CN103509185B - A kind of modified polyarylether ketone and preparation method thereof - Google Patents
A kind of modified polyarylether ketone and preparation method thereof Download PDFInfo
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- CN103509185B CN103509185B CN201310440166.0A CN201310440166A CN103509185B CN 103509185 B CN103509185 B CN 103509185B CN 201310440166 A CN201310440166 A CN 201310440166A CN 103509185 B CN103509185 B CN 103509185B
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Abstract
The invention provides a kind of modified polyarylether ketone and preparation method thereof, this modified polyarylether ketone as shown in the formula (I).Compared with existing polyaryletherketone, first, instead of the bis-phenol structure of ether-containing key with imidazole fragment in modified polyarylether ketone main chain of the present invention, oxygen atom content in backbone structure is reduced, ether link content reduces, thus decrease molecular chain by thermogenetic ether exchange interaction, improve the thermotolerance of polymerization; Secondly, invention introduces imidazoles monomer, the introducing of imidazole ring also improves main chain rigidity, and then the thermotolerance of modified polyarylether ketone is improved; Again, the present invention introduces larger side base or aliphatic chain on the main chain of modified polyarylether ketone, to adjust the structure of main chain, improves its aggregated structure, thus its solubleness is improved.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly relate to a kind of modified polyarylether ketone 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 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 one in following formula (1) ~ formula (2) structure:
Described-Ar
2-be selected from one 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 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; R
5with R
6be selected from the alkyl of the alkyl of C1 ~ C5 or the C1 ~ C5 of fluorine replacement independently of one another; M and n is the polymerization degree.
Preferably, described R
1with R
2be selected from H, NH independently of one another
2, NO
2with CH
3in one.
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).
Present invention also offers 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 one in following formula (1) ~ formula (2) structure:
Described-Ar
2-be selected from one 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 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; R
5with R
6be selected from alkyl or fluorine substituted alkyl independently of one another; M and 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 120 DEG C ~ 160 DEG C, and the time is 1 ~ 3h.
Preferably, described 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).Compared with existing polyaryletherketone, first, instead of the bis-phenol structure of ether-containing key with imidazole fragment in modified polyarylether ketone main chain of the present invention, oxygen atom content in backbone structure is reduced, ether link content reduces, thus decrease molecular chain by thermogenetic ether exchange interaction, improve the thermotolerance of polymerization; Secondly, invention introduces imidazoles monomer, the introducing of imidazole ring also improves main chain rigidity, and then the thermotolerance of modified polyarylether ketone is improved; Again, the present invention introduces larger side base or aliphatic chain on the main chain of modified polyarylether ketone, to adjust the structure of main chain, improves its aggregated structure, thus its solubleness is improved.
Experimental result shows, the second-order transition temperature of modified polyarylether ketone prepared by the present invention can up to 270 DEG C, and 5% thermal weight loss temperature can up to 541 DEG C, 600 DEG C of carbon yields can reach 70.7%, and this polyaryletherketone equal solubilized in DMF, N,N-dimethylacetamide and chloroform.
Accompanying drawing explanation
The hydrogen nuclear magnetic resonance spectrogram of the modified polyarylether ketone shown in formula (I-a) that Fig. 1 prepares for the embodiment of the present invention 1;
The infrared spectrogram of the modified polyarylether ketone shown in formula (I-a) that Fig. 2 prepares for the embodiment of the present invention 1;
The modified polyarylether ketone DSC secondary temperature elevation graphic representation shown in formula (I-a) that Fig. 3 prepares for 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) that 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 one in following formula (1) ~ formula (2) structure:
Described-Ar
2-be selected from one 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 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; R
5with R
6be selected from the alkyl of the alkyl of C1 ~ C5 or the C1 ~ C5 of fluorine replacement independently of one another, be preferably CH
3or CF
3; M and n is the polymerization degree, and the ratio of m and n is preferably (99:1) ~ (1:99), is more preferably (80:1) ~ (1:80), then is preferably (40:1) ~ (1:40), most preferably be (10:1) ~ (1:10).
Instead of the bis-phenol structure of ether-containing key in modified polyarylether ketone main chain of the present invention with imidazole fragment, oxygen atom content in backbone structure is reduced, and ether link content reduces, thus decreases molecular chain by thermogenetic ether exchange interaction, improves the thermotolerance of polymerization; Further, invention introduces imidazoles monomer, the introducing of imidazole ring also improves main chain rigidity, and then the thermotolerance of modified polyarylether ketone is improved; In addition, the main chain of the modified polyarylether ketone shown in formula (I) introduces larger side base or aliphatic chain, to adjust the structure of main chain, improve its aggregated structure, thus its solubleness is improved.
Present invention also offers 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 one in following formula (1) ~ formula (2) structure:
Described-Ar
2-be selected from one 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 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; R
5with R
6be selected from alkyl or fluorine substituted alkyl independently of one another; M and n is 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 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, 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 one or more in benzimidazolone, 5-methyl benzimidazolone, 5-Amino-2-benzimidazolinone, 5-Nitro-2-benzimidazolinone, 5,6-dimethylbenzimidazole quinoline ketone, 5,6-diamino Benzimidazolinones and thioketones thereof; Described biphenol monomer is preferably one or more in dihydroxyphenyl propane, hexafluoro bisphenol-a, phenolphthalein and bisphenol fluorene, is more preferably dihydroxyphenyl propane, hexafluoro bisphenol-a, phenolphthalein or bisphenol fluorene; Two substituted diphenylamine ketone of described formula (IV) structure are preferably 4,4 '-dichlorobenzophenone and/or 4,4 '-difluoro benzophenone; The mol ratio of imidazoles monomer and biphenol monomer is preferably (99:1) ~ (1:99), is more preferably (80:1) ~ (1:80), then is preferably (40:1) ~ (1:40), most preferably be (10:1) ~ (1:10); The ratio of the amount of substance of the amount of substance sum of described imidazoles monomer and biphenol monomer and two substituted diphenylamine ketone of formula (IV) structure is preferably (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, biphenol monomer and formula (IV) 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; 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), 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 120 DEG C ~ 160 DEG C, and be more preferably 130 DEG C ~ 160 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 ~ 230 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 modified polyarylether ketone shown in formula (I).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 protonic solvent 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, biphenol 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 modified polyarylether ketone prepared by the present invention can up to 270 DEG C, and 5% thermal weight loss temperature can up to 541 DEG C, 600 DEG C of carbon yields can reach 70.7%, and this polyaryletherketone 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.
Reagent used in following examples is commercially available.
Embodiment 1
0.671g(0.005mol is added successively in 100ml tri-mouthfuls of round-bottomed flasks) benzimidazolone (HBI), 1.141g(0.005mol) dihydroxyphenyl propane (BPA), 2.182g difluoro benzophenone (DFK), 2.763g salt of wormwood, 1.500g calcium carbonate, 15mlN-methyl-2-pyrrolidone (NMP) and 20ml toluene, be heated to 132 DEG C of insulation 2.5h, azeotropic water removing, heat up removing toluene, continue to be heated to 195 DEG C, reaction 6h, cooling, add 20mlN, N-N,N-DIMETHYLACETAMIDE dilutes, 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 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 obtained 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 obtained 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 is 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 obtained 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 carbonyl C=O double bond stretching vibration absorption peak on imidazole ring, 1657cm
-1for carbonyl C=O double bond stretching vibration absorption peak on benzophenone, 1244cm
-1for the stretching vibration absorption peak of the Ar-O-Ar of formation.
Utilize differential scanning calorimetry to the modified polyarylether ketone shown in the formula obtained in embodiment 1 (I-a) test (testing method be nitrogen atmosphere, 25 DEG C ~ 350 DEG C, temperature rate is 20K/min), obtain its DSC secondary temperature elevation graphic representation, as shown in Figure 3.Its Tg is 216 DEG C as shown in Figure 3, illustrates that this modified polyarylether ketone has higher heat resisting temperature.
Utilize thermogravimetric analyzer to the modified polyarylether ketone shown in the formula obtained in embodiment 1 (I-a) test (testing method be nitrogen atmosphere, 30 DEG C ~ 600 DEG C, temperature rate is 20K/min), obtain its thermogravimetric analysis figure, as shown in Figure 4.As shown in Figure 4, its 5% thermal weight loss temperatures as high 541 DEG C, 600 DEG C of carbon yields are 70.7%, illustrate that the thermal decomposition performance of this modified polyarylether ketone is good, have higher ablation resistance.
Embodiment 2
1.487g(0.0099mol is added successively in 100ml tri-mouthfuls of round-bottomed flasks) benzimidazolothione (MBI), 0.032g(0.0001mol) phenolphthalein (PHI), 2.511g(0.01mol) dichloro benzophenone (DCK), 2.763g salt of wormwood, 15gN-cyclohexyl pyrrolidone (CHP) and 12ml toluene, be heated to 130 DEG C of azeotropic water removings, insulation 2.5h, heat up removing toluene, continue to be heated to 185 DEG C, reaction 3h, cooling, add 20mlN, 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 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 obtained in embodiment 2 (I-b) is equal solubilized in DMF, N,N-dimethylacetamide and chloroform.
Carry out second-order transition temperature test to the modified polyarylether ketone shown in the formula obtained in embodiment 2 (I-b), obtaining its Tg is 181 DEG C.
Embodiment 3
0.013g(0.0001mol is added successively in 100ml tri-mouthfuls of round-bottomed flasks) 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 DEG C of azeotropic water removings, insulation 2.5h, heat up removing toluene, continue to be heated to 185 DEG C, reaction 4.5h, cooling, add 30mlN, N-N,N-DIMETHYLACETAMIDE dilutes, 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 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 obtained in embodiment 3 (I-c) is equal solubilized in DMF, N,N-dimethylacetamide and chloroform.
Carry out second-order transition temperature test to the modified polyarylether ketone shown in the formula obtained in embodiment 3 (I-c), obtaining its Tg is 238 DEG C.
Embodiment 4
0.811g(0.005mol is added successively in 100ml tri-mouthfuls of round-bottomed flasks) 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 DEG C of insulation 3h, azeotropic water removing, heat up removing toluene, continue to be heated to 230 DEG C, reaction 4h, cooling, add 20mlN, N-N,N-DIMETHYLACETAMIDE dilutes, 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 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 obtained in embodiment 4 (I-d) is equal solubilized in DMF, N,N-dimethylacetamide and chloroform.
Carry out second-order transition temperature test to the modified polyarylether ketone shown in the formula obtained in embodiment 2 (I-d), obtaining its Tg is 232 DEG C.
Embodiment 5
0.473g(0.002mol is added successively in 100ml tri-mouthfuls of round-bottomed flasks) 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 DEG C of insulation 1h, azeotropic water removing, heat up except removal xylene, continue to be heated to 185 DEG C, reaction 4.5h, cooling, add 20mlN, N-N,N-DIMETHYLACETAMIDE dilutes, 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 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 obtained in embodiment 5 (I-e) is equal solubilized in DMF, N,N-dimethylacetamide and chloroform.
Carry out second-order transition temperature test to the modified polyarylether ketone shown in the formula obtained in embodiment 5 (I-e), obtaining its Tg is 203 DEG C.
Embodiment 6
0.896g(0.005mol is added successively in 100ml tri-mouthfuls of round-bottomed flasks) 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, 18mlN-methyl-2-pyrrolidone (NMP) and 15ml toluene, be heated to 130 DEG C of insulation 2h, azeotropic water removing, heat up removing toluene, continue to be heated to 195 DEG C, reaction 8h, cooling, add the dilution of 12mlN-methyl-2-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 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 obtained in embodiment 6 (I-f) is equal solubilized in DMF, N,N-dimethylacetamide and chloroform.
Carry out second-order transition temperature test to the modified polyarylether ketone shown in the formula obtained in embodiment 2 (I-f), obtaining its Tg is 270 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 (9)
1. a modified polyarylether ketone, shown in (I):
Described-Ar
1-be selected from one in following formula (1) ~ formula (2) structure:
Described-Ar
2-be selected from one 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 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; R
5with R
6be selected from the alkyl of the alkyl of C1 ~ C5 or the C1 ~ C5 of fluorine replacement independently of one another; M and n is the polymerization degree, and the ratio of described m and n is (99:1) ~ (1:99).
2. modified polyarylether ketone according to claim 1, is characterized in that, described R
1with R
2be selected from H, NH independently of one another
2, NO
2with CH
3in one.
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. 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 one in following formula (1) ~ formula (2) structure:
Described-Ar
2-be selected from one 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 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; R
5with R
6be selected from the alkyl of the alkyl of C1 ~ C5 or the C1 ~ C5 of fluorine replacement independently of one another; M and n is the polymerization degree, and the ratio of described m and n is (99:1) ~ (1:99); X is halogen atom or NO
2.
5. preparation method according to claim 4, is characterized in that, steps A) also comprise: before reacting by heating, add water entrainer, carry out the reaction of band water.
6. preparation method according to claim 5, is characterized in that, described water entrainer is toluene and/or dimethylbenzene.
7. preparation method according to claim 5, is characterized in that, the temperature of described band water reaction is 120 DEG C ~ 160 DEG C, and the time is 1 ~ 3h.
8. preparation method according to claim 4, is characterized in that, described first aprotic solvent add-on is 10% ~ 40% for making solid content.
9. preparation method according to claim 4, 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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