CN105985521B - A kind of polybenzimidazoles acid imide and preparation method thereof - Google Patents
A kind of polybenzimidazoles acid imide and preparation method thereof Download PDFInfo
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- CN105985521B CN105985521B CN201510056614.6A CN201510056614A CN105985521B CN 105985521 B CN105985521 B CN 105985521B CN 201510056614 A CN201510056614 A CN 201510056614A CN 105985521 B CN105985521 B CN 105985521B
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- 0 CC(C)(*)[n]1c(ccc(-c(cc2)cc3c2nc[n]3-c(cc2C(N3c(cc4)ccc4Oc4ccc(C(C)(*)c(cc5)ccc5Oc(cc5)ccc5N(C(c5ccc(C(C)(*)*)cc55)=O)C5=O)cc4)=O)ccc2C3=N)c2)c2nc1 Chemical compound CC(C)(*)[n]1c(ccc(-c(cc2)cc3c2nc[n]3-c(cc2C(N3c(cc4)ccc4Oc4ccc(C(C)(*)c(cc5)ccc5Oc(cc5)ccc5N(C(c5ccc(C(C)(*)*)cc55)=O)C5=O)cc4)=O)ccc2C3=N)c2)c2nc1 0.000 description 1
- KMGVOJQEQVDNQS-UHFFFAOYSA-N CC(C)(c(cc1)ccc1Oc(cc1)ccc1N(C(c(c1c2)ccc2F)O)C1=O)c(cc1)ccc1Oc(cc1)ccc1N(C(c(cc1)c2cc1F)=O)C2=O Chemical compound CC(C)(c(cc1)ccc1Oc(cc1)ccc1N(C(c(c1c2)ccc2F)O)C1=O)c(cc1)ccc1Oc(cc1)ccc1N(C(c(cc1)c2cc1F)=O)C2=O KMGVOJQEQVDNQS-UHFFFAOYSA-N 0.000 description 1
- ZSIACQWHDVUCHB-UHFFFAOYSA-N Cc(c(C)c1)ccc1S(c1cc(C)c(C)cc1)(=O)=O Chemical compound Cc(c(C)c1)ccc1S(c1cc(C)c(C)cc1)(=O)=O ZSIACQWHDVUCHB-UHFFFAOYSA-N 0.000 description 1
- HYMNWZVNHRYZRC-UHFFFAOYSA-N O=[O](c1ccccc1)(c1ccccc1)=O Chemical compound O=[O](c1ccccc1)(c1ccccc1)=O HYMNWZVNHRYZRC-UHFFFAOYSA-N 0.000 description 1
- MSQGYVACVAASTG-UHFFFAOYSA-N c1nc(cc(cc2)-c(cc3)cc4c3nc[nH]4)c2[nH]1 Chemical compound c1nc(cc(cc2)-c(cc3)cc4c3nc[nH]4)c2[nH]1 MSQGYVACVAASTG-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention provides a kind of polybenzimidazoles acid imide, structural formula is：Wherein, m is greater than or equal to 1 integer, and n is greater than or equal to 0 integer；Ar1Group connects two imidazole rings and forms benzimidazole group, Ar2It is the residue of diamine compounds, Ar3It is the residue of diphenols compound；Benzimidazole group be present in acid imide phenyl ring the positions 3- and/or 4-；Oxygen atom be present in acid imide phenyl ring the positions 3- and/or 4-.The present invention uses benzimidazole, biphenol monomer and disubstituted dant monomer for raw material, and the polybenzimidazoles acid imide is prepared through aromatic nucleophilic substitution reaction.The polybenzimidazoles acid imide has the characteristics that heat-resist, dissolubility is good, processability is good, good mechanical property, has good application prospect in fields such as heat safe engineering plastics, proton exchange membrane, fiber, adhesive, coating and advanced composite materials.
Description
Technical field
The invention belongs to polyimides preparation method technical fields, and in particular to a kind of polybenzimidazoles acid imide and its system
Preparation Method.
Background technology
Polyimides is the resin material of a kind of excellent combination property, has good thermal stability, excellent mechanicalness
Energy, preferable dimensional stability, excellent chemical stability, high-breakdown-voltage, low-k, high flame retardant, low bulk system
The advantages that number, it is widely used in the high-tech areas such as electronic apparatus, aerospace, automobile, chemical machinery.
Polybenzimidazoles is the high performance engineering plastics of a kind of excellent combination property, especially its heat resistance and mechanical performance
It is prominent, it is widely used in the fields such as aerospace, electronic apparatus, fuel battery proton exchange film, existing oneself becomes national economy, point
The important materials of end technology and new high-tech industry.
It is combined to obtain polybenzimidazoles with polyimides currently, numerous research institutions have carried out in relation to benzimidazole unit
The research of acid imide material has simultaneously obtained related research result, such as Nippon Mektron KK CN1446840A, Beijing
Work university martial virtue treasure CN102345177A, Donghua University Zhang Qinghua CN102604091A, the seas Donghua University Yu Xin
CN102942310A and CN103102796A, Jilin University report some in the patent documents such as dawn intelligent CN103422253A and contain
The polyimide material of benzimidazole unit.But these materials are all made of the dianhydride containing glyoxaline structure or contain imidazoles knot
The diamines of structure is prepared with conventional diamines or dianhydride polymerisation, the preparation method complex steps, complicated for operation, is significantly limited
The research and application of material.
Invention content
The present invention provides a kind of polybenzimidazoles acid imides to be suitble to good heat resistance and mechanical performance
Injection molding, extrusion, molding, melt spinning and solution-polymerized SBR processing, in heat safe engineering plastics, proton exchange membrane, fiber, gluing
The related fields such as agent, coating and advanced composite material have a good application prospect.
The imido method of the polybenzimidazoles is prepared the present invention also provides a kind of, this method is coupled nucleophilic using C-N
N-H keys on simultaneously imidazole ring are polymerize to form polybenzimidazoles by substitution reaction by nucleophilic displacement of fluorine with disubstituted dant monomer
Acid imide.
The structural formula of polybenzimidazoles imide resin provided by the invention is as follows：
Wherein, m is greater than or equal to 1 integer, and n is greater than or equal to 0 integer；Ar1Group connects two imidazole rings
Form benzimidazole group, Ar2It is the residue of diamine compounds, Ar3It is the residue of diphenols compound；Benzimidazole group
Be present in acid imide phenyl ring the positions 3- and/or 4-；Oxygen atom be present in acid imide phenyl ring the positions 3- and/or 4-.
Preferably, m, n value in structure above are the integers between 10 to 1000.
The Ar1Can be one or more of following groups：
The Ar2Can be one or more of following groups：
The Ar3Can be one or more of following groups：
That is, the present invention introduces benzimidazole unit in the stiff backbone of polyimides, obtained polybenzimidazoles acyl is sub-
Polyimide resin has good heat resistance and mechanical performance.When solvent is N-Methyl pyrrolidone, polybenzimidazoles acid imide exists
In the solvent when a concentration of 0.5g/dL, by determination of ubbelohde viscometer its 30 DEG C logarithmic viscosity number be 0.16dL/g~
1.20dL/g, preferably 0.3dL/g~0.8dL/g, more preferably 0.35dL/g~0.55dL/g.Pass through differential scanning calorimetry
It is 180 DEG C~350 DEG C to measure its glass transition temperature；Preferably 200 DEG C~340 DEG C；More preferably 250 DEG C~330 DEG C.It is logical
It is 400 DEG C~550 DEG C to cross thermal gravimetric analyzer and measure its 5% heat decomposition temperature；Preferably 420 DEG C~520 DEG C；More preferably
450 DEG C~500 DEG C.Tensile stress is 70MPa~120MPa, preferably 80~110MPa；Stretch modulus be 2000MPa~
3000Mpa, preferably 2200MPa~2800MPa；Elongation at break is 5.0%~20%, preferably 10%~20%.
Therefore, which has good application value, such as can be applicable to hot environment work
The correlative technology fields such as engineering plastics, proton exchange membrane, fiber, adhesive, coating and advanced composite material.
The above-mentioned polybenzimidazoles imido method provided by the invention for preparing is：By benzimidazole monomer, biphenol monomer
And with disubstituted dant monomer aromatic nucleophilic substitution reaction occurs for disubstituted dant monomer mixing, benzimidazole ring, together
When biphenol monomer and disubstituted dant monomer aromatic nucleophilic substitution reaction occurs, polybenzimidazoles acid imide is formed after condensation.
That is, the preparation method is specific as follows：
Benzimidazole monomer is added in the reaction vessel, biphenol monomer, disubstituted dant monomer, basic catalyst, has
Solvent, water entrainer mix well carry out aromatic nucleophilic substitution reaction, and reaction route is as follows, react postcooling, will be anti-
Answer liquid to pour into precipitating reagent, refilter, collect precipitation after fully wash, dry, polybenzimidazoles imide resin is made；
Wherein, X is nitro or halogen atom fluorine, chlorine, X be in acid imide phenyl ring the positions 3- or 4-；M is greater than
Or the integer equal to 1, n are greater than or equal to 0 integer.
The basic catalyst can be selected from but be not limited to carbonate (such as potassium carbonate, sodium carbonate, lithium carbonate), carbonic acid
Hydrogen salt (such as sodium bicarbonate, saleratus), organic base (such as triethylamine, tri-n-butylamine, pyridine, pyrimidine, isoquinolin), alcohol
Alkali metal salt (such as sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, tert-butyl alcohol lithium), metal hydride (such as sodium hydride, lithium hydride, hydrogen
Change potassium etc.) etc. compounds.
Preferably, the basic catalyst dosage is the 100%~150% of benzimidazole and bis-phenol integral molar quantity.
The organic solvent includes but not limited to N, N '-dimethylformamides, N, N '-dimethylacetylamides, N- methyl-
2-Pyrrolidone, dimethyl sulfoxide (DMSO), sulfolane, diphenyl sulphone (DPS) etc..
The water entrainer is unlimited, can be toluene, chlorobenzene, dimethylbenzene, dichloro-benzenes etc..
Preferably, the nucleophilic substitution is carried out in inert gas shielding atmosphere.
Preferably, during the reaction, reaction system is warming up to 160 DEG C~250 DEG C.
Preferably, the reaction time of the aromatic nucleophilic substitution reaction is 6 hours~24 hours, more preferably 8 is small
When~12 hours.
Preferably, the molecular weight of the prepared polybenzimidazoles imide resin of end-capping reagent regulation and control may be used, that is, work as parent
End-capping reagent is added after core substitution reaction, the reaction was continued, and certain time is blocked.The end-capping reagent can be with following knot
The compound of structure：
Wherein X is the halogen atoms such as nitro or fluorine, chlorine, can be at 3- or 4-.End-capping reagent can be N- phenyl -3- fluorine
For phthalimide, N- phenyl -4- fluoro phthalimide, N- phenyl -3- chlorophthalimides, N- benzene
Base -4- chlorophthalimides, N- phenyl -3- nitroaromatics phthalimide, N- phenyl -4- nitroaromatic O-phthalics
Acid imide etc..Preferably 1 hour~2 hours time that the reaction was continued after end-capping reagent is added.
Compared with existing preparation method, the present invention prepares polybenzimidazoles acid imide using nucleophilic substitution condensation,
This method is simple and practicable, and cost is relatively low.
Specific implementation mode
Below in conjunction with specific embodiment, present invention is further described in detail, it is necessary to be pointed out that the present embodiment is only used
It is further detailed in the present invention, should not be understood as limiting the scope of the invention.Technology in the field is ripe
Some nonessential modifications and adaptations can be made according to the content of foregoing invention by practicing personnel.
Embodiment 1：
In the present embodiment, polybenzimidazoles acid imide has the following structure formula：
The above-mentioned imido reaction route of polybenzimidazoles is as follows：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
4.96g (0.01mol) 4,4 '-bis- fluoro dant monomers are added in the 250mL there-necked flasks of dried and clean,
1.64g (0.007mol) benzimidazole, 0.685g (0.003mol) bisphenol-A, 1.16g (0.011mol) sodium carbonate, 40mL diformazans
Benzene, 40mL n-methyl-2-pyrrolidone, under nitrogen protection, 200 DEG C of reflux band water are reacted 12 hours；It is then cooled to room
Reaction solution is poured slowly into 500mL ethyl alcohol by temperature, filtering, gained filter cake is boiled with ethyl alcohol to be washed 2 times, be placed in 120 DEG C of baking ovens
It is 8 hours dry, obtain faint yellow polybenzimidazoles acid imide powder 6.62g, yield 91%.
The polybenzimidazoles acid imide is tested for the property, it is as a result as follows：
(1) logarithmic viscosity number measured in the n-methyl-2-pyrrolidone of 30 DEG C of a concentration of 0.5g/dL is
0.38dL/g；
(2) it is 322 DEG C by the glass transition temperature that differential scanning calorimetry measures；
(3) it is 432 DEG C by 5% heat decomposition temperature that thermal gravimetric analyzer measures.
The imido n-methyl-2-pyrrolidone solution (solid content 10%) of the polybenzimidazoles is coated uniformly on cleaning
Glass plate on, glass plate is positioned in drying box, is heated up according to following procedure：80 DEG C, 8 hours；100 DEG C, 1 is small
When；150 DEG C, 1 hour；200 DEG C, 1 hour；250 DEG C, 1 hour；300 DEG C, 1 hour.Wait for that temperature is cooled to room temperature taking-up glass
Plate places it in demoulding in water, and film is then placed in 100 DEG C of drying boxes dry water removal, obtains polybenzimidazoles acid imide
Film, thickness 20um.Hot property, the mechanical performance of its film see attached list 1.
Embodiment 2：
In the present embodiment, polybenzimidazoles acid imide has the following structure formula：
The above-mentioned imido reaction route of polybenzimidazoles is as follows：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
4.96g (0.01mol) 4,4 '-bis- fluoro dant monomers are added in the 250mL there-necked flasks of dried and clean,
1.17g (0.005mol) benzimidazole, 1.14g (0.005mol) bisphenol-A, 1.16g (0.011mol) sodium carbonate, 40mL diformazans
Benzene, 40mL n-methyl-2-pyrrolidone, under nitrogen protection, 200 DEG C of reflux band water are reacted 12 hours；It is then cooled to room
Reaction solution is poured slowly into 500mL ethyl alcohol by temperature, filtering, gained filter cake is boiled with ethyl alcohol to be washed 2 times, be placed in 120 DEG C of baking ovens
It is 8 hours dry, obtain faint yellow polybenzimidazoles acid imide powder 6.76g, yield 93%.
The polybenzimidazoles acid imide is tested for the property, it is as a result as follows：
(1) logarithmic viscosity number measured in the n-methyl-2-pyrrolidone of 30 DEG C of a concentration of 0.5g/dL is
0.36dL/g；
(2) it is 317 DEG C by the glass transition temperature that differential scanning calorimetry measures；
(3) it is 421 DEG C by 5% heat decomposition temperature that thermal gravimetric analyzer measures.
The imido n-methyl-2-pyrrolidone solution (solid content 10%) of the polybenzimidazoles is coated uniformly on cleaning
Glass plate on, glass plate is positioned in drying box, is heated up according to following procedure：80 DEG C, 8 hours；100 DEG C, 1 is small
When；150 DEG C, 1 hour；200 DEG C, 1 hour；250 DEG C, 1 hour；300 DEG C, 1 hour.Wait for that temperature is cooled to room temperature taking-up glass
Plate places it in demoulding in water, and film is then placed in 100 DEG C of drying boxes dry water removal, obtains polybenzimidazoles acid imide
Film, thickness 20um.Hot property, the mechanical performance of its film see attached list 1.
Embodiment 3：
In the present embodiment, polybenzimidazoles acid imide has the following structure formula：
The above-mentioned imido reaction route of polybenzimidazoles is as follows：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
4.96g (0.01mol) 4,4 '-bis- fluoro dant monomers are added in the 250mL there-necked flasks of dried and clean,
0.70g (0.003mol) benzimidazole, 1.60g (0.007mol) bisphenol-A, 1.16g (0.011mol) sodium carbonate, 40mL diformazans
Benzene, 40mL n-methyl-2-pyrrolidone, under nitrogen protection, 200 DEG C of reflux band water are reacted 12 hours；It is then cooled to room
Reaction solution is poured slowly into 500mL ethyl alcohol by temperature, filtering, gained filter cake is boiled with ethyl alcohol to be washed 2 times, be placed in 120 DEG C of baking ovens
It is 8 hours dry, obtain faint yellow polybenzimidazoles acid imide powder 6.88g, yield 95%.
The polybenzimidazoles acid imide is tested for the property, it is as a result as follows：
(1) logarithmic viscosity number measured in the n-methyl-2-pyrrolidone of 30 DEG C of a concentration of 0.5g/dL is
0.40dL/g；
(2) it is 253 DEG C by the glass transition temperature that differential scanning calorimetry measures；
(3) it is 416 DEG C by 5% heat decomposition temperature that thermal gravimetric analyzer measures.
The imido n-methyl-2-pyrrolidone solution (solid content 10%) of the polybenzimidazoles is coated uniformly on cleaning
Glass plate on, glass plate is positioned in drying box, is heated up according to following procedure：80 DEG C, 8 hours；100 DEG C, 1 is small
When；150 DEG C, 1 hour；200 DEG C, 1 hour；250 DEG C, 1 hour；300 DEG C, 1 hour.Wait for that temperature is cooled to room temperature taking-up glass
Plate places it in demoulding in water, and film is then placed in 100 DEG C of drying boxes dry water removal, obtains polybenzimidazoles acid imide
Film, thickness 20um.Hot property, the mechanical performance of its film see attached list 1.
Embodiment 4：
In the present embodiment, polybenzimidazoles acid imide has the following structure formula：
The above-mentioned imido reaction route of polybenzimidazoles is as follows：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
4.96g (0.01mol) 4,4 '-bis- fluoro dant monomers are added in the 250mL there-necked flasks of dried and clean,
1.41g (0.006mol) benzimidazole, 1.27g (0.004mol) phenolphthalein, 1.41g (0.011mol) potassium carbonate, 40mL dimethylbenzene,
40mL sulfolane, under nitrogen protection, 180 DEG C of reflux band water react 12 hours；It is then cooled to which room temperature, slow by reaction solution
Pour into 500mL ethyl alcohol, filter, gained filter cake is boiled with ethyl alcohol to be washed 2 times, be placed in 120 DEG C of baking ovens 8 hours dry, obtain
Faint yellow polybenzimidazoles acid imide powder 6.87g, yield 90%.
The polybenzimidazoles acid imide is tested for the property, it is as a result as follows：
(1) logarithmic viscosity number measured in the n-methyl-2-pyrrolidone of 30 DEG C of a concentration of 0.5g/dL is
0.41dL/g；
(2) it is 332 DEG C by the glass transition temperature that differential scanning calorimetry measures；
(3) it is 420 DEG C by 5% heat decomposition temperature that thermal gravimetric analyzer measures.
The imido n-methyl-2-pyrrolidone solution (solid content 10%) of the polybenzimidazoles is coated uniformly on cleaning
Glass plate on, glass plate is positioned in drying box, is heated up according to following procedure：80 DEG C, 8 hours；100 DEG C, 1 is small
When；150 DEG C, 1 hour；200 DEG C, 1 hour；250 DEG C, 1 hour；300 DEG C, 1 hour.Wait for that temperature is cooled to room temperature taking-up glass
Plate places it in demoulding in water, and film is then placed in 100 DEG C of drying boxes dry water removal, obtains polybenzimidazoles acid imide
Film, thickness 20um.Hot property, the mechanical performance of its film see attached list 1.
Embodiment 5：
In the present embodiment, polybenzimidazoles acid imide has the following structure formula：
The above-mentioned imido reaction route of polybenzimidazoles is as follows：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
4.96g (0.01mol) 4,4 '-bis- fluoro dant monomers are added in the 250mL there-necked flasks of dried and clean,
1.17g (0.005mol) benzimidazole, 1.59g (0.005mol) phenolphthalein, 1.41g (0.011mol) potassium carbonate, 40mL dimethylbenzene,
40mL sulfolane, under nitrogen protection, 180 DEG C of reflux band water react 12 hours；It is then cooled to which room temperature, slow by reaction solution
Pour into 500mL ethyl alcohol, filter, gained filter cake is boiled with ethyl alcohol to be washed 2 times, be placed in 120 DEG C of baking ovens 8 hours dry, obtain
Faint yellow polybenzimidazoles acid imide powder 6.02g, yield 91%.
The polybenzimidazoles acid imide is tested for the property, it is as a result as follows：
(1) logarithmic viscosity number measured in the n-methyl-2-pyrrolidone of 30 DEG C of a concentration of 0.5g/dL is
0.39dL/g；
(2) it is 319 DEG C by the glass transition temperature that differential scanning calorimetry measures；
(3) it is 440 DEG C by 5% heat decomposition temperature that thermal gravimetric analyzer measures.
The imido n-methyl-2-pyrrolidone solution (solid content 10%) of the polybenzimidazoles is coated uniformly on cleaning
Glass plate on, glass plate is positioned in drying box, is heated up according to following procedure：80 DEG C, 8 hours；100 DEG C, 1 is small
When；150 DEG C, 1 hour；200 DEG C, 1 hour；250 DEG C, 1 hour；300 DEG C, 1 hour.Wait for that temperature is cooled to room temperature taking-up glass
Plate places it in demoulding in water, and film is then placed in 100 DEG C of drying boxes dry water removal, obtains polybenzimidazoles acid imide
Film, thickness 20um.Hot property, the mechanical performance of its film see attached list 1.
Embodiment 6：
In the present embodiment, polybenzimidazoles acid imide has the following structure formula：
The above-mentioned imido reaction route of polybenzimidazoles is as follows：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
4.96g (0.01mol) 4,4 '-bis- fluoro dant monomers are added in the 250mL there-necked flasks of dried and clean,
0.94g (0.004mol) benzimidazole, 1.91g (0.006mol) phenolphthalein, 1.41g (0.011mol) potassium carbonate, 40mL dimethylbenzene,
40mL sulfolane, under nitrogen protection, 180 DEG C of reflux band water react 12 hours；It is then cooled to which room temperature, slow by reaction solution
Pour into 500mL ethyl alcohol, filter, gained filter cake is boiled with ethyl alcohol to be washed 2 times, be placed in 120 DEG C of baking ovens 8 hours dry, obtain
Faint yellow polybenzimidazoles acid imide powder 6.79g, yield 87%.
The polybenzimidazoles acid imide is tested for the property, it is as a result as follows：
(1) logarithmic viscosity number measured in the n-methyl-2-pyrrolidone of 30 DEG C of a concentration of 0.5g/dL is
0.35dL/g；
(2) it is 316 DEG C by the glass transition temperature that differential scanning calorimetry measures；
(3) it is 415 DEG C by 5% heat decomposition temperature that thermal gravimetric analyzer measures.
The imido n-methyl-2-pyrrolidone solution (solid content 10%) of the polybenzimidazoles is coated uniformly on cleaning
Glass plate on, glass plate is positioned in drying box, is heated up according to following procedure：80 DEG C, 8 hours；100 DEG C, 1 is small
When；150 DEG C, 1 hour；200 DEG C, 1 hour；250 DEG C, 1 hour；300 DEG C, 1 hour.Wait for that temperature is cooled to room temperature taking-up glass
Plate places it in demoulding in water, and film is then placed in 100 DEG C of drying boxes dry water removal, obtains polybenzimidazoles acid imide
Film, thickness 20um.Hot property, the mechanical performance of its film see attached list 1.
Embodiment 7：
In the present embodiment, polybenzimidazoles acid imide has the following structure formula：
The above-mentioned imido reaction route of polybenzimidazoles is as follows：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
5.50g (0.01mol) 4,4 '-bis- nitroaromatic dant monomers are added in the 250mL there-necked flasks of dried and clean,
2.34g (0.01mol) benzimidazole, 1.41g (0.011mol) potassium carbonate, 15mL toluene, 30mL n-methyl-2-pyrrolidone,
Under nitrogen protection, 200 DEG C of reflux band water react 12 hours；It is then cooled to which room temperature, 500mL second is poured slowly by reaction solution
In alcohol, filtering, gained filter cake is boiled with ethyl alcohol to be washed 2 times, be placed in 120 DEG C of baking ovens 8 hours dry, obtain faint yellow polyphenyl simultaneously
Imidazoles acid imide powder 6.76g, yield 93%.
The polybenzimidazoles acid imide is tested for the property, it is as a result as follows：
(1) logarithmic viscosity number measured in the n-methyl-2-pyrrolidone of 30 DEG C of a concentration of 0.5g/dL is
0.50dL/g；
(2) it is 336 DEG C by the glass transition temperature that differential scanning calorimetry measures；
(3) it is 483 DEG C by 5% heat decomposition temperature that thermal gravimetric analyzer measures.
Embodiment 8：
In the present embodiment, polybenzimidazoles acid imide has the following structure formula：
The above-mentioned imido reaction route of polybenzimidazoles is as follows：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
5.29g (0.01mol) 3,3 '-bis- chloro dant monomers are added in the 250mL there-necked flasks of dried and clean,
2.34g (0.01mol) benzimidazole, 1.41g (0.011mol) potassium carbonate, 15mL toluene, 30mL n-methyl-2-pyrrolidone,
Under nitrogen protection, 200 DEG C of reflux band water react 12 hours；It is then cooled to which room temperature, 500mL second is poured slowly by reaction solution
In alcohol, filtering, gained filter cake is boiled with ethyl alcohol to be washed 2 times, be placed in 120 DEG C of baking ovens 8 hours dry, obtain faint yellow polyphenyl simultaneously
Imidazoles acid imide powder 5.62g, yield 77%.
The polybenzimidazoles acid imide is tested for the property, it is as a result as follows：
(1) logarithmic viscosity number measured in the n-methyl-2-pyrrolidone of 30 DEG C of a concentration of 0.5g/dL is
0.16dL/g；
(2) it is 340 DEG C by the glass transition temperature that differential scanning calorimetry measures；
(3) it is 465 DEG C by 5% heat decomposition temperature that thermal gravimetric analyzer measures.
Embodiment 9：
In the present embodiment, polybenzimidazoles acid imide has the following structure formula：
The above-mentioned imido reaction route of polybenzimidazoles is as follows：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
2.48g (0.005mol) 4,4 '-bis- fluoro dant monomers are added in the 250mL there-necked flasks of dried and clean,
2.48g (0.005mol), 3,3 '-bis- fluoro dant monomers, 2.34g (0.01mol) benzimidazole, 1.41g (0.011mol)
Potassium carbonate, 15mL toluene, 30mL n-methyl-2-pyrrolidone, under nitrogen protection, 200 DEG C of reflux band water are reacted 12 hours；
It is then cooled to room temperature, reaction solution is poured slowly into 500mL ethyl alcohol, filtering, gained filter cake is boiled with ethyl alcohol to be washed 2 times, postposition
It is 8 hours dry in 120 DEG C of baking ovens, obtain faint yellow polybenzimidazoles acid imide powder 8.37g, yield 89%.
The polybenzimidazoles acid imide is tested for the property, it is as a result as follows：
(1) logarithmic viscosity number measured in the n-methyl-2-pyrrolidone of 30 DEG C of a concentration of 0.5g/dL is
0.27dL/g；
(2) it is 325 DEG C by the glass transition temperature that differential scanning calorimetry measures；
(3) it is 523 DEG C by 5% heat decomposition temperature that thermal gravimetric analyzer measures.
Embodiment 10：
In the present embodiment, polybenzimidazoles acid imide has the following structure formula：
The above-mentioned imido reaction route of polybenzimidazoles is as follows：
The above-mentioned imido preparation method of polybenzimidazoles is as follows：
7.07g (0.01mol) 4,4 '-bis- fluoro dant monomers are added in the 250mL there-necked flasks of dried and clean,
2.34g (0.01mol) benzimidazole, 1.41g (0.011mol) potassium carbonate, 15mL toluene, 30mL n-methyl-2-pyrrolidone,
Under nitrogen protection, 200 DEG C of reflux band water react 12 hours；It is then cooled to which room temperature, 500mL second is poured slowly by reaction solution
In alcohol, filtering, gained filter cake is boiled with ethyl alcohol to be washed 2 times, be placed in 120 DEG C of baking ovens 8 hours dry, obtain faint yellow polyphenyl simultaneously
Imidazoles acid imide powder 8.37g, yield 89%.
The polybenzimidazoles acid imide is tested for the property, it is as a result as follows：
(1) logarithmic viscosity number measured in the n-methyl-2-pyrrolidone of 30 DEG C of a concentration of 0.5g/dL is
0.41dL/g；
(2) it is 314 DEG C by the glass transition temperature that differential scanning calorimetry measures；
(3) it is 429 DEG C by 5% heat decomposition temperature that thermal gravimetric analyzer measures.
The characterization of polybenzimidazoles acid imide hot property and mechanical performance made from table 1, embodiment 1-6.
aAt 30 DEG C, a concentration of 0.5g/dL polybenzimidazoles acid imide of measurement is in n-methyl-2-pyrrolidone solution
Logarithmic viscosity number.bUnder nitrogen atmosphere, heating rate is 20 DEG C/min, the glass transition temperature of measurement.
cUnder nitrogen atmosphere, temperature when thermal weight loss 5%.
The arbitrary combination of benzimidazole, biphenol monomer, disubstituted dant monomer can be achieved in preparation method of the present invention
The imido preparation of polybenzimidazoles.Details are not described herein.
Technical scheme of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in the spirit of the present invention,
Supplement or similar fashion replacement etc., should all be included in the protection scope of the present invention.
Claims (16)
1. a kind of polybenzimidazoles acid imide, it is characterized in that：Structural formula is：
Wherein, m is greater than or equal to 1 integer, and n is greater than or equal to 0 integer；Ar1Group connects two imidazole rings and forms benzene
And imidazole group, Ar2It is the residue of diamine compounds, Ar3It is the residue of diphenols compound；Benzimidazole group is present in
The positions 3- of acid imide phenyl ring and/or 4-；Oxygen atom be present in acid imide phenyl ring the positions 3- and/or 4-；
The imido preparation method of the polybenzimidazoles it is characterized in that：Benzimidazole monomer, double is added in the reaction vessel
Phenol monomer, disubstituted dant monomer, basic catalyst, organic solvent, water entrainer, mix well, and carry out following aromatic nucleophilic
Substitution reaction reacts postcooling, reaction solution is poured into precipitating reagent, refilter, collects precipitation after fully wash, dry, it is obtained
Polybenzimidazoles imide resin,
Wherein, X is nitro or halogen atom fluorine, chlorine, X be in acid imide phenyl ring the positions 3- or 4-；
The imido tensile stress of the polybenzimidazoles is 70MPa~120MPa；Stretch modulus be 2000MPa~
3000Mpa；Elongation at break is 5.0%~20%.
2. polybenzimidazoles acid imide according to claim 1, feature：The Ar1Be one kind in following groups or
It is several：
3. polybenzimidazoles acid imide according to claim 1, feature：
The Ar2It is one or more of following groups：
4. polybenzimidazoles acid imide according to claim 1, feature：
The Ar3It is one or more of following groups：
5. polybenzimidazoles acid imide according to claim 1, it is characterized in that：Polybenzimidazoles acid imide is in N- methyl pyrroles
When a concentration of 0.5g/dL in pyrrolidone, measured at 30 DEG C by Ubbelohde viscometer its logarithmic viscosity number be 0.16dL/g~
1.20dL/g。
6. polybenzimidazoles acid imide according to claim 5, it is characterized in that：Logarithmic viscosity number be 0.3dL/g~
0.8dL/g。
7. polybenzimidazoles acid imide according to claim 5, it is characterized in that：Logarithmic viscosity number be 0.35dL/g~
0.55dL/g。
8. polybenzimidazoles acid imide according to claim 1, it is characterized in that：Its glass is measured by differential scanning calorimetry
Glass transition temperature is 180 DEG C~350 DEG C.
9. polybenzimidazoles acid imide according to claim 8, it is characterized in that：Glass transition temperature is 200 DEG C~340
℃。
10. polybenzimidazoles acid imide according to claim 8, it is characterized in that：Glass transition temperature be 250 DEG C~
330℃。
11. polybenzimidazoles acid imide according to claim 1, it is characterized in that：By thermal gravimetric analyzer measure its 5%
Heat decomposition temperature is 400 DEG C~550 DEG C.
12. polybenzimidazoles acid imide according to claim 11, it is characterized in that：It is measured by thermal gravimetric analyzer
5% heat decomposition temperature is 420 DEG C~520 DEG C；.
13. polybenzimidazoles acid imide according to claim 11, it is characterized in that：It is measured by thermal gravimetric analyzer
5% heat decomposition temperature is 410 DEG C~450 DEG C.
14. the polybenzimidazoles acid imide according to any claim in claim 1 to 13, which is characterized in that described
Basic catalyst be carbonate, bicarbonate, organic amine, alcohol alkali metal salt or metal hydride, dosage be benzimidazole and
The 100%~150% of bis-phenol integral molar quantity.
15. the polybenzimidazoles acid imide according to any claim in claim 1 to 13, which is characterized in that described
Aromatic nucleophilic substitution reaction be to be carried out in inert gas shielding atmosphere；During the reaction, temperature of reaction system is at 150 DEG C
Between~250 DEG C.
16. the polybenzimidazoles acid imide according to any claim in claim 1 to 13, which is characterized in that described
Organic solvent be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, sulfolane, methyl sulfoxide, N-Methyl pyrrolidone,
Diphenyl sulphone (DPS), water entrainer are toluene, chlorobenzene, dimethylbenzene, dichloro-benzenes.
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