CN103509185A - Modified polyarylether ketone and preparation method thereof - Google Patents
Modified polyarylether ketone and preparation method thereof Download PDFInfo
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- CN103509185A CN103509185A CN201310440166.0A CN201310440166A CN103509185A CN 103509185 A CN103509185 A CN 103509185A CN 201310440166 A CN201310440166 A CN 201310440166A CN 103509185 A CN103509185 A CN 103509185A
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Abstract
The present invention provides a kind of modified polyarylether ketone and preparation method thereof, the modified polyarylether ketone is as shown in the formula (I). Compared with existing poly(aryl ether ketone),Firstly,In modified polyarylether ketone main chain of the present invention with imidazole fragment instead of ether-containing key bis-phenol structure,So that oxygen atom content reduces in backbone structure,Ether bond content reduces,To reduce strand by thermogenetic ether exchange interaction,Improve the heat resistance of polymerization; Secondly,Invention introduces imidazoles monomer,The introducing of imidazole ring also improves main chain rigidity,So that the heat resistance of modified polyarylether ketone improves; Again,The present invention introduces biggish side group or aliphatic chain on the main chain of modified polyarylether ketone,To adjust the structure of main chain,Improve its aggregated structure,To which degree of making it dissolve is improved.
.
Description
Technical field
The invention belongs to technical field of polymer materials, relate in particular to a kind of modified polyarylether ketone 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 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 Super Engineering plastics, at many high-technology fields such as aerospace, electronic information, the energy, there is purposes widely, 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 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 declines very fast.In addition, 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 more easily novel ketone-grouped resin 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 replacing is different, makes the diversity of polymer architecture become possibility, 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 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 modified polyarylether ketone and preparation method thereof, and this modified polyarylether ketone thermotolerance is higher and solvability is better.
The invention provides a kind of modified polyarylether ketone, as shown in the formula (I):
Described-Ar
1-be selected from a kind of in following formula (1)～formula (2) structure:
Described-Ar
2-be selected from a kind of in following formula (4)～formula (6) 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 the alkyl of C1～C5; R
3with R
4be selected from independently of one another a kind of in H, phenyl and substituted-phenyl; R
5with R
6be selected from independently of one another the alkyl of C1～C5 or the alkyl of C1～C5 that fluorine replaces; M and n are the polymerization degree.
Preferably, described R
1with R
2be selected from independently of one another H, NH
2, NO
2with CH
3in a kind of.
Preferably, described R
5with R
6be CH independently of one another
3or CF
3.
Preferably, the ratio of described m and n is (99:1)～(1:99).
The present invention also provides a kind of preparation method of modified polyarylether ketone, comprising:
A) under the condition of protection of inert gas, imidazoles monomer, biphenol monomer are mixed with the first aprotic solvent with two substituted diphenylamine ketone of formula (IV) structure, under carbonate effect, reacting by heating, obtains the modified polyarylether ketone shown in formula (I);
Described imidazoles monomer has formula (II-1) structure or formula (II-2) structure;
Described biphenol monomer has formula (III-1) structure, formula (III-2) structure or formula (III-3) structure;
Described-Ar
1-be selected from a kind of in following formula (1)～formula (2) structure:
Described-Ar
2-be selected from a kind of in following formula (4)～formula (6) 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 the alkyl of C1～C5; R
3with R
4be selected from independently of one another a kind of in H, phenyl and substituted-phenyl; R
5with R
6be selected from independently of one another alkyl or fluorine substituted alkyl; M and n are the polymerization degree; X is halogen atom or NO
2.
Preferably, steps A) also comprise: before reacting by heating, add band aqua, be with water reaction.
Preferably, described band aqua is toluene and/or dimethylbenzene.
Preferably, the described temperature with water reaction is 120 ℃～160 ℃, and the time is 1～3h.
Preferably, described the first aprotic solvent add-on is 10%～40% for making solid content.
Preferably, described steps A) also comprise: after reacting by heating, add the second aprotic solvent dilution, then add precipitation agent precipitation, obtain the modified polyarylether ketone shown in formula (I).
The invention provides a kind of modified polyarylether ketone and preparation method thereof, this modified polyarylether ketone as shown in the formula (I).Compare with existing polyaryletherketone, first, in modified polyarylether ketone main chain of the present invention, with imidazoles, partly replaced the bis-phenol structure of ether-containing key, oxygen atom content in backbone structure is reduced, ether link content reduces, thereby reduced molecular chain, be subject to thermogenetic ether exchange interaction, improved the thermotolerance of polymerization; Secondly, the present invention has introduced imidazoles monomer, and the introducing of imidazole ring has also improved main chain rigidity, and then the thermotolerance of modified polyarylether ketone is improved; Again, the present invention has introduced larger side group or aliphatic chain on the main chain of modified polyarylether ketone, to adjust the structure of main chain, improves its aggregated structure, thereby its solubleness is improved.
Experimental result shows, the second-order transition temperature of modified polyarylether ketone prepared by the present invention can be up to 270 ℃, and 5% thermal weight loss temperature can be up to 541 ℃, 600 ℃ of carbon yields can reach 70.7%, and this polyaryletherketone is equal solubilized in DMF, N,N-dimethylacetamide and chloroform.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the modified polyarylether ketone shown in the formula (I-a) for preparing of the embodiment of the present invention 1;
Fig. 2 is the infrared spectrogram of the modified polyarylether ketone shown in the formula (I-a) for preparing of the embodiment of the present invention 1;
Fig. 3 is the modified polyarylether ketone DSC secondary temperature elevation graphic representation shown in the formula (I-a) for preparing of the embodiment of the present invention 1;
Fig. 4 is the thermogravimetric analysis figure of the modified polyarylether ketone shown in the formula (I-a) being obtained by the embodiment of the present invention 1.
Embodiment
The invention provides a kind of modified polyarylether ketone, as shown in the formula (I):
Described-Ar
1-be selected from a kind of in following formula (1)～formula (2) structure:
Described-Ar
2-be selected from a kind of in following formula (4)～formula (6) 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 the alkyl of C1～C5, is 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; R
5with R
6be selected from independently of one another the alkyl of C1～C5 or the alkyl of C1～C5 that fluorine replaces, be preferably CH
3or CF
3; M and n are the polymerization degree, and the ratio of m and n is preferably (99:1)～(1:99), more preferably (80:1)～(1:80), then be preferably (40:1)～(1:40), most preferably be (10:1)～(1:10).
In modified polyarylether ketone main chain of the present invention, with imidazoles, partly replaced the bis-phenol structure of ether-containing key, oxygen atom content in backbone structure is reduced, ether link content reduces, thereby reduced molecular chain, is subject to thermogenetic ether exchange interaction, has improved the thermotolerance of polymerization; And the present invention has introduced imidazoles monomer, the introducing of imidazole ring has also improved main chain rigidity, and then the thermotolerance of modified polyarylether ketone is improved; In addition, on the main chain of the modified polyarylether ketone shown in formula (I), introduced larger side group or aliphatic chain, to adjust the structure of main chain, improved its aggregated structure, thereby its solubleness is improved.
The present invention also provides the preparation method of the modified polyarylether ketone shown in above-mentioned formula (I), comprising:
A) under the condition of protection of inert gas, imidazoles monomer, biphenol monomer are mixed with the first aprotic solvent with two substituted diphenylamine ketone of formula (IV) structure, under carbonate effect, reacting by heating, obtains the modified polyarylether ketone shown in formula (I);
Described imidazoles monomer has formula (II-1) structure or formula (II-2) structure;
Described biphenol monomer has formula (III-1) structure, formula (III-2) structure or formula (III-3) structure;
Described-Ar
1-be selected from a kind of in following formula (1)～formula (2) structure:
Described-Ar
2-be selected from a kind of in following formula (4)～formula (6) 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 the alkyl of C1～C5; R
3with R
4be selected from independently of one another a kind of in H, phenyl and substituted-phenyl; R
5with R
6be selected from independently of one another alkyl or fluorine substituted alkyl; M and n are the polymerization degree; X is halogen atom or NO
2.Described R
1, R
2, R
3, R
4, R
5with R
6all 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.
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, imidazoles monomer, biphenol monomer are mixed with the first aprotic solvent with two substituted diphenylamine ketone of formula (IV) structure.Wherein, described imidazoles monomer is preferably benzimidazolone, 5-methyl benzimidazolone, 5-Amino-2-benzimidazolinone, 5-Nitro-2-benzimidazolinone, 5,6-dimethylbenzimidazole quinoline ketone, 5, one or more in 6-diamino benzo imidazolone and thioketones thereof; Described biphenol monomer is preferably one or more in dihydroxyphenyl propane, hexafluoro bisphenol-a, phenolphthalein and bisphenol fluorene, more preferably dihydroxyphenyl propane, hexafluoro bisphenol-a, phenolphthalein or bisphenol fluorene; Two substituted diphenylamine ketone of described formula (IV) structure are preferably 4,4 '-bis-chloro benzophenones and/or 4,4 '-difluoro benzophenone; The mol ratio of imidazoles monomer and biphenol monomer is preferably (99:1)～(1:99), and more preferably (80:1)～(1:80), then be preferably (40:1)～(1:40), most preferably be (10:1)～(1:10); The ratio of the amount of substance of two substituted diphenylamine ketone of the amount of substance sum of described imidazoles monomer and biphenol monomer and formula (IV) structure is preferably (1:1)～(1:1.01).
The first aprotic solvent is aprotic solvent well known to those skilled in the art, there is no special restriction, in the present invention, be preferably N-Methyl pyrrolidone, N-cyclohexyl pyrrolidone, N, one or more in dinethylformamide, N,N-dimethylacetamide, tetramethylene sulfone, methylimidazole ketone and sulfobenzide; The amount that described the first aprotic solvent adds is preferably and makes the solid content of reaction system is 10%～40%, more preferably 15%～35%, then be preferably 18%～30%.
In the present invention, imidazoles monomer, biphenol monomer react the polyaryletherketone of synthesis type (I) structure with two substituted diphenylamine ketone of formula (IV) 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; The amount of substance of imidazoles monomer and biphenol monomer and be preferably 1:(1～5 with the ratio of the amount of substance of carbonate), 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 band aqua, is with water reaction.Described band aqua is band aqua well known to those skilled in the art, there is no special restriction, is preferably that to take toluene and/or dimethylbenzene be band aqua in the present invention; The described temperature with water reaction is preferably 120 ℃～160 ℃, and more preferably 130 ℃～160 ℃, the time is preferably 1～3h, more preferably 1.5～2.5h.
After the reaction of band water, preferably remove after band aqua, then carry out reacting by heating.Described method of removing with aqua preferably adopts to heat up and removes.
Under 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 ℃～230 ℃, 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 dilute, then add precipitation agent precipitation, obtain the modified polyarylether ketone shown in formula (I).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; The amount that the second aprotic solvent adds is preferably and makes the solid content of reaction system is 5～10%, more preferably 8%～10%; Described precipitation agent is precipitation agent protonic solvent well known to those skilled in the art, there is no special restriction, in the present invention, be preferably one or more in water, ethanol and acetic acid, more preferably three's mixing solutions, the present invention, to three's ratio unrestricted, can be arbitrary proportion and mixes.
The present invention carries out solution polycondensation by imidazoles monomer, biphenol 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 modified polyarylether ketone prepared by the present invention can be up to 270 ℃, and 5% thermal weight loss temperature can be up to 541 ℃, 600 ℃ of carbon yields can reach 70.7%, and this polyaryletherketone is equal solubilized in DMF, N,N-dimethylacetamide and chloroform.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of modified polyarylether ketone provided by the invention and preparation method thereof is described in detail.
In following examples, reagent used is commercially available.
In tri-mouthfuls of round-bottomed flasks of 100ml, add successively 0.671g(0.005mol) benzimidazolone (HBI), 1.141g(0.005mol) dihydroxyphenyl propane (BPA), 2.182g difluoro benzophenone (DFK), 2.763g salt of wormwood, 1.500g calcium carbonate, 15ml N-Methyl pyrrolidone (NMP) and 20ml toluene, be heated to 132 ℃ of insulation 2.5h, azeotropic water removing, toluene is removed in intensification, continue to be heated to 195 ℃, reaction 6h, cooling, add 20ml N, the dilution of N-N,N-DIMETHYLACETAMIDE, at ethanol, in the mixing solutions of water and acetic acid, precipitate, after throw out filters, in apparatus,Soxhlet's, use deionized water extraction 12h, remove inorganic salt and reaction solvent, dry, obtain the modified polyarylether ketone shown in formula (I-a), yield is 94%, its reaction formula is as follows:
The results show, the modified polyarylether ketone shown in the formula obtaining in embodiment 1 (I-a) is equal solubilized in DMF, N,N-dimethylacetamide and chloroform.
Utilize nucleus magnetic resonance to test the modified polyarylether ketone shown in the formula obtaining in embodiment 1 (I-a), obtain its hydrogen nuclear magnetic resonance spectrogram, as shown in Figure 1.As shown in Figure 1,1.72ppm place is the fignal center of methyl H on dihydroxyphenyl propane unit, and 8.1ppm and 7.2ppm place are respectively the fignal center of aromatic ring H in benzimidazolone structural unit, and 6.9～8.0ppm is the fignal center of aromatic ring H in polymkeric substance.
Utilize infrared spectrometer to test the modified polyarylether ketone shown in the formula obtaining in embodiment 1 (I-a), obtain its infrared spectrogram, as shown in Figure 2.As shown in Figure 2,2969cm
-1for dihydroxyphenyl propane methyl C-H stretching vibration absorption peak, 1726cm
-1for the two key stretching vibration absorption peaks of carbonyl C=O on imidazole ring, 1657cm
-1for the two key stretching vibration absorption peaks of carbonyl C=O on benzophenone, 1244cm
-1stretching vibration absorption peak for the Ar-O-Ar that forms.
Utilize differential scanning calorimetry the modified polyarylether ketone shown in the formula obtaining in embodiment 1 (I-a) to be tested to (testing method is nitrogen atmosphere, 25 ℃～350 ℃, temperature rate is 20K/min), obtain its DSC secondary temperature elevation graphic representation, as shown in Figure 3.Its Tg is 216 ℃ as shown in Figure 3, illustrates that this modified polyarylether ketone has higher heat resisting temperature.
Utilize thermogravimetric analyzer to test (testing method is nitrogen atmosphere, 30 ℃～600 ℃, and temperature rate is 20K/min) to the modified polyarylether ketone shown in the formula obtaining in embodiment 1 (I-a), obtain its thermogravimetric analysis figure, as shown in Figure 4.As shown in Figure 4, its 5% thermal weight loss temperature is up to 541 ℃, and 600 ℃ of carbon yields are 70.7%, illustrate that the thermal decomposition performance of this modified polyarylether ketone is good, have higher ablation resistance.
In tri-mouthfuls of round-bottomed flasks of 100ml, add successively 1.487g(0.0099mol) benzoglyoxaline thioketones (MBI), 0.032g(0.0001mol) phenolphthalein (PHI), 2.511g(0.01mol) dichloro benzophenone (DCK), 2.763g salt of wormwood, 15g N-cyclohexyl pyrrolidone (CHP) and 12ml toluene, be heated to 130 ℃ of azeotropic water removings, insulation 2.5h, toluene is removed in intensification, continue to be heated to 185 ℃, reaction 3h, cooling, add 20ml N, the dilution of N-N,N-DIMETHYLACETAMIDE, in the mixing solutions of ethanol and water, precipitate, after throw out filters, in apparatus,Soxhlet's, use deionized water extraction 12h, remove inorganic salt and reaction solvent, dry, obtain the modified polyarylether ketone shown in formula (I-b), yield is 92.5%, its reaction formula is as follows:
The results show, the modified polyarylether ketone shown in the formula obtaining in embodiment 2 (I-b) is equal solubilized in DMF, N,N-dimethylacetamide and chloroform.
Modified polyarylether ketone shown in the formula obtaining in embodiment 2 (I-b) is carried out to second-order transition temperature test, and obtaining its Tg is 181 ℃.
Embodiment 3
In tri-mouthfuls of round-bottomed flasks of 100ml, add successively 0.013g(0.0001mol) benzimidazolone (HBI), 3.154g(0.0099mol) phenolphthalein (PHI), 2.204g(0.0101mol) difluoro benzophenone (DFK), 1.589g salt of wormwood, 25g tetramethylene sulfone and 12ml toluene, be heated to 130 ℃ of azeotropic water removings, insulation 2.5h, toluene is removed in intensification, continue to be heated to 185 ℃, reaction 4.5h, cooling, add 30ml N, the dilution of N-N,N-DIMETHYLACETAMIDE, at ethanol, in the mixing solutions of water and acetic acid, precipitate, after throw out filters, in apparatus,Soxhlet's, use deionized water extraction 12h, remove inorganic salt and reaction solvent, dry, obtain the modified polyarylether ketone shown in formula (I-c), yield is 96.2%, its reaction formula is as follows:
The results show, the modified polyarylether ketone shown in the formula obtaining in embodiment 3 (I-c) is equal solubilized in DMF, N,N-dimethylacetamide and chloroform.
Modified polyarylether ketone shown in the formula obtaining in embodiment 3 (I-c) is carried out to second-order transition temperature test, and obtaining its Tg is 238 ℃.
Embodiment 4
In tri-mouthfuls of round-bottomed flasks of 100ml, add successively 0.811g(0.005mol) 4, 5-dimethylbenzimidazole ketone (DmHBI), 1.141g(0.005mol) dihydroxyphenyl propane (BPA), 2.182g difluoro benzophenone (DFK), 2.763g salt of wormwood, 1.500g calcium carbonate, 15g sulfobenzide and 12ml toluene, be heated to 135 ℃ of insulation 3h, azeotropic water removing, toluene is removed in intensification, continue to be heated to 230 ℃, reaction 4h, cooling, add 20ml N, the dilution of N-N,N-DIMETHYLACETAMIDE, at ethanol, in the mixing solutions of water and acetic acid, precipitate, after throw out filters, in apparatus,Soxhlet's, use deionized water extraction 12h, remove inorganic salt and reaction solvent, dry, obtain the modified polyarylether ketone shown in formula (I-e), yield is 92%, its reaction formula is as follows:
The results show, the modified polyarylether ketone shown in the formula obtaining in embodiment 4 (I-d) is equal solubilized in DMF, N,N-dimethylacetamide and chloroform.
Modified polyarylether ketone shown in the formula obtaining in embodiment 2 (I-d) is carried out to second-order transition temperature test, and obtaining its Tg is 232 ℃.
Embodiment 5
In tri-mouthfuls of round-bottomed flasks of 100ml, add successively 0.473g(0.002mol) 4, 5-imidazole diphenyl ketone (DPHBI), 2.690g(0.008mol) hexafluoro bisphenol-a (HFBPA), 2.182g(0.01mol) difluoro benzophenone (DFK), 1.382g salt of wormwood, 3.000g calcium carbonate, 15ml methylimidazole ketone (DMI) and 20ml dimethylbenzene, be heated to 160 ℃ of insulation 1h, azeotropic water removing, heat up except removal xylene, continue to be heated to 185 ℃, reaction 4.5h, cooling, add 20ml N, the dilution of N-N,N-DIMETHYLACETAMIDE, at ethanol, in the mixing solutions of water and acetic acid, precipitate, after throw out filters, in apparatus,Soxhlet's, use deionized water extraction 12h, remove inorganic salt and reaction solvent, dry, obtain the modified polyarylether ketone shown in formula (I-e), yield is 91.5%, its reaction formula is as follows:
The results show, the modified polyarylether ketone shown in the formula obtaining in embodiment 5 (I-e) is equal solubilized in DMF, N,N-dimethylacetamide and chloroform.
Modified polyarylether ketone shown in the formula obtaining in embodiment 5 (I-e) is carried out to second-order transition temperature test, and obtaining its Tg is 203 ℃.
Embodiment 6
In tri-mouthfuls of round-bottomed flasks of 100ml, add successively 0.896g(0.005mol) 5-Nitro-2-benzimidazolinone (nHBI), 1.752g(0.005mol) bisphenol fluorene (BPF), 2.524g(0.01005mol) dichloro benzophenone (DCK), 2.073g salt of wormwood, 0.500g calcium carbonate, 18ml N-Methyl pyrrolidone (NMP) and 15ml toluene, be heated to 130 ℃ of insulation 2h, azeotropic water removing, toluene is removed in intensification, continue to be heated to 195 ℃, reaction 8h, cooling, add the dilution of 12ml N-Methyl pyrrolidone, at ethanol, in the mixing solutions of water and acetic acid, precipitate, after throw out filters, in apparatus,Soxhlet's, use deionized water extraction 12h, remove inorganic salt and reaction solvent, dry, obtain the modified polyarylether ketone shown in formula (I-f), its reaction formula is as follows:
The results show, the modified polyarylether ketone shown in the formula obtaining in embodiment 6 (I-f) is equal solubilized in DMF, N,N-dimethylacetamide and chloroform.
Modified polyarylether ketone shown in the formula obtaining in embodiment 2 (I-f) is carried out to second-order transition temperature test, and obtaining its Tg is 270 ℃.
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 modified polyarylether ketone, as shown in the formula (I):
Described-Ar
1-be selected from a kind of in following formula (1)～formula (2) structure:
Described-Ar
2-be selected from a kind of in following formula (4)～formula (6) 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 the alkyl of C1～C5; R
3with R
4be selected from independently of one another a kind of in H, phenyl and substituted-phenyl; R
5with R
6be selected from independently of one another the alkyl of C1～C5 or the alkyl of C1～C5 that fluorine replaces; M and n are the polymerization degree.
2. modified polyarylether ketone according to claim 1, is characterized in that, described R
1with R
2be selected from independently of one another H, NH
2, NO
2with CH
3in a kind of.
3. modified polyarylether ketone according to claim 1, is characterized in that, described R
5with R
6be CH independently of one another
3or CF
3.
4. modified polyarylether ketone according to claim 1, is characterized in that, the ratio of described m and n is (99:1)～(1:99).
5. a preparation method for modified polyarylether ketone, is characterized in that, comprising:
A) under the condition of protection of inert gas, imidazoles monomer, biphenol monomer are mixed with the first aprotic solvent with two substituted diphenylamine ketone of formula (IV) structure, under carbonate effect, reacting by heating, obtains the modified polyarylether ketone shown in formula (I);
Described imidazoles monomer has formula (II-1) structure or formula (II-2) structure;
Described biphenol monomer has formula (III-1) structure, formula (III-2) structure or formula (III-3) structure;
Described-Ar
1-be selected from a kind of in following formula (1)～formula (2) structure:
Described-Ar
2-be selected from a kind of in following formula (4)～formula (6) 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 the alkyl of C1～C5; R
3with R
4be selected from independently of one another a kind of in H, phenyl and substituted-phenyl; R
5with R
6be selected from independently of one another the alkyl of C1～C5 or the alkyl of C1～C5 that fluorine replaces; M and n are the polymerization degree; X is halogen atom or NO
2.
6. preparation method according to claim 5, is characterized in that, steps A) also comprise: before reacting by heating, add band aqua, be with water reaction.
7. preparation method according to claim 6, is characterized in that, described band aqua is toluene and/or dimethylbenzene.
8. preparation method according to claim 6, is characterized in that, the described temperature with water reaction is 120 ℃～160 ℃, and the time is 1～3h.
9. preparation method according to claim 5, is characterized in that, described the first aprotic solvent add-on is 10%～40% for making solid content.
10. preparation method according to claim 5, 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 modified polyarylether ketone shown in formula (I).
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| CN104761717A (en) * | 2015-04-17 | 2015-07-08 | 中国科学院长春应用化学研究所 | Polyaryletherketone quadripolymer and preparation method thereof |
| CN113717377A (en) * | 2020-05-25 | 2021-11-30 | 中国科学院大连化学物理研究所 | Amorphous polyaryletherketone (sulfone) 3D printing polymer and preparation and printing methods thereof |
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| EP4116356A1 (en) * | 2021-07-07 | 2023-01-11 | Ht Materials Corporation | Aromatic polysulfone copolymers |
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| CN104761717B (en) * | 2015-04-17 | 2018-03-20 | 中国科学院长春应用化学研究所 | A kind of PAEK quadripolymer and preparation method thereof |
| CN104761717A (en) * | 2015-04-17 | 2015-07-08 | 中国科学院长春应用化学研究所 | Polyaryletherketone quadripolymer and preparation method thereof |
| CN113717377B (en) * | 2020-05-25 | 2023-04-07 | 中国科学院大连化学物理研究所 | Amorphous polyaryletherketone (sulfone) 3D printing polymer and preparation and printing methods thereof |
| CN113717377A (en) * | 2020-05-25 | 2021-11-30 | 中国科学院大连化学物理研究所 | Amorphous polyaryletherketone (sulfone) 3D printing polymer and preparation and printing methods thereof |
| US20210380762A1 (en) * | 2020-06-09 | 2021-12-09 | Ht Materials Corporation | Semicrystalline Poly(aryl ether ketone) Copolymers |
| 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 |
| WO2022010587A1 (en) * | 2020-07-05 | 2022-01-13 | Ht Materials Corporation | High temperature semicrystalline poly(aryl ether ketone) copolymers |
| US20220002484A1 (en) * | 2020-07-05 | 2022-01-06 | Ht Materials Corporation | High Temperature Semicrystalline Poly(aryl ether ketone) Copolymers |
| US11692094B2 (en) | 2020-09-17 | 2023-07-04 | Ht Materials Corporation | High temperature polyketone copolymers |
| CN115594849A (en) * | 2021-07-07 | 2023-01-13 | 奥瑞隆新材料（山东）有限公司（Cn） | Aromatic polysulfone copolymers |
| EP4116356A1 (en) * | 2021-07-07 | 2023-01-11 | Ht Materials Corporation | Aromatic polysulfone copolymers |
| US11851532B2 (en) | 2021-07-07 | 2023-12-26 | Ht Materials Corporation | Aromatic polysulfone copolymers |
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