CN101659747B - Method for synthesizing polybenzimidazole by taking ionic liquid as solvent - Google Patents
Method for synthesizing polybenzimidazole by taking ionic liquid as solvent Download PDFInfo
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- CN101659747B CN101659747B CN2009101967020A CN200910196702A CN101659747B CN 101659747 B CN101659747 B CN 101659747B CN 2009101967020 A CN2009101967020 A CN 2009101967020A CN 200910196702 A CN200910196702 A CN 200910196702A CN 101659747 B CN101659747 B CN 101659747B
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- 239000004693 Polybenzimidazole Substances 0.000 title claims abstract description 55
- 229920002480 polybenzimidazole Polymers 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002904 solvent Substances 0.000 title claims abstract description 29
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract 3
- 239000012024 dehydrating agents Substances 0.000 claims abstract 3
- 239000000047 product Substances 0.000 claims description 43
- -1 1-butyl- 3-methylimidazolium tetrafluoroborate Chemical compound 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 150000001412 amines Chemical group 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims 1
- GWQYPLXGJIXMMV-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C)=C1 GWQYPLXGJIXMMV-UHFFFAOYSA-M 0.000 claims 1
- QVRCRKLLQYOIKY-UHFFFAOYSA-M 1-methyl-3-prop-2-enylimidazol-1-ium;chloride Chemical compound [Cl-].C[N+]=1C=CN(CC=C)C=1 QVRCRKLLQYOIKY-UHFFFAOYSA-M 0.000 claims 1
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 claims 1
- 150000001642 boronic acid derivatives Chemical class 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 230000001988 toxicity Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000006068 polycondensation reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920000137 polyphosphoric acid Polymers 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 230000004927 fusion Effects 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 150000007520 diprotic acids Chemical class 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NTYJJOPFIAHURM-UHFFFAOYSA-N Histamine Chemical group NCCC1=CN=CN1 NTYJJOPFIAHURM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- YSTQDJNWDMBAOZ-UHFFFAOYSA-N [Br].C(C)N1CN(C=C1)C Chemical compound [Br].C(C)N1CN(C=C1)C YSTQDJNWDMBAOZ-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WWFKDEYBOOGHKL-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound Br.CCN1CN(C)C=C1 WWFKDEYBOOGHKL-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical group C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- ADQDTIAWIXUACV-UHFFFAOYSA-N CCCc1ccc(CC)cc1 Chemical compound CCCc1ccc(CC)cc1 ADQDTIAWIXUACV-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- FBWADIKARMIWNM-UHFFFAOYSA-N N-3,5-dichloro-4-hydroxyphenyl-1,4-benzoquinone imine Chemical compound C1=C(Cl)C(O)=C(Cl)C=C1N=C1C=CC(=O)C=C1 FBWADIKARMIWNM-UHFFFAOYSA-N 0.000 description 1
- YUDUIQNHAYCTQA-VAWYXSNFSA-N [O-][NH+](/C=C/[NH+]([O-])Oc1ccccc1)Oc1ccccc1 Chemical compound [O-][NH+](/C=C/[NH+]([O-])Oc1ccccc1)Oc1ccccc1 YUDUIQNHAYCTQA-VAWYXSNFSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229960001340 histamine Drugs 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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 the prior art and remedies the insufficiencies of the prior art.
Description
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
R
2For
, n=0～5, or-o-, or
The general structure of described dicarboxyl component composition is
R
1Form by a kind of in the following structure or any two kinds:
The ortho position, a position or contraposition;
1,4, prosposition, 2,6 or 2,7;
Or
X is:
N=0-10 wherein
Y is:
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, 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:
M=10～2000 wherein;
R
1Form by a kind of in the following structure or any two kinds:
Y is:
R
2For
N=0～5, or-o-, or
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:
R wherein
1, R
2, X such as preamble define.
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:
The structural formula of the dicarboxyl component composition that adopts is as follows:
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:
The structural formula of the dicarboxyl component composition that adopts is as follows:
With as above tetramines aromatic and the dicarboxyl component and the 1-butyl-3-methyl imidazolium tetrafluoroborate and the P of structure
2O5 with 1: 0.8: 20: 3 mol ratio joins 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:
The structural formula of the dicarboxyl component composition that adopts is as follows:
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:
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:
The structural formula of the dicarboxyl component composition that adopts is as follows:
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.
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