CN101659747A - Method for synthesizing polybenzimidazole by taking ionic liquid as solvent - Google Patents

Method for synthesizing polybenzimidazole by taking ionic liquid as solvent Download PDF

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CN101659747A
CN101659747A CN200910196702A CN200910196702A CN101659747A CN 101659747 A CN101659747 A CN 101659747A CN 200910196702 A CN200910196702 A CN 200910196702A CN 200910196702 A CN200910196702 A CN 200910196702A CN 101659747 A CN101659747 A CN 101659747A
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polybenzimidazole
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ionic liquid
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CN101659747B (en
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文志伟
王彪
李江
王华平
张玉梅
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Donghua University
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Abstract

The invention relates to a method for synthesizing polybenzimidazole, in particular to a method for synthesizing polybenzimidazole by taking ionic liquid as a solvent. The method comprises the following steps: adding at least one of aromatic tetramine, dicarboxyl constituent compound, ionic liquid and dehydrating agent to a reaction vessel; mixing under the nitrogen protection, heating at a constant temperature of 140 DEG C for 0-5 hours; carrying out prepolymerization reaction to obtain a prepolymer; subsequently, continuously raising the temperature to 160-220 DEG C, and enabling the prepolymer to stay for 5-30 hours, and finally obtaining a polybenzimidazole product. The invention solves the problems of the toxicity and the corrosivity of the solvent during the operating process of theprior art and remedies the insufficiencies of the prior art.

Description

With the method for ionic liquid as the synthetic polybenzimidazole of solvent
Technical field
The present invention relates to a kind of method of synthetic polybenzimidazole, particularly relate to a kind of with the method for ionic liquid as the synthetic polybenzimidazole of solvent.
Background technology
Polybenzimidazole 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 that fiber, tackiness agent, porous plastics and laminated product or fiber winding product are used.Particularly the polybenzimidazole of full aromatic structure has outstanding mechanical property, dielectric properties, outstanding high temperature resistance and good fiber and film performance.Because polybenzimidazole has excellent thermostability, chemical stability and dimensional stability, the research of acid or alkali doping polybenzimidazole proton exchange membrane has caused investigator's great interest.
The synthetic method of polybenzimidazole mainly contains four kinds at present: the parent method, being that tetramine monomers is synthetic does not also proceed to before the final step, when promptly obtaining binary nitro and binary amido substitution product, directly this material and diprotic acid are reacted, obtain the parent of polybenzimidazole, afterwards this material is reduced, making nitroreduction is amido, again this reactant is carried out the polymkeric substance that high-temperature heat treatment obtains polybenzimidazole; The nucleophilic substitution method is by synthesizing the intermediate that the nucleophilic substitution position is arranged that contains the benzoglyoxaline ring earlier, obtaining polybenzimidazole with pure reaction then under alkaline condition; Melt-polycondensation promptly makes monomer tetramino biphenyl and the polycondensation of m-phthalic acid benzene methyl fusion body synthesize polybenzimidazole under protection of inert gas by a certain percentage; Solution polymerization process is earlier tetramine or tetramine hydrochloride to be added in the polyphosphoric acid; nitrogen protection; heated and stirred makes it dissolving; add the diprotic acid or derivatives thereof then; in 200 ℃ of insulation reaction 12 hours; reaction is poured reaction mixture in excessive water precipitating after finishing, and through washing, drying, promptly gets product again.
During with the synthetic polybenzimidazole of parent method, though avoided the synthetic of tetramine, the experiment condition of synthetic parent is comparatively harsh, and temperature required higher when being converted into polybenzimidazole by the polybenzimidazole parent.The advantage of nucleophilic substitution method is that reaction monomers more easily prepares, and has enlarged available polybenzimidazole kind.Shortcoming is relative direct polycondensation method, and the nucleophilic reaction method requires more strict to the removal of the small-molecule substance that generates in the reaction process.
Two kinds of methods commonly used now are melt-polycondensation and solution polycondensation, and melt-polycondensation can be divided into two classes: single stage method and two-step approach.The two step method melt phase polycondensation is that tetramine, diprotic acid or derivatives thereof are reacted about 220 ℃ with equimolar amount, and product begins foaming more than 250 ℃, stops to stir, and the thing that will foam is incubated about 1.5 hours about 290 ℃, obtain prepolymer.Resulting foaming shape prepolymer is cooled to room temperature, grinds, be reentered in the reactor, nitrogen protection was reacted 3 hours down at 380 ℃, thereby is obtained high-molecular weight PBI.Solid state polymerization 2-3 hour, make the granular PBI resin of yellowish brown.The single stage method melt polymerization be with tetramine, diprotic acid or derivatives thereof with equimolar quantitative response, temperature is warming up to 310 ℃ from 200 ℃, stirring velocity increases with viscosity and slows down in this process, finally stop to stir, and insulation 45min, be warming up to again about 415 ℃, insulation 1h promptly obtains the PBI product.
Both key distinctions: the principal monomer of two step method is 3,3 ', 4,4 '-tetramine biphenyl (DAB) and phenylbenzene between phenyl ester (DPIP), the by product that obtains is phenol and water, foams by the reaction process decision, not necessarily will use catalyzer, cost is higher; The principal monomer of single stage method is 3,3 ', 4,4 '-tetramine biphenyl (DAB) and m-phthalic acid (IPA), the by product that obtains is a water, does not foam in the reaction process, must use catalyzer, cost is medium, and the temperature of reaction of two kinds of methods and time relation are also inconsistent.
Solution polymerization process is earlier tetramine or tetramine hydrochloride to be added in the polyphosphoric acid (PPA); nitrogen protection; heated and stirred makes it dissolving; add the diprotic acid or derivatives thereof then; in 200 ℃ of insulation reaction 12h; reaction is poured reaction mixture in excessive water precipitating after finishing, and through washing, drying, promptly gets product [10] again.
The advantage of comparing solution polymerization with melt polymerization has: (1) single stage method replaces two step method; (2) require not tight to temperature control; (3) the polar group in the solvent can make the product solvation of transition state, thereby reduces activation energy, makes reaction to finish in lower temperature with in than the short time, thereby has reduced crosslinked possibility; (4) in entire reaction course, can guarantee the reactant thorough mixing, thereby active end group can be contacted well, and end group might can not be contacted by embedding in melt polycondensation reaction; (5) Fan Ying by product can be taken out of reaction system by the ebullient solvent as water, phenol etc., then is comprised in the system raising of impact polymer molecular weight in melt phase polycondensation; (6) monomer in solution state or the suspended state is than easier removing in molten state.
Solution polymerization has many advantages, so solution polymerization is used to prepare polybenzimidazole more.But in the general experiment, can adopt polyphosphoric acid as reaction solvent.But polyphosphoric acid is corrosive, and decomposes produces the phosphorus oxide flue gas of severe toxicity, therefore is inconvenient to operate.The polyphosphoric acid viscosity is very big and can exert an influence to polyreaction with the miscible ortho-phosphoric acid that is hydrolyzed to of water, has influenced the synthetic of high-molecular weight polybenzimidazole.
Summary of the invention
The present invention is exactly a new solution that proposes at the problems referred to above, the purpose of this invention is to provide a kind of method of synthetic polybenzimidazole, just provides a kind of with the method for ionic liquid as the synthetic polybenzimidazole of solvent.The invention solves the toxicity and the corrosion problems of solvent in the prior art operating process, remedied the deficiencies in the prior art.
Of the present invention with the method for ionic liquid as the synthetic polybenzimidazole of solvent, may further comprise the steps:
The first step: at least a tetramines aromatic and dicarboxyl component composition, ionic liquid and dewatering agent are joined in the reaction vessel stirring reaction under protection of nitrogen gas with 1: 0.8～1.5: 20～50: 3～8 mol ratio; Described tetramines aromatic contains two histamine substituting groups, and the amine substituting group in every group is positioned on relative to each other the ortho position, and its general structure is
Figure G2009101967020D00031
R 2For N=0～5,
Figure G2009101967020D00033
The general structure of described dicarboxyl component composition is
Figure G2009101967020D00034
R 1Form by a kind of in the following structure or any two kinds:
Figure G2009101967020D00035
Wherein: n=0～28;
Figure G2009101967020D00036
The ortho position, a position or contraposition;
Figure G2009101967020D00037
The ortho position, a position or contraposition;
Figure G2009101967020D00038
1,4, prosposition, 2,6 or 2,7;
Figure G2009101967020D00039
2,2 ' position, 3,3 ' position or 4,4 ' position, Y=-O wherein, S, SO 2, CO, CH 2, C (CH 3) 2Or C (CF 3) 2
Figure G2009101967020D000310
Y is H,
Figure G2009101967020D000311
N=0～10 wherein;
Second step: when temperature rises to 140～150 ℃, stop to heat up, prepolymerization reaction is carried out in isothermal reaction 1～5 hour, obtains prepolymer;
The 3rd step: continue elevated temperature afterwards, when treating that temperature reaches 160～220 ℃ of temperature of reaction, allow prepolymer stop 5～30 hours, get final product the end product polybenzimidazole.
As optimized technical scheme:
Wherein, aforesaid with the method for ionic liquid as the synthetic polybenzimidazole of solvent, described ionic liquid is a kind of in 1-methyl-3-butyl imidazole villaumite, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-Methylimidazole bromine salt, 1-allyl group-3-Methylimidazole villaumite or the 1-butyl-3-methyl imidazolium tetrafluoroborate.
Aforesaid with the method for ionic liquid as the synthetic polybenzimidazole of solvent, described dewatering agent is P 2O 5
Aforesaid with the method for ionic liquid as the synthetic polybenzimidazole of solvent, described solvent is deionized water, acetone or dehydrated alcohol.
Aforesaid with the method for ionic liquid as the synthetic polybenzimidazole of solvent, allow prepolymer stop 5～30 hours in described the 3rd step, the fusion mashed prod is taken out the back product is washed till in the container, use alkaline solution adjust pH to 7 then, the product suction filtration is come out with solvent; The product that suction filtration is come out places apparatus,Soxhlet's, continues to carry out extracting with solvent, with the impurity in the wash products; Product after the extracting is taken out, place vacuum drying oven dry, can obtain purified end product polybenzimidazole.
Of the present invention with the method for ionic liquid as the synthetic polybenzimidazole of solvent, the polybenzimidazole of preparation is the repeated structural unit with following general formula:
Figure G2009101967020D00041
M=10～2000 wherein;
R 1Form by a kind of in the following structure or any two kinds:
Figure G2009101967020D00042
Wherein: n=0～28; The ortho position, a position or contraposition;
Figure G2009101967020D00044
The ortho position, a position or contraposition; 1,4, prosposition, 2,6 or 2,7;
Figure G2009101967020D00046
2,2 ' position, 3,3 ' position or 4,4 ' position, Y=-O wherein, S, SO 2, CO, CH 2, C (CH 3) 2Or C (CF 3) 2
Figure G2009101967020D00047
R 2For
Figure G2009101967020D00048
N=0～5,
Figure G2009101967020D00049
Following universal equation formula has illustrated in formation to have the condensation reaction that takes place in the polybenzimidazole of above-mentioned general formula repeated structural unit:
Figure G2009101967020D00051
R wherein 1, R 2Define as preamble, Y is H,
Figure G2009101967020D00052
N=0～10 wherein.
The invention has the beneficial effects as follows:
Of the present invention with the method for ionic liquid as the synthetic polybenzimidazole of solvent, utilize ionic liquid to come the polybenzimidazole of synthetic macromolecule amount as solvent, avoided the toxicity and the corrosion problems of solvent in the operating process, ionic liquid zero vapour pressure, pollution-free, easy recovery, solved the environmental problem of bringing with polyphosphoric acid, and the problem that has solved many synthetic macromolecules of polyphosphoric acid amount polybenzimidazole existence influence.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment one
With 1-butyl-3-Methylimidazole villaumite is the synthetic polybenzimidazole of solvent
The structural formula of the tetramines aromatic that adopts is as follows:
Figure G2009101967020D00053
The structural formula of the dicarboxyl component composition that adopts is as follows:
Figure G2009101967020D00054
With as above tetramines aromatic and the dicarboxyl component composition and the 1-butyl-3-Methylimidazole villaumite and the P of structure 2O 5With 1: 1: 25: 4 mol ratio joined in the reaction vessel, placed in the oil bath pan stirring reaction under protection of nitrogen gas.When temperature rises to 140 ℃, stop to heat up, reacted 3 hours, carry out prepolymerization reaction, obtain prepolymer.Continue elevated temperature, when treating that temperature reaches 200 ℃, allow prepolymer stop 30 hours, after question response finishes, the fusion mashed prod is taken out the back product is washed till in the beaker, use alkaline solution adjust pH to 7 then, the product suction filtration is come out with deionized water.The product that suction filtration is come out places apparatus,Soxhlet's, continues to carry out extracting with acetone, with the impurity in the wash products.Product after the extracting is taken out, place vacuum drying oven, dried overnight can get the polybenzimidazole end product.
Embodiment two
With 1-butyl-3-methyl imidazolium tetrafluoroborate is the synthetic polybenzimidazole of solvent
The structural formula of the tetramines aromatic that adopts is as follows:
Figure G2009101967020D00061
The structural formula of the dicarboxyl component composition that adopts is as follows:
Figure G2009101967020D00062
With as above tetramines aromatic and the dicarboxyl component and the 1-butyl-3-methyl imidazolium tetrafluoroborate and the P of structure 2O 5With 1: 0.8: 20: 3 mol ratio joined in the reaction vessel, in oil bath pan under protection of nitrogen gas stirring reaction.When temperature rises to 146 ℃, stop to heat up, reacted 1 hour, carry out prepolymerization reaction, obtain prepolymer.Continue elevated temperature, when treating that temperature reaches 180 ℃ of temperature of reaction, allow prepolymer stop 5 hours, after question response finishes, the fusion mashed prod is taken out the back product is washed till in the beaker, use alkaline solution adjust pH to 7 then, the product suction filtration is come out with deionized water.The product that suction filtration is come out places apparatus,Soxhlet's, continues to carry out extracting with acetone, with the impurity in the wash products.Product after the extracting is taken out, place vacuum drying oven, dried overnight can get the polybenzimidazole end product.
Embodiment three
With 1-ethyl-3-Methylimidazole bromine salt is the synthetic polybenzimidazole of solvent
The structural formula of the tetramines aromatic that adopts is as follows:
Figure G2009101967020D00063
The structural formula of the dicarboxyl component composition that adopts is as follows:
Figure G2009101967020D00071
With as above tetramines aromatic and the dicarboxyl component and the 1-ethyl-3-Methylimidazole Bromide and the P of structure 2O 5With 1: 1.5: 50: 8 mol ratio joined in the reaction vessel, in oil bath pan under protection of nitrogen gas stirring reaction.When temperature rises to 150 ℃, stop to heat up, reacted 2 hours, carry out prepolymerization reaction, obtain prepolymer.Continue elevated temperature, when treating that temperature reaches 220 ℃, allow prepolymer stop 20 hours, after question response finishes, the fusion mashed prod is taken out the back product is washed till in the beaker, use alkaline solution adjust pH to 7 then, the product suction filtration is come out with deionized water.The product that suction filtration is come out places apparatus,Soxhlet's, continues to carry out extracting with acetone, with the impurity in the wash products.Product after the extracting is taken out, place vacuum drying oven, dried overnight can get the polybenzimidazole end product.
Embodiment four
With 1-allyl group-3-Methylimidazole villaumite is the synthetic polybenzimidazole of solvent
The structural formula of the tetramines aromatic that adopts is as follows:
The structural formula of the dicarboxyl component composition that adopts is as follows:
Figure G2009101967020D00073
With as above tetramines aromatic and the dicarboxyl component and the 1-allyl group-3-Methylimidazole muriate and the P of structure 2O 5With 1: 1.2: 30: 6 mol ratio joined in the reaction vessel, in oil bath pan under protection of nitrogen gas stirring reaction.When temperature rises to 145 ℃, stop to heat up, reacted 5 hours, carry out prepolymerization reaction, obtain prepolymer.Continue elevated temperature, when treating that temperature reaches 160 ℃, allow prepolymer stop 26 hours, after question response finishes, the fusion mashed prod is taken out the back product is washed till in the beaker, use alkaline solution adjust pH to 7 then, the product suction filtration is come out with deionized water.The product that suction filtration is come out places apparatus,Soxhlet's, continues to carry out extracting with acetone, with the impurity in the wash products.Product after the extracting is taken out, place vacuum drying oven, dried overnight can get the polybenzimidazole end product.
Embodiment five
With 1-butyl-3-methyl imidazolium tetrafluoroborate is the synthetic polybenzimidazole of solvent
The structural formula of the tetramines aromatic that adopts is as follows:
Figure G2009101967020D00081
The structural formula of the dicarboxyl component composition that adopts is as follows:
Figure G2009101967020D00082
With as above tetramines aromatic and the dicarboxyl component and the 1-butyl-3-methyl imidazolium tetrafluoroborate and the P of structure 2O 5With 1: 0.9: 40: 5 mol ratio joined in the reaction vessel, in oil bath pan under protection of nitrogen gas stirring reaction.When temperature rises to 143 ℃, stop to heat up, prepolymerization reaction is carried out in isothermal reaction 4 hours, obtains prepolymer.Continue elevated temperature, when treating that temperature reaches 200 ℃ of temperature of reaction, allow prepolymer stop 15 hours, after question response finishes, the fusion mashed prod is taken out the back product is washed till in the beaker, use alkaline solution adjust pH to 7 then, the product suction filtration is come out with deionized water.The product that suction filtration is come out places apparatus,Soxhlet's, continues to carry out extracting with acetone, with the impurity in the wash products.Product after the extracting is taken out, place vacuum drying oven, dried overnight can get the polybenzimidazole end product.

Claims (5)

1. with the method for ionic liquid, it is characterized in that may further comprise the steps as the synthetic polybenzimidazole of solvent:
The first step: at least a tetramines aromatic and dicarboxyl component composition, ionic liquid and dewatering agent are joined in the reaction vessel with 1: 0.8～1.5: 20～50: 3～8 mol ratio, again reaction vessel is placed in the oil bath pan stirring reaction under protection of nitrogen gas; Described tetramines aromatic contains two histamine substituting groups, and the amine substituting group in every group is positioned on relative to each other the ortho position, and its general structure is
Figure A2009101967020002C1
R 2For
Figure A2009101967020002C2
N=0～5, or-o-, or
Figure A2009101967020002C3
The general structure of described dicarboxyl component composition is
Figure A2009101967020002C4
R 1Form by a kind of in the following structure or any two kinds:
Figure A2009101967020002C5
Wherein: n=0～28; The ortho position, a position or contraposition;
Figure A2009101967020002C7
The ortho position, a position or contraposition;
Figure A2009101967020002C8
1,4, prosposition, 2,6 or 2,7;
2,2 ' position, 3,3 ' position or 4,4 ' position, Y=-O wherein, S, SO 2, CO, CH 2, C (CH 3) 2Or C (CF 3) 2
Figure A2009101967020002C10
Y is H, N=0～10 wherein
Second step: when temperature rises to 140～150 ℃, stop to heat up, prepolymerization reaction is carried out in isothermal reaction 1～5 hour, obtains prepolymer;
The 3rd step: continue elevated temperature, treat that temperature reaches 160-220 ℃, allow prepolymer stop 5～30 hours, get final product the end product polybenzimidazole.
2. as claimed in claim 1 with the method for ionic liquid as the synthetic polybenzimidazole of solvent, it is characterized in that described ionic liquid is a kind of in 1-methyl-3-butyl imidazole villaumite, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-Methylimidazole bromine salt, 1-allyl group-3-Methylimidazole villaumite or the 1-butyl-3-methyl imidazolium tetrafluoroborate.
3. as claimed in claim 1 with the method for ionic liquid as the synthetic polybenzimidazole of solvent, it is characterized in that described dewatering agent is P 2O 5
4. as claimed in claim 1 with the method for ionic liquid as the synthetic polybenzimidazole of solvent, it is characterized in that described solvent is deionized water, acetone or dehydrated alcohol.
5. as claimed in claim 1 with the method for ionic liquid as the synthetic polybenzimidazole of solvent, it is characterized in that, allow prepolymer stop 5～30 hours in described the 3rd step, the fusion mashed prod is taken out the back to be washed till product in the container with solvent, use alkaline solution adjust pH to 7 then, the product suction filtration is come out; The product that suction filtration is come out places apparatus,Soxhlet's, continues to carry out extracting with solvent, with the impurity in the wash products; Product after the extracting is taken out, place vacuum drying oven dry, can obtain purified end product polybenzimidazole.
CN2009101967020A 2009-09-29 2009-09-29 Method for synthesizing polybenzimidazole by taking ionic liquid as solvent Expired - Fee Related CN101659747B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102776790A (en) * 2012-07-10 2012-11-14 东华大学 Waterless dyeing method of dispersed dye
CN103769031A (en) * 2014-02-24 2014-05-07 北京中聚科技有限公司 Reaction kettle for polybenzimidazole fusion synthesis
CN109021012A (en) * 2018-08-01 2018-12-18 江苏理工学院 A kind of synthesis technology of pyridoxime 5'-phosphate

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102776790A (en) * 2012-07-10 2012-11-14 东华大学 Waterless dyeing method of dispersed dye
CN103769031A (en) * 2014-02-24 2014-05-07 北京中聚科技有限公司 Reaction kettle for polybenzimidazole fusion synthesis
CN103769031B (en) * 2014-02-24 2016-05-18 北京中聚科技有限公司 The synthetic reactor of using of a kind of polybenzimidazoles melting
CN109021012A (en) * 2018-08-01 2018-12-18 江苏理工学院 A kind of synthesis technology of pyridoxime 5'-phosphate
CN109021012B (en) * 2018-08-01 2021-04-20 南通香地生物有限公司 Synthesis process of pyridoxal 5' -phosphate

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