CN103450478A - Polyaryletherketone and method for preparing same - Google Patents
Polyaryletherketone and method for preparing same Download PDFInfo
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Abstract
The present invention provides a kind of poly(aryl ether ketone) and preparation method thereof, the poly(aryl ether ketone) is as shown in the formula (I). Compared with existing poly(aryl ether ketone),Firstly,Aromatic rings in poly(aryl ether ketone) main chain of the present invention be using carbon-carbon bond and ketone carbonyl key as connecting key,So that the oxygen atom content in backbone structure reduces,Not ether-containing key,Strand is avoided by thermogenetic ether exchange interaction,To improve the heat resistance of polymer; Secondly,Aromatic ring structure increases in main chain,Main chain rigidity is also improved,Strand warm-up movement is restricted,So that poly(aryl ether ketone) has preferable dimensional stability; Again,Invention introduces imidazoles monomer,So that the key of connection main chain with carbonnitrogen bond instead of ehter bond,The introducing of imidazole ring also improves main chain rigidity,So that the heat resistance of poly(aryl ether ketone) improves.
Description
Technical field
The invention belongs to technical field of polymer materials, relate in particular to a kind of polyaryletherketone and preparation method thereof.
Background technology
Polyaryletherketone is the novel semi-crystalline state aromatic series of class fire resistant resin, it has that temperature classification is high, mechanical property, electrical property and radiation resistance excellence, chemical-resistant resistance, antifatigue, shock-resistant, creep resistance, the advantage such as wear-resisting, fire-retardant, be especially suitable for use as high-performance compound resin matrix and Super Engineering plastics, at many high-technology fields such as aerospace, electronic information, the energy, purposes is widely arranged, become a large focus of macromolecular material research field.
The more polyaryletherketone of existing application mainly contains polyether-ether-ketone (PEEK), polyetherketone (PEK), polyether-ether-ketone (PEKK) and polyetherketoneetherketoneketone (PEKEKK).Polyaryletherketone belongs to the high temperature heat-resistant thermoplastic plastic, although its resistance toheat is fine, and its T
g(second-order transition temperature) is still not high, when temperature surpasses T
gafter, the modulus of material descends very fast.In addition, the polyaryletherketone fusing point is very high, and fluidity of molten is poor, and insensitive to temperature variation, makes its processing very difficult.In addition, Vicat softening point and the heat-drawn wire of polyaryletherketone are lower, and mechanical behavior under high temperature has much room for improvement.In recent years, along with new and high technology further develops, also more and more higher to the requirement of material, higher with physically modified research and development temperature classification by chemistry, processing novel ketone-grouped resin more easily is a very active problem.
Can write-Ar of the general structure of polyaryletherketone
1-X-Ar
2-Y-, Ar
1with Ar
2be aromatic group, X, Y are connector element ehter bond or ketonic bond.Aromatic group is phenyl, naphthyl normally, or more senior aromatic hydrocarbon, can replace, and can be also unsubstituted.Ehter bond or ketonic bond can be adjacent, or para-orientation.The arrangement mode of multiple aromatic group, ehter bond and ketonic bond, and the position difference replaced, make the diversity of polymer architecture become possibility, and every kind of structure is characteristic form, second-order transition temperature, rheological, processibility, solvability and other many performances all.
Most of polyaryletherketone of application is owing to containing a large amount of ehter bonds in molecular backbone chain at present, make in polymeric constituent oxygen level higher, thermotolerance reduces, and reduces ether link content to improve the rigidity of main polymer chain in main chain, is the polyaryletherketone thermotolerance to be carried out to an effective approach of modification.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of polyaryletherketone and preparation method thereof, and this polyaryletherketone thermotolerance is higher.
The invention provides a kind of polyaryletherketone, as shown in the formula (I):
Described-Ar-is selected from a kind of in following formula (1)～formula (2) structure:
Wherein, A
1with A
2be S or O independently of one another; R
1with R
2be selected from independently of one another H, NH
2, NO
2a kind of with in the alkyl of C1～C5; R
3with R
4be selected from independently of one another a kind of in H, phenyl and substituted-phenyl; N is the polymerization degree.
Preferably, R
1with R
2be selected from independently of one another H, NH
2, NO
2with CH
3in a kind of.
The present invention also provides a kind of preparation method of polyaryletherketone, comprising:
A) under the condition of protection of inert gas, two substituted diphenylamine ketone of imidazoles monomer, formula (III) structure are mixed with the first aprotic solvent, under carbonate effect, reacting by heating, obtain the polyaryletherketone of formula (I) structure, described imidazoles monomer has formula (II-1) structure or formula (II-2) structure;
Described-Ar-is selected from a kind of in following formula (1)～formula (2) structure:
Wherein, A
1with A
2be S or O independently of one another; R
1with R
2be selected from independently of one another H, NH
2, NO
2a kind of with in the alkyl of C1～C5; R
3with R
4be selected from independently of one another a kind of in H, phenyl and substituted-phenyl; N is the polymerization degree; X is halogen atom or NO
2.
Preferably, steps A) also comprise: before reacting by heating, add the band aqua, be with the water reaction.
Preferably, described band aqua is toluene and/or dimethylbenzene.
Preferably, the described temperature with the water reaction is 90 ℃～155 ℃, and the time is 1～3h.
Preferably, described the first aprotic solvent is selected from one or more in N-Methyl pyrrolidone, N-cyclohexyl pyrrolidone, DMF, N,N-dimethylacetamide, tetramethylene sulfone, methylimidazole ketone and sulfobenzide.
Preferably, described the first aprotic solvent add-on is 10%～40% for making solid content.
Preferably, the temperature of described reacting by heating is 130 ℃～300 ℃, and the time is 1～8h.
Preferably, described steps A) also comprise: after reacting by heating, add the second aprotic solvent dilution, then add the precipitation agent precipitation, obtain the polyaryletherketone of formula (I) structure.
The invention provides a kind of polyaryletherketone and preparation method thereof, this polyaryletherketone as shown in the formula (I).With existing polyaryletherketone, compare, at first, aromatic nucleus in polyaryletherketone main chain of the present invention is all that to take carbon-carbon bond and ketone ketonic linkage be connecting key, make the oxygen atom content in backbone structure reduce, ether-containing key not, avoid molecular chain to be subject to thermogenetic ether exchange interaction, thereby improved the thermotolerance of polymkeric substance; Secondly, the increasing of aromatic ring structure in main chain, also improved the rigidity of main chain, and the molecular chain thermal motion is restricted, thereby makes polyaryletherketone have dimensional stability preferably; Again, the present invention has introduced the imidazoles monomer, makes the key that connects main chain replace ehter bond with carbonnitrogen bond, and the introducing of imidazole ring has also improved the rigidity of main chain, and then makes the thermotolerance of polyaryletherketone improve.
Experimental result shows, the second-order transition temperature of polyaryletherketone prepared by the present invention can be up to 326 ℃, and 5% thermal weight loss temperature can be up to 557 ℃, and 800 ℃ of carbon yields can reach 64.0%.
The accompanying drawing explanation
The quantitative carbon spectrogram of solid state nmr that Fig. 1 is the polyaryletherketone shown in the formula (I-a) for preparing of the embodiment of the present invention 1;
Fig. 2 is the polyaryletherketone DSC secondary temperature elevation graphic representation shown in the formula (I-a) for preparing of the embodiment of the present invention 1;
Fig. 3 is the thermogravimetric analysis figure of the polyaryletherketone shown in the formula (I-a) obtained by the embodiment of the present invention 1.
Embodiment
The invention provides a kind of polyaryletherketone, as shown in the formula (I):
Described-Ar-is selected from a kind of in following formula (1)～formula (2) structure:
Wherein, A
1with A
2be S or O independently of one another; R
1with R
2be selected from independently of one another H, NH
2, NO
2a kind of with in the alkyl of C1～C5, be preferably H, NH
2, NO
2or the alkyl of C1～C3, more preferably H, NH
2, NO
2or CH
3, R in the present invention
1with R
2structure can be identical, also can be different, do not have special restriction; R
3with R
4be selected from independently of one another a kind of in H, phenyl and substituted-phenyl, be preferably H or phenyl, phenyl more preferably, R in the present invention
3with R
4structure can be identical, also can be different, do not have special restriction; N is the polymerization degree.
Aromatic nucleus in polyaryletherketone main chain of the present invention is all that to take carbon-carbon bond and ketone ketonic linkage be connecting key, make the oxygen atom content in backbone structure reduce, ether-containing key not, avoided molecular chain to be subject to thermogenetic ether exchange interaction, thereby improved the thermotolerance of polymkeric substance, simultaneously, in main chain, aromatic ring structure increases, also improved the rigidity of main chain, the molecular chain thermal motion is restricted, thereby make polyaryletherketone there is dimensional stability preferably, and, the present invention has introduced the imidazoles monomer, make the key that connects main chain replace ehter bond with carbonnitrogen bond, the introducing of imidazole ring has also improved the rigidity of main chain, and then make the thermotolerance of polyaryletherketone improve.
The present invention also provides the preparation method of the polyaryletherketone shown in above-mentioned formula (I), comprising:
A) under the condition of protection of inert gas, two substituted diphenylamine ketone of imidazoles monomer, formula (III) structure are mixed with the first aprotic solvent, under carbonate effect, reacting by heating, obtain the polyaryletherketone of formula (I) structure, described imidazoles monomer has formula (II-1) structure or formula (II-2) structure;
Described-Ar-is selected from a kind of in following formula (1)～formula (2) structure:
Wherein, A
1with A
2be S or O independently of one another; R
1with R
2be selected from independently of one another H, NH
2, NO
2a kind of with in C1～C5 alkyl; R
3with R
4be selected from independently of one another a kind of in H, phenyl and substituted-phenyl; N is polymkeric substance; X is halogen atom or NO
2, be preferably Cl, F or NO
2.Described R
1, R
2, R
3with R
4all same as above, do not repeat them here.
The present invention does not have special restriction to the source of all raw materials, for commercially available, gets final product.
Described rare gas element is that rare gas element well known to those skilled in the art gets final product, and there is no special restriction, preferred nitrogen and/or argon gas in the present invention.
Under the condition of protection of inert gas, two substituted diphenylamine ketone of imidazoles monomer, formula (III) structure are mixed with aprotic solvent.Wherein, described imidazoles monomer is preferably benzimidazolone, 5-methyl benzimidazolone, 5-Amino-2-benzimidazolinone, 5-Nitro-2-benzimidazolinone, 5, one or more in 6-dimethylbenzimidazole quinoline ketone and 5,6-diamino benzo imidazolone; Two substituted diphenylamine ketone of described formula (III) structure be preferably 4,4 '-bis-chloro benzophenones, 4,4 '-dinitrobenzene benzophenone and 4,4 '-one or more in difluoro benzophenone; Two substituted diphenylamine ketone of described imidazoles monomer and formula (III) structure preferably add according to the ratio of mol ratio (1:1)～(1:1.01).
The first aprotic solvent is that aprotic solvent well known to those skilled in the art gets final product, there is no special restriction, be preferably N-Methyl pyrrolidone, N-cyclohexyl pyrrolidone, N in the present invention, one or more in dinethylformamide, N,N-dimethylacetamide, tetramethylene sulfone, methylimidazole ketone and sulfobenzide; It is 10%～40% that the amount that described the first aprotic solvent adds is preferably the solid content that makes reaction system, more preferably 15%～35%, then be preferably 18%～30%.
In the present invention, the imidazoles monomer reacts the polyaryletherketone of synthesis type (I) structure with two substituted diphenylamine ketone of formula (III) structure under hot conditions by solution condensation, this reaction need be carried out under the effect of catalyzer, the present invention be take carbonate as catalyzer, and described carbonate is preferably salt of wormwood and/or calcium carbonate; For the generation that reacts fully, in the present invention, the amount of catalyst carbon hydrochlorate is excessive, and preferably the mol ratio according to imidazoles monomer and carbonate is 1:(1～5) ratio add, 1:(1～3 more preferably), then be preferably 1:(1～2).
Condensation reaction produces water, for impelling the generation of reaction, preferably before reacting by heating, adds the band aqua, is with the water reaction.Described band aqua is that band aqua well known to those skilled in the art gets final product, and there is no special restriction, is preferably in the present invention that to take toluene and/or dimethylbenzene be the band aqua; The described temperature with the water reaction is preferably 90 ℃～155 ℃, and more preferably 120 ℃～155 ℃, the time is preferably 1～3h, more preferably 1.5～2.5h.
After the reaction of band water, after preferably removing the band aqua, then carry out reacting by heating.Described method of removing with aqua preferably adopts to heat up and removes.
Under the catalyzer carbonate effect, reacting by heating, the temperature of this reacting by heating is preferably 130 ℃～300 ℃, and more preferably 180 ℃～250 ℃, then be preferably 180 ℃～200 ℃, the time is preferably 1～8h, 3～7h more preferably, then be preferably 3～6h.
According to the present invention, after reacting by heating, preferably add the second aprotic solvent to be diluted, then add the precipitation agent precipitation, obtain the polyaryletherketone of formula (I) structure.Wherein, described the second aprotic solvent is preferably N-Methyl pyrrolidone, N-cyclohexyl pyrrolidone, N, dinethylformamide, N, one or more in N-N,N-DIMETHYLACETAMIDE, tetramethylene sulfone, methylimidazole ketone and sulfobenzide, itself and the first aprotic solvent can be the same or different, and there is no special restriction; It is 5～10% that the amount that the second aprotic solvent adds is preferably the solid content that makes reaction system, more preferably 8%～10%; Described precipitation agent is that precipitation agent well known to those skilled in the art gets final product, there is no special restriction, be preferably one or more in water, ethanol and acetic acid in the present invention, more preferably three's mixing solutions, the present invention is also unrestricted to three's ratio, can be arbitrary proportion and mixes.
The present invention carries out solution polycondensation by imidazoles monomer and two substituted diphenylamine ketone and reacts and can obtain polyaryletherketone under hot conditions, and synthetic method is simple, and cost is lower.
Experimental result shows, the second-order transition temperature of polyaryletherketone prepared by the present invention can be up to 326 ℃, and 5% thermal weight loss temperature can be up to 557 ℃, and 800 ℃ of carbon yields can reach 64.0%.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of polyaryletherketone provided by the invention and preparation method thereof is described in detail.
In following examples, reagent used is commercially available.
Embodiment 1
Add successively 1.341g(0.01mol in tri-mouthfuls of round-bottomed flasks of 100ml) benzimidazolone (HBI), 2.182g(0.01mol) difluoro benzophenone (DFK), 2.763g salt of wormwood, 25g tetramethylene sulfone and 12ml toluene, be heated to 130 ℃ of azeotropic water removings, insulation 2h, toluene is removed in intensification, continue to be heated to 185 ℃, reaction 4.5h, cooling, add the dilution of 20ml N,N-DIMETHYLACETAMIDE, at ethanol, in the mixing solutions of water and acetic acid, precipitate, after throw out filters, use deionized water extraction 12h in apparatus,Soxhlet's, remove inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-a), its reaction formula is as follows:
Utilize nucleus magnetic resonance to be tested the polyaryletherketone shown in the formula (I-a) obtained in embodiment 1, obtain the quantitative carbon spectrogram of its solid state nmr, as shown in Figure 1.As shown in Figure 1,190.68ppm locate the fignal center into carbonyl C in the benzimidazolone structural unit, 150.39ppm locate the fignal center into benzophenone structural unit carbonyl C, the two integral area is 1:1, the product of proof synthesized is the polyaryletherketone shown in formula (I-a), the fignal center that 120～105ppm place is C on phenyl ring.
Utilize differential scanning calorimetry to be tested the polyaryletherketone shown in the formula (I-a) obtained in embodiment 1, obtain its DSC secondary temperature elevation graphic representation, as shown in Figure 2.Its Tg is 226 ℃ as shown in Figure 2, illustrates that this polyaryletherketone has higher heat resisting temperature.
Utilize thermogravimetric analyzer to be tested the polyaryletherketone shown in the formula (I-a) obtained in embodiment 1, obtain its thermogravimetric analysis figure, as shown in Figure 3.As shown in Figure 3, its 5% thermal weight loss temperature is up to 557 ℃, and 800 ℃ of carbon yields are 64.0%, illustrate that the thermal decomposition performance of this polyaryletherketone is good, and higher ablation resistance is arranged.
Embodiment 2
Add successively 1.482g(0.01mol in tri-mouthfuls of round-bottomed flasks of 100ml) 5-methyl benzimidazolone (mHBI), 2.182g(0.01mol) difluoro benzophenone (DFK), 1.590g salt of wormwood, 12.5g N-cyclohexyl pyrrolidone (CHP) and 12ml toluene, be heated to 150 ℃, insulation 2h, azeotropic water removing, toluene is removed in intensification, continue to be heated to 190 ℃, reaction 4.5h, reheat to 205 ℃, reaction 2h, cooling, add the dilution of 10ml N,N-DIMETHYLACETAMIDE, at ethanol, in the mixing solutions of water and hydrochloric acid, precipitate, after throw out filters, use deionized water extraction 12h in apparatus,Soxhlet's, remove inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-b), its reaction formula is as follows:
Polyaryletherketone shown in the formula (I-b) obtained in embodiment 2 is carried out to the second-order transition temperature test, and obtaining its Tg is 235 ℃.
Embodiment 3
Add successively 1.622g5 in tri-mouthfuls of round-bottomed flasks of 100ml, 6-dimethylbenzimidazole ketone (DmHBI), 2.182g difluoro benzophenone (DFK), 2.763g salt of wormwood, 1.000g calcium carbonate, 25g tetramethylene sulfone and 12ml toluene, be heated to 130 ℃, insulation 2h, azeotropic water removing, toluene is removed in intensification, continue to be heated to 200 ℃, reaction 3.5h, cooling, add the dilution of 20ml N,N-DIMETHYLACETAMIDE, at ethanol, in the mixing solutions of water and acetic acid, precipitate, after throw out filters, use deionized water extraction 12h in apparatus,Soxhlet's, remove inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-c), its reaction formula is as follows:
Polyaryletherketone shown in the formula (I-c) obtained in embodiment 3 is carried out to the second-order transition temperature test, and obtaining its Tg is 326 ℃.
Embodiment 4
Add successively 2.363g4 in tri-mouthfuls of round-bottomed flasks of 100ml, the 5-imidazole diphenyl ketone, 2.182g difluoro benzophenone (DFK), 2.763g salt of wormwood, 1.500g calcium carbonate, 25g tetramethylene sulfone and 12ml toluene, be heated to 130 ℃, insulation 2h, azeotropic water removing, toluene is removed in intensification, continue to be heated to 185 ℃, reaction 7h, cooling, add the dilution of 20ml N,N-DIMETHYLACETAMIDE, at ethanol, in the mixing solutions of water and acetic acid, precipitate, after throw out filters, use deionized water extraction 12h in apparatus,Soxhlet's, remove inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-d), its reaction formula is as follows:
Polyaryletherketone shown in the formula (I-d) obtained in embodiment 4 is carried out to the second-order transition temperature test, and obtaining its Tg is 247 ℃.
Embodiment 5
Add successively 1.502g2-mercaptobenzimidazole (MBI) in tri-mouthfuls of round-bottomed flasks of 100ml, 2.182g difluoro benzophenone (DFK), 2.763g salt of wormwood, 1.500g calcium carbonate, 25g tetramethylene sulfone and 12ml toluene, be heated to 130 ℃, insulation 2h, azeotropic water removing, toluene is removed in intensification, continue to be heated to 175 ℃, reaction 3h, cooling, add the dilution of 20ml N,N-DIMETHYLACETAMIDE, at ethanol, in the mixing solutions of water and acetic acid, precipitate, after throw out filters, use deionized water extraction 12h in apparatus,Soxhlet's, remove inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-e), its reaction formula is as follows:
Polyaryletherketone shown in the formula (I-e) obtained in embodiment 5 is carried out to the second-order transition temperature test, and obtaining its Tg is 165 ℃.
Embodiment 6
Add successively 0.896g5-nitrobenzimidazole ketone (nHBI) in tri-mouthfuls of round-bottomed flasks of 100ml, 1.256g difluoro benzophenone (DFK), 1.382g salt of wormwood, 10ml tetramethylene sulfone and 12ml toluene, be heated to 130 ℃, insulation 2h, azeotropic water removing, toluene is removed in intensification, continue to be heated to 185 ℃, reaction 7h, cooling, add the dilution of 12ml N,N-DIMETHYLACETAMIDE, at ethanol, in the mixing solutions of water and acetic acid, precipitate, after throw out filters, use deionized water extraction 12h in apparatus,Soxhlet's, remove inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-f), its reaction formula is as follows:
Polyaryletherketone shown in the formula (I-f) obtained in embodiment 6 is carried out to the second-order transition temperature test, and obtaining its Tg is 292 ℃.
Embodiment 7
Add successively 1.492g5-aminobenzimidazole ketone (aHBI) in tri-mouthfuls of round-bottomed flasks of 100ml, 2.182g difluoro benzophenone (DFK), 1.590g salt of wormwood, 12.5g N-cyclohexyl pyrrolidone and 12ml toluene, be heated to 150 ℃, insulation 2h, azeotropic water removing, toluene is removed in intensification, continue to be heated to 190 ℃, reaction 4.5h, reheat to 205 ℃, reaction 2h, cooling, add the dilution of 10ml N-cyclohexyl pyrrolidone, at ethanol, in the mixing solutions of water and acetic acid, precipitate, after throw out filters, use deionized water extraction 12h in apparatus,Soxhlet's, remove inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-h), its reaction formula is as follows:
Polyaryletherketone shown in the formula (I-h) obtained in embodiment 7 is carried out to the second-order transition temperature test, and obtaining its Tg is 281 ℃.
Embodiment 8
Add successively 1.642g5 in tri-mouthfuls of round-bottomed flasks of 100ml, 6-diamino benzo imidazolone (DaHBI), 2.182g difluoro benzophenone (DFK), 2.765g salt of wormwood, 13g N, N-methylimidazole ketone (DMI) and 12ml toluene, be heated to 135 ℃, insulation 2h, azeotropic water removing, toluene is removed in intensification, continue to be heated to 188 ℃, reaction 0.5h viscosity rise, add 10g DMI and continue reaction 1h, cooling, add 15ml N, the dilution of N-N,N-DIMETHYLACETAMIDE, in the mixing solutions of ethanol and water, precipitate, after throw out filters, use deionized water extraction 12h in apparatus,Soxhlet's, remove inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-i), its reaction formula is as follows:
Polyaryletherketone shown in the formula (I-i) obtained in embodiment 8 is carried out to the second-order transition temperature test, and obtaining its Tg is 270 ℃.
Embodiment 9
Add successively 1.341g benzimidazolone (HBI) in tri-mouthfuls of round-bottomed flasks of 100ml, 2.182g difluoro benzophenone (DFK), 2.765g salt of wormwood, 13g N, N-methylimidazole ketone (DMI) and 12ml toluene, be heated to 135 ℃, insulation 2h, azeotropic water removing, toluene is removed in intensification, continue to be heated to 188 ℃, reaction 8h, cooling, add 20ml N, the dilution of N-N,N-DIMETHYLACETAMIDE, in the mixing solutions of ethanol and water, precipitate, after throw out filters, use deionized water extraction 12h in apparatus,Soxhlet's, remove inorganic salt and reaction solvent, dry, obtain polyaryletherketone.
The polyaryletherketone obtained in embodiment 9 is carried out to the second-order transition temperature test, and obtaining its Tg is 229 ℃.
Embodiment 10
Add successively 1.341g benzimidazolone (HBI) in tri-mouthfuls of round-bottomed flasks of 100ml, 2.182g difluoro benzophenone (DFK), 2.765g salt of wormwood, 15g sulfobenzide (DPS) and 12ml toluene, be heated to 155 ℃, insulation 2h, azeotropic water removing, toluene is removed in intensification, continue to be heated to 300 ℃, viscosity rise after reaction 0.5h, add 10g methylimidazole ketone (DMI) and continue reaction 1h, cooling, add 20ml N, the dilution of N-N,N-DIMETHYLACETAMIDE, in the mixing solutions of ethanol and water, precipitate, after throw out filters, use deionized water extraction 12h in apparatus,Soxhlet's, remove inorganic salt and reaction solvent, dry, obtain polyaryletherketone.
The polyaryletherketone obtained in embodiment 10 is carried out to the second-order transition temperature test, and obtaining its Tg is 255 ℃.
Embodiment 11
Add successively 1.341g benzimidazolone (HBI) in tri-mouthfuls of round-bottomed flasks of 100ml, 2.185g difluoro benzophenone (DFK), 2.765g salt of wormwood, 13g N, N-methylimidazole ketone (DMI) and 12ml toluene, be heated to 135 ℃, insulation 2h, azeotropic water removing, toluene is removed in intensification, continue to be heated to 200 ℃, reaction 5h, cooling, add 20ml N, the dilution of N-N,N-DIMETHYLACETAMIDE, in the mixing solutions of ethanol and water, precipitate, after throw out filters, use deionized water extraction 12h in apparatus,Soxhlet's, remove inorganic salt and reaction solvent, dry, obtain polyaryletherketone.
The polyaryletherketone obtained in embodiment 11 is carried out to the second-order transition temperature test, and obtaining its Tg is 225 ℃.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a polyaryletherketone, as shown in the formula (I):
Described-Ar-is selected from a kind of in following formula (1)～formula (2) structure:
Wherein, A
1with A
2be S or O independently of one another; R
1with R
2be selected from independently of one another H, NH
2, NO
2a kind of with in the alkyl of C1～C5; R
3with R
4be selected from independently of one another a kind of in H, phenyl and substituted-phenyl; N is the polymerization degree.
2. polyaryletherketone according to claim 1, is characterized in that, R
1with R
2be selected from independently of one another H, NH
2, NO
2with CH
3in a kind of.
3. the preparation method of a polyaryletherketone, is characterized in that, comprising:
A) under the condition of protection of inert gas, two substituted diphenylamine ketone of imidazoles monomer, formula (III) structure are mixed with the first aprotic solvent, under carbonate effect, reacting by heating, obtain the polyaryletherketone of formula (I) structure, described imidazoles monomer has formula (II-1) structure or formula (II-2) structure;
Described-Ar-is selected from a kind of in following formula (1)～formula (2) structure:
Wherein, A
1with A
2be S or O independently of one another; R
1with R
2be selected from independently of one another H, NH
2, NO
2a kind of with in the alkyl of C1～C5; R
3with R
4be selected from independently of one another a kind of in H, phenyl and substituted-phenyl; N is the polymerization degree; X is halogen atom or NO
2.
4. preparation method according to claim 3, is characterized in that, steps A) also comprise: before reacting by heating, add the band aqua, be with the water reaction.
5. preparation method according to claim 4, is characterized in that, described band aqua is toluene and/or dimethylbenzene.
6. preparation method according to claim 4, is characterized in that, the described temperature with the water reaction is 90 ℃～155 ℃, and the time is 1～3h.
7. preparation method according to claim 3, it is characterized in that, described the first aprotic solvent is selected from one or more in N-Methyl pyrrolidone, N-cyclohexyl pyrrolidone, DMF, N,N-dimethylacetamide, tetramethylene sulfone, methylimidazole ketone and sulfobenzide.
8. preparation method according to claim 3, is characterized in that, described the first aprotic solvent add-on is 10%～40% for making solid content.
9. preparation method according to claim 3, is characterized in that, the temperature of described reacting by heating is 130 ℃～300 ℃, and the time is 1～8h.
10. preparation method according to claim 3, is characterized in that, described steps A) also comprise: after reacting by heating, add the second aprotic solvent dilution, then add the precipitation agent precipitation, obtain the polyaryletherketone of formula (I) structure.
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