravimetric analyzer to characterize, testing method is with embodiment 1, the temperature of its weightlessness 5% and 10% o'clock correspondence is respectively 449.7 ℃ and 473.8 ℃, and its maximum weight loss rate temperature is 482.7 ℃.
Claims (9)
1. benzoglyoxaline and benzoxazole multipolymer with a sulfonic acid or a pendant sulfonate is characterized in that having following repeated structural unit:
(x+z)/(y+n)=0.98-1.02 wherein, 0＜x/ (x+z)≤100%, 0≤z/ (x+z)＜100%, 0＜y/ (y+n)＜100%, 0＜n/ (y+n)＜100%, 4＜m＜2000;
R
1Be hydrogen, lithium, sodium, potassium, caesium, magnesium, calcium, barium, lead or iron;
Ar
1Structure is as follows:
Or
Wherein can include a kind of or two or more Ar in the repeated structural unit with the benzoglyoxaline of sulfonic acid or pendant sulfonate and benzoxazole multipolymer
1Structure, and Ar
1Two imino-s in the structure can be cis or trans; Ar
2Structure is as follows:
1,4, prosposition, 2,6 or 2,7;
Or
Ar
3Structure 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 Ar in the repeated structural unit with the benzoglyoxaline of sulfonic acid or pendant sulfonate and benzoxazole multipolymer
3Structure.
2. preparation method with the benzoglyoxaline and the benzoxazole multipolymer of sulfonic acid or pendant sulfonate 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 aromatic series quaternary amine and dihydroxyl 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 sum of above-mentioned aromatic series quaternary amine and dihydroxyl 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 150-250 ℃, 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, wash with water repeatedly then to remove solvent remaining in the product, 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 the benzoglyoxaline and the benzoxazole multipolymer of band sulfonic acid or pendant sulfonate.
3. the benzoglyoxaline of band sulfonic acid according to claim 2 or pendant sulfonate and the preparation method of benzoxazole multipolymer 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 benzoglyoxaline of band sulfonic acid according to claim 2 or pendant sulfonate and the preparation method of benzoxazole multipolymer, it is characterized in that employed dihydroxyl aromatic diamine monomers is selected from 2,5-dihydroxyl Ursol D, 4,6-dihydroxyl mphenylenediamine, 3,5-diamino-2,6-pyridine diphenol, 1,5-diamino-2, the 6-naphthalenediol, 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 or 1 of 4-, two [the 3-amino-4-hydroxy phenoxy group] benzene of 4-.
5. the benzoglyoxaline of band sulfonic acid according to claim 2 or pendant sulfonate and the preparation method of benzoxazole multipolymer is characterized in that employed aromatic series quaternary amine monomer is selected from 1,2,4,5-tetramino benzene, 1,2,5,6-tetramino naphthalene, 3,3 '-diaminobenzidine, 3,3 ', 4,4 '-tetramino sulfobenzide, 3,3 ', 4,4 '-tetramino diphenyl sulfide, 3,3 ', 4,4 '-tetramino phenyl ether, 3,3 ', 4,4 '-tetramino benzophenone, 3,3 ', 4,4 '-tetramino ditane, 2,2-is two, and [4-(3, the 4-diamino phenoxy) phenyl] propane, 1, two [3, the 4-diamino phenoxy] benzene of 4-, 2,2-two [3, the 4-diamino-phenyl] propane or 2, two [3, the 4-diamino-phenyl] HFC-236fa of 2-.
6. the benzoglyoxaline of band sulfonic acid according to claim 2 or pendant sulfonate and the preparation method of benzoxazole multipolymer, 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.
7. the benzoglyoxaline of band sulfonic acid according to claim 2 or pendant sulfonate and the preparation method of benzoxazole multipolymer, the content that it is characterized in that Vanadium Pentoxide in FLAKES in the polyphosphoric acid is between 83-89wt%.
8. the benzoglyoxaline of band sulfonic acid according to claim 2 or pendant sulfonate and the preparation method of benzoxazole multipolymer is characterized in that thinner is selected from phosphoric acid, polyphosphoric acid, methylsulfonic acid or the vitriol oil; Its quality consumption is the 0.1-200 times of add polyphosphoric acid.
9. the benzoglyoxaline of band sulfonic acid according to claim 2 or pendant sulfonate and the preparation method of benzoxazole multipolymer is characterized in that precipitation agent is selected from water, methyl alcohol, ethanol, tetrahydrofuran (THF) or ether.
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