CN103450478B - A kind of polyaryletherketone and preparation method thereof - Google Patents
A kind of polyaryletherketone and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of polyaryletherketone and preparation method thereof, this polyaryletherketone as shown in the formula (I).Compared with existing polyaryletherketone, first, aromatic nucleus in polyaryletherketone main chain of the present invention is all for connecting key with carbon-carbon bond and ketone ketonic linkage, oxygen atom content in backbone structure is reduced, not ether-containing key, avoid molecular chain by thermogenetic ether exchange interaction, thus improve the thermotolerance of polymkeric substance; Secondly, the increasing of aromatic ring structure in main chain, also improve main chain rigidity, molecular chain thermal motion is restricted, thus makes polyaryletherketone have good dimensional stability; Again, invention introduces imidazoles monomer, make the key connecting main chain instead of ehter bond with carbonnitrogen bond, the introducing of imidazole ring also improves main chain rigidity, and then the thermotolerance of polyaryletherketone is improved.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly relate to a kind of polyaryletherketone and preparation method thereof.
Background technology
Polyaryletherketone is a class novel semi-crystalline state aromatic series fire resistant resin, it has, and temperature classification is high, mechanical property, electrical property and radiation resistance excellent, 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 superengineering plastics, there is purposes widely at many high-technology fields such as aerospace, electronic information, the energy, 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 high-temperature-resistant thermoplastic plastics, although its resistance toheat is fine, and its T
g(second-order transition temperature) is still not high, when temperature is more than T
gafter, the modulus of material declines very fast.In addition, polyaryletherketone fusing point is very high, and fluidity of molten is poor, and insensitive to temperature variation, makes it process 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, research and develop temperature classification by chemistry and physically modified higher, processing more easily novel ketone-grouped resin is a very active problem.
The general structure of polyaryletherketone can write-Ar
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 be to replace, and also can be 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 replaced is different, makes the diversity of polymer architecture become possibility, often kind of all characteristic form of structure, second-order transition temperature, rheological, processibility, solvability and other many performances.
Most of polyaryletherketone of current application is owing to containing a large amount of ehter bonds in molecular backbone chain, make oxygen level in polymeric constituent higher, thermotolerance reduces, and in main chain, reducing ether link content to improve the rigidity of main polymer chain, is effective approach polyaryletherketone thermotolerance being carried out to 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 the one 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 H, NH independently of one another
2, NO
2with the one in the alkyl of C1 ~ C5; R
3with R
4be selected from the one in H, phenyl and substituted-phenyl independently of one another; N is the polymerization degree.
Preferably, R
1with R
2be selected from H, NH independently of one another
2, NO
2with CH
3in one.
Present invention also offers 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 the one 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 H, NH independently of one another
2, NO
2with the one in the alkyl of C1 ~ C5; R
3with R
4be selected from the one in H, phenyl and substituted-phenyl independently of one another; N is the polymerization degree; X is halogen atom or NO
2.
Preferably, steps A) also comprise: before reacting by heating, add water entrainer, carry out the reaction of band water.
Preferably, described water entrainer is toluene and/or dimethylbenzene.
Preferably, the temperature of described band water reaction is 90 DEG C ~ 155 DEG C, and the time is 1 ~ 3h.
Preferably, described 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 first aprotic solvent add-on is 10% ~ 40% for making solid content.
Preferably, the temperature of described reacting by heating is 130 DEG C ~ 300 DEG C, and the time is 1 ~ 8h.
Preferably, described steps A) also comprise: after reacting by heating, add the second aprotic solvent dilution, then add 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).Compared with existing polyaryletherketone, first, aromatic nucleus in polyaryletherketone main chain of the present invention is all for connecting key with carbon-carbon bond and ketone ketonic linkage, oxygen atom content in backbone structure is reduced, not ether-containing key, avoid molecular chain by thermogenetic ether exchange interaction, thus improve the thermotolerance of polymkeric substance; Secondly, the increasing of aromatic ring structure in main chain, also improve main chain rigidity, molecular chain thermal motion is restricted, thus makes polyaryletherketone have good dimensional stability; Again, invention introduces imidazoles monomer, make the key connecting main chain instead of ehter bond with carbonnitrogen bond, the introducing of imidazole ring also improves main chain rigidity, and then the thermotolerance of polyaryletherketone is improved.
Experimental result shows, the second-order transition temperature of polyaryletherketone prepared by the present invention can up to 326 DEG C, and 5% thermal weight loss temperature can up to 557 DEG C, and 800 DEG C of carbon yields can reach 64.0%.
Accompanying drawing explanation
The quantitative carbon spectrogram of solid state nmr of the polyaryletherketone shown in formula (I-a) that Fig. 1 prepares for the embodiment of the present invention 1;
The polyaryletherketone DSC secondary temperature elevation graphic representation shown in formula (I-a) that Fig. 2 prepares for the embodiment of the present invention 1;
Fig. 3 is the thermogravimetric analysis figure of the polyaryletherketone shown in the formula (I-a) that 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 the one 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 H, NH independently of one another
2, NO
2with the one in the alkyl of C1 ~ C5, be preferably H, NH
2, NO
2or the alkyl of C1 ~ C3, be more preferably H, NH
2, NO
2or CH
3, R in the present invention
1with R
2structure can be identical, also can be different, not special restriction; R
3with R
4be selected from the one in H, phenyl and substituted-phenyl independently of one another, be preferably H or phenyl, be more preferably phenyl, R in the present invention
3with R
4structure can be identical, also can be different, not special restriction; N is the polymerization degree.
Aromatic nucleus in polyaryletherketone main chain of the present invention is all for connecting key with carbon-carbon bond and ketone ketonic linkage, oxygen atom content in backbone structure is reduced, not ether-containing key, avoid molecular chain by thermogenetic ether exchange interaction, thus improve the thermotolerance of polymkeric substance, simultaneously, in main chain, aromatic ring structure increases, also improve main chain rigidity, molecular chain thermal motion is restricted, thus make polyaryletherketone have good dimensional stability, and, invention introduces imidazoles monomer, the key connecting main chain is made to instead of ehter bond with carbonnitrogen bond, the introducing of imidazole ring also improves main chain rigidity, and then the thermotolerance of polyaryletherketone is improved.
Present invention also offers 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 the one 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 H, NH independently of one another
2, NO
2with the one in C1 ~ C5 alkyl; R
3with R
4be selected from the one in H, phenyl and substituted-phenyl independently of one another; 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 restriction that the present invention is not special to the source of all raw materials, for commercially available.
Described rare gas element is rare gas element well known to those skilled in the art, 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 one or more in benzimidazolone, 5-methyl benzimidazolone, 5-Amino-2-benzimidazolinone, 5-Nitro-2-benzimidazolinone, 5,6-dimethylbenzimidazole quinoline ketone and 5,6-diamino Benzimidazolinone; Two substituted diphenylamine ketone of described formula (III) structure are preferably 4,4 '-dichlorobenzophenone, 4,4 '-dinitrobenzene benzophenone and 4, one or more in 4 '-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).
First aprotic solvent is aprotic solvent well known to those skilled in the art, there is no special restriction, N-Methyl pyrrolidone, N-cyclohexyl pyrrolidone, N is preferably in the present invention, one or more in dinethylformamide, N,N-dimethylacetamide, tetramethylene sulfone, methylimidazole ketone and sulfobenzide; The amount that described first aprotic solvent adds preferably makes the solid content of reaction system be 10% ~ 40%, is more preferably 15% ~ 35%, then is preferably 18% ~ 30%.
In the present invention, two substituted diphenylamine ketone of imidazoles monomer and formula (III) structure are under the high temperature conditions by the polyaryletherketone of solution condensation Reactive Synthesis formula (I) structure, this reaction need be carried out under the effect of catalyzer, the present invention take carbonate as catalyzer, and described carbonate is preferably salt of wormwood and/or calcium carbonate; In order to the generation that reacts fully, in the present invention, the amount of catalyst carbon hydrochlorate is excessive, is preferably 1:(1 ~ 5 according to the mol ratio of imidazoles monomer and carbonate) ratio add, be more preferably 1:(1 ~ 3), then be preferably 1:(1 ~ 2).
Condensation reaction produces water, for impelling the generation of reaction, preferably before reacting by heating, adds water entrainer, carries out the reaction of band water.Described water entrainer is water entrainer well known to those skilled in the art, there is no special restriction, is preferably with toluene and/or dimethylbenzene as water entrainer in the present invention; The temperature of described band water reaction is preferably 90 DEG C ~ 155 DEG C, and be more preferably 120 DEG C ~ 155 DEG C, the time is preferably 1 ~ 3h, is more preferably 1.5 ~ 2.5h.
After the reaction of band water, preferably after removing water entrainer, then carry out reacting by heating.The method of described water entrainer removing preferably adopts the removing that heats up.
Under catalyzer carbonate effect, reacting by heating, the temperature of this reacting by heating is preferably 130 DEG C ~ 300 DEG C, is more preferably 180 DEG C ~ 250 DEG C, then is preferably 180 DEG C ~ 200 DEG C, and the time is preferably 1 ~ 8h, is more preferably 3 ~ 7h, then is preferably 3 ~ 6h.
According to the present invention, after reacting by heating, preferably add the second aprotic solvent and dilute, then add precipitation agent precipitation, obtain the polyaryletherketone of formula (I) structure.Wherein, described 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; The amount that second aprotic solvent adds preferably makes the solid content of reaction system be 5 ~ 10%, is more preferably 8% ~ 10%; Described precipitation agent is precipitation agent well known to those skilled in the art, there is no special restriction, be preferably one or more in water, ethanol and acetic acid in the present invention, be more preferably the mixing solutions of three, the present invention is also unrestricted to the ratio of three, can be arbitrary proportion mixing.
The present invention carries out solution polycondensation under the high temperature conditions by imidazoles monomer and two substituted diphenylamine ketone and reacts and can obtain polyaryletherketone, 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 up to 326 DEG C, and 5% thermal weight loss temperature can up to 557 DEG C, and 800 DEG C 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.
Reagent used in following examples is commercially available.
Embodiment 1
1.341g(0.01mol is added successively in 100ml tri-mouthfuls of round-bottomed flasks) benzimidazolone (HBI), 2.182g(0.01mol) difluoro benzophenone (DFK), 2.763g salt of wormwood, 25g tetramethylene sulfone and 12ml toluene, be heated to 130 DEG C of azeotropic water removings, insulation 2h, heat up removing toluene, continue to be heated to 185 DEG C, reaction 4.5h, cooling, add the dilution of 20ml N,N-DIMETHYLACETAMIDE, at ethanol, precipitate in the mixing solutions of water and acetic acid, after throw out filters, deionized water extraction 12h is used in apparatus,Soxhlet's, removing 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 test the polyaryletherketone shown in the formula obtained in embodiment 1 (I-a), obtain the quantitative carbon spectrogram of its solid state nmr, as shown in Figure 1.As shown in Figure 1,190.68ppm place is the fignal center of carbonyl C in benzimidazolone structural unit, 150.39ppm place is the fignal center of benzophenone structural unit carbonyl C, the two integral area is 1:1, product synthesized by proof is the polyaryletherketone shown in formula (I-a), and 120 ~ 105ppm place is the fignal center of C on phenyl ring.
Utilize differential scanning calorimetry to test the polyaryletherketone shown in the formula obtained in embodiment 1 (I-a), obtain its DSC secondary temperature elevation graphic representation, as shown in Figure 2.Its Tg is 226 DEG C as shown in Figure 2, illustrates that this polyaryletherketone has higher heat resisting temperature.
Utilize thermogravimetric analyzer to test the polyaryletherketone shown in the formula obtained in embodiment 1 (I-a), obtain its thermogravimetric analysis figure, as shown in Figure 3.As shown in Figure 3, its 5% thermal weight loss temperatures as high 557 DEG C, 800 DEG C of carbon yields are 64.0%, illustrate that the thermal decomposition performance of this polyaryletherketone is good, have higher ablation resistance.
Embodiment 2
1.482g(0.01mol is added successively in 100ml tri-mouthfuls of round-bottomed flasks) 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 DEG C, insulation 2h, azeotropic water removing, heat up removing toluene, continue to be heated to 190 DEG C, reaction 4.5h, reheat to 205 DEG C, reaction 2h, cooling, add the dilution of 10ml N,N-DIMETHYLACETAMIDE, at ethanol, precipitate in the mixing solutions of water and hydrochloric acid, after throw out filters, deionized water extraction 12h is used in apparatus,Soxhlet's, removing inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-b), its reaction formula is as follows:
Carry out second-order transition temperature test to the polyaryletherketone shown in the formula obtained in embodiment 2 (I-b), obtaining its Tg is 235 DEG C.
Embodiment 3
1.622g5 is added successively in 100ml tri-mouthfuls of round-bottomed flasks, 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 DEG C, insulation 2h, azeotropic water removing, heat up removing toluene, continue to be heated to 200 DEG C, reaction 3.5h, cooling, add the dilution of 20ml N,N-DIMETHYLACETAMIDE, at ethanol, precipitate in the mixing solutions of water and acetic acid, after throw out filters, deionized water extraction 12h is used in apparatus,Soxhlet's, removing inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-c), its reaction formula is as follows:
Carry out second-order transition temperature test to the polyaryletherketone shown in the formula obtained in embodiment 3 (I-c), obtaining its Tg is 326 DEG C.
Embodiment 4
2.363g4 is added successively in 100ml tri-mouthfuls of round-bottomed flasks, 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 DEG C, insulation 2h, azeotropic water removing, heat up removing toluene, continue to be heated to 185 DEG C, reaction 7h, cooling, add the dilution of 20ml N,N-DIMETHYLACETAMIDE, at ethanol, precipitate in the mixing solutions of water and acetic acid, after throw out filters, deionized water extraction 12h is used in apparatus,Soxhlet's, removing inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-d), its reaction formula is as follows:
Carry out second-order transition temperature test to the polyaryletherketone shown in the formula obtained in embodiment 4 (I-d), obtaining its Tg is 247 DEG C.
Embodiment 5
1.502g2-mercaptobenzimidazole (MBI) is added successively in 100ml tri-mouthfuls of round-bottomed flasks, 2.182g difluoro benzophenone (DFK), 2.763g salt of wormwood, 1.500g calcium carbonate, 25g tetramethylene sulfone and 12ml toluene, be heated to 130 DEG C, insulation 2h, azeotropic water removing, heat up removing toluene, continue to be heated to 175 DEG C, reaction 3h, cooling, add the dilution of 20ml N,N-DIMETHYLACETAMIDE, at ethanol, precipitate in the mixing solutions of water and acetic acid, after throw out filters, deionized water extraction 12h is used in apparatus,Soxhlet's, removing inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-e), its reaction formula is as follows:
Carry out second-order transition temperature test to the polyaryletherketone shown in the formula obtained in embodiment 5 (I-e), obtaining its Tg is 165 DEG C.
Embodiment 6
0.896g5-nitrobenzimidazole ketone (nHBI) is added successively in 100ml tri-mouthfuls of round-bottomed flasks, 1.256g difluoro benzophenone (DFK), 1.382g salt of wormwood, 10ml tetramethylene sulfone and 12ml toluene, be heated to 130 DEG C, insulation 2h, azeotropic water removing, heat up removing toluene, continue to be heated to 185 DEG C, reaction 7h, cooling, add the dilution of 12ml N,N-DIMETHYLACETAMIDE, at ethanol, precipitate in the mixing solutions of water and acetic acid, after throw out filters, deionized water extraction 12h is used in apparatus,Soxhlet's, removing inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-f), its reaction formula is as follows:
Carry out second-order transition temperature test to the polyaryletherketone shown in the formula obtained in embodiment 6 (I-f), obtaining its Tg is 292 DEG C.
Embodiment 7
1.492g5-aminobenzimidazole ketone (aHBI) is added successively in 100ml tri-mouthfuls of round-bottomed flasks, 2.182g difluoro benzophenone (DFK), 1.590g salt of wormwood, 12.5g N-cyclohexyl pyrrolidone and 12ml toluene, be heated to 150 DEG C, insulation 2h, azeotropic water removing, heat up removing toluene, continue to be heated to 190 DEG C, reaction 4.5h, reheat to 205 DEG C, reaction 2h, cooling, add the dilution of 10ml N-cyclohexyl pyrrolidone, at ethanol, precipitate in the mixing solutions of water and acetic acid, after throw out filters, deionized water extraction 12h is used in apparatus,Soxhlet's, removing inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-h), its reaction formula is as follows:
Carry out second-order transition temperature test to the polyaryletherketone shown in the formula obtained in embodiment 7 (I-h), obtaining its Tg is 281 DEG C.
Embodiment 8
1.642g5 is added successively in 100ml tri-mouthfuls of round-bottomed flasks, 6-diamino benzimidazolone (DaHBI), 2.182g difluoro benzophenone (DFK), 2.765g salt of wormwood, 13g N, N-methylimidazole ketone (DMI) and 12ml toluene, be heated to 135 DEG C, insulation 2h, azeotropic water removing, heat up removing toluene, continue to be heated to 188 DEG C, reaction 0.5h viscosity rises, add 10g DMI and continue reaction 1h, cooling, add 15ml N, N-N,N-DIMETHYLACETAMIDE dilutes, precipitate in the mixing solutions of ethanol and water, after throw out filters, deionized water extraction 12h is used in apparatus,Soxhlet's, removing inorganic salt and reaction solvent, dry, obtain the polyaryletherketone shown in formula (I-i), its reaction formula is as follows:
Carry out second-order transition temperature test to the polyaryletherketone shown in the formula obtained in embodiment 8 (I-i), obtaining its Tg is 270 DEG C.
Embodiment 9
1.341g benzimidazolone (HBI) is added successively in 100ml tri-mouthfuls of round-bottomed flasks, 2.182g difluoro benzophenone (DFK), 2.765g salt of wormwood, 13g N, N-methylimidazole ketone (DMI) and 12ml toluene, be heated to 135 DEG C, insulation 2h, azeotropic water removing, heat up removing toluene, continue to be heated to 188 DEG C, reaction 8h, cooling, add 20ml N, N-N,N-DIMETHYLACETAMIDE dilutes, precipitate in the mixing solutions of ethanol and water, after throw out filters, deionized water extraction 12h is used in apparatus,Soxhlet's, removing inorganic salt and reaction solvent, dry, obtain polyaryletherketone.
Carry out second-order transition temperature test to the polyaryletherketone obtained in embodiment 9, obtaining its Tg is 229 DEG C.
Embodiment 10
1.341g benzimidazolone (HBI) is added successively in 100ml tri-mouthfuls of round-bottomed flasks, 2.182g difluoro benzophenone (DFK), 2.765g salt of wormwood, 15g sulfobenzide (DPS) and 12ml toluene, be heated to 155 DEG C, insulation 2h, azeotropic water removing, heat up removing toluene, continue to be heated to 300 DEG C, after reaction 0.5h, viscosity rises, add 10g methylimidazole ketone (DMI) and continue reaction 1h, cooling, add 20ml N, N-N,N-DIMETHYLACETAMIDE dilutes, precipitate in the mixing solutions of ethanol and water, after throw out filters, deionized water extraction 12h is used in apparatus,Soxhlet's, removing inorganic salt and reaction solvent, dry, obtain polyaryletherketone.
Carry out second-order transition temperature test to the polyaryletherketone obtained in embodiment 10, obtaining its Tg is 255 DEG C.
Embodiment 11
1.341g benzimidazolone (HBI) is added successively in 100ml tri-mouthfuls of round-bottomed flasks, 2.185g difluoro benzophenone (DFK), 2.765g salt of wormwood, 13g N, N-methylimidazole ketone (DMI) and 12ml toluene, be heated to 135 DEG C, insulation 2h, azeotropic water removing, heat up removing toluene, continue to be heated to 200 DEG C, reaction 5h, cooling, add 20ml N, N-N,N-DIMETHYLACETAMIDE dilutes, precipitate in the mixing solutions of ethanol and water, after throw out filters, deionized water extraction 12h is used in apparatus,Soxhlet's, removing inorganic salt and reaction solvent, dry, obtain polyaryletherketone.
Carry out second-order transition temperature test to the polyaryletherketone obtained in embodiment 11, obtaining its Tg is 225 DEG C.
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 poly aryl ketone, shown in (I):
Described-Ar-is selected from the one 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 H, NH independently of one another
2, NO
2with the one in the alkyl of C1 ~ C5; R
3with R
4be selected from H or phenyl independently of one another; N is the polymerization degree.
2. poly aryl ketone according to claim 1, is characterized in that, R
1with R
2be selected from H, NH independently of one another
2, NO
2with CH
3in one.
3. a preparation method for poly aryl ketone, 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 poly aryl ketone of formula (I) structure, described imidazoles monomer has formula (II-1) structure or formula (II-2) structure;
Described-Ar-is selected from the one 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 H, NH independently of one another
2, NO
2with the one in the alkyl of C1 ~ C5; R
3with R
4be selected from H or phenyl independently of one another; 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 water entrainer, carry out the reaction of band water.
5. preparation method according to claim 4, is characterized in that, described water entrainer is toluene and/or dimethylbenzene.
6. preparation method according to claim 4, is characterized in that, the temperature of described band water reaction is 90 DEG C ~ 155 DEG C, and the time is 1 ~ 3h.
7. preparation method according to claim 3, it is characterized in that, described 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 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 DEG C ~ 300 DEG C, 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 precipitation agent precipitation, obtain the poly aryl ketone of formula (I) structure.
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| JP7130367B2 (en) * | 2017-12-05 | 2022-09-05 | 日本バイリーン株式会社 | An organic resin solution, a spinning solution, a method for producing a fiber assembly using the spinning solution, and a method for producing a film and a composite using the organic resin solution |
| CN109679090A (en) * | 2018-12-29 | 2019-04-26 | 福州通尔达电线电缆有限公司 | A kind of poly(aryl ether ketone) and its synthetic method containing nitrogen, sulphur cooperative flame retardant material |
| US11649323B2 (en) * | 2020-06-09 | 2023-05-16 | Ht Materials Corporation | Semicrystalline poly(aryl ether ketone) copolymers |
| US11634542B2 (en) | 2020-07-05 | 2023-04-25 | Ht Materials Corporation | High temperature semicrystalline poly(aryl ether ketone) copolymers |
| US11851532B2 (en) | 2021-07-07 | 2023-12-26 | Ht Materials Corporation | Aromatic polysulfone copolymers |
| CN115677759A (en) * | 2022-11-10 | 2023-02-03 | 中国科学院长春应用化学研究所 | Phosphonimide polycondensation monomer, preparation method of phosphonimide precursor polymer and preparation method of polyaryletherketone |
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| CN101230137B (en) * | 2007-12-29 | 2011-05-25 | 浙江工业大学 | Polybenzimidazole containing ether ketone/ether sulfone structure as well as sulfonated polymer and preparation method thereof |
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