CN103709404A - PBO (poly(p-phenylene-2,6-benzobisoxazole)) copolycondensation modification method - Google Patents
PBO (poly(p-phenylene-2,6-benzobisoxazole)) copolycondensation modification method Download PDFInfo
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Abstract
The invention discloses a PBO (poly(p-phenylene-2,6-benzobisoxazole)) copolycondensation modification method. The method can be used for modification to prepare a PBO copolymer and prepare polymers with higher heat stability. The method comprises the following steps: (1) titrating a NaOH solution of terephthalic acid and second dicarboxylic acid monomer mixed in any ratio into an equal molar weight of 4,6-diamino-resorcinol hydrochloride water solution, or (2) titrating an equal molar weight of terephthalic acid NaOH solution into a mixed solution of 4,6-diamino-resorcinol hydrochloride and polyamine salt monomer mixed in any ratio; and salifying, precipitating, and directly polymerizing the salt in a PPA solution to obtain the PBO copolymer. The result indicates that the heat stability of the PBO copolymer prepared by copolymerization modification of small amounts of third monomer is enhanced to some extent.
Description
Technical field
The present invention relates to the preparation method of PBO multipolymer, particularly relate to by synthetic DAR-TA salt mixing salt and then prepare the method for PBO multipolymer, and the method for improving PBO thermal stability by copolymerization, genus chemical synthesis technical field.
Background technology
Polyparaphenylene's benzoxazole fiber (Poly-p-phenylene-benzobisoxazole is called for short PBO), commodity are called bavin grand (Zylon), are described as 21 century super fiber.Early than the eighties in 20th century U.S. by development aerospace cause, developed, rear patent is spun company by Japanese Japan and is proceeded to, and realizes industrialization.So far, Japan spins and remains unique enterprise that has this technology in the world.
Pbo fiber is that main chain is the conjugation rigid macromolecule of aromatic nucleus family heterocycle structure, height-oriented due to molecular structure, make its easy fibroblast, and the component units of fiber and fento and fine unit also all height-oriented, further macromolecular fibre orientation, makes PBO have outstanding especially performance at mechanics and the aspect such as high temperature resistant in conjunction with the high linkage force of its fragrance and heterocycle.Its resistance to elevated temperatures is the highest in current organic materials, and its tensile strength and modular ratio carbon fiber are also high, and it has the highest firing resistance etc. equally.
Due to the various outstanding performance characteristics of PBO, it has important application in the keys such as defence and military, aerospace, fire prevention fire-fighting and special dimension.And along with going deep into that PBO studies, its application is more and more found and develops.And along with going deep into of applying, also more and more higher to the requirement of its performance.Therefore in order to overcome the deficiency itself existing and further to improve its high-performance, PBO is carried out to modification and have great importance.
PBO is the best organic fibrous material of current resistance to elevated temperatures, and its most outstanding performance is exactly that its resistance to elevated temperatures can reach 650 ℃, is one of most important, superior performance of PBO.And the application that relates to the PBO that resistance to elevated temperatures is relevant is also very extensive, demand is also quite urgent.Along with it is answered land used popularization and gos deep into, also more and more higher to the requirement of its resistance to elevated temperatures.Therefore, by modification, improving its resistance to elevated temperatures has great importance.
Synthetic and the PBO modification by copolymerization of conventional P BO all adopt 4; 6-diamino resorcin (DAR) hydrochloride monomer, terephthalic acid and the 3rd monomer directly in PPA polycondensation form (Cui Tianfang; Chen Ping; Ma Xiaoyu; Shu Yan. the synthetic and performance study [J] of polyphenyl two uh azoles series polymer. material engineering, 2008; Lee, J. K.; Kim, J. H.; Kim, Y. J., Synthesis and characterization of fluorine-containing polybenzoxazoles by high-temperature direct polycondensation[J]. B. Kor. Chem. Soc. 2003,24,1029-1031.).And this method is due to the problems such as solvability of dehydrogenation and terephthalic acid, technological process is quite complicated, and reaction time is very long, serious etc. to equipment corrosion.
In recent years occur 4; 6-diamino resorcin and terephthalic acid are prepared into 4; 6-diamino resorcin-terephthalic acid (DAR-TA) salt; further be prepared into again the method for PBO homopolymer; not only the reaction times shortens greatly; technique is simple, and due to strict etc. mole of two kinds of monomers, can prepare the relatively large PBO polymkeric substance of molecular weight (Zhang Chunyan; Shi Zixing; Cold dimension; Yin Jie; Zhu Zikang, adopts the synthetic polyhenylene benzene of 4,6-diaminoresorcinol terephthalate two oxazoles [J]. Shanghai Communications University's journal 2003,37,646-649).The method is with 4,6-diamino resorcin hydrochlorate and terephthalic acid are raw material, have prepared 4,6-diaminoresorcinol-terephthalate (TA salt), take polyphosphoric acid as medium again, the polycondensation of TA salt is obtained having to the PBO of viscosity higher.The method is that mixed polycondensation becomes homopolymer, is only the problems such as important means prepared by PBO homopolymer, the preparation difficulty of unresolved PBO analog copolymer.At present still effectively do not improve the preparation method of PBO multipolymer, need a kind of novel process of improving preparation PBO multipolymer of exploitation badly, with the key propertys such as thermostability to PBO, improve.
Summary of the invention
In order to improve PBO thermal stability, a kind of method of the PBO of preparation analog copolymer is provided simultaneously, and improve the problems such as the polymerization technique that exists in polymerization process is complicated, polymerization time is long, molecular weight is low, the present invention proposes the PBO copolycondensation method of modifying that a kind of technique is simple, polymerization time is short, by copolycondensation modification, also effectively improved the thermal stability of PBO multipolymer.
PBO copolycondensation method of modifying of the present invention, comprises the steps:
(1) 4,6-diaminoresorcinol hydrochloride is dissolved in deionized water; The second dicarboxylic acid monomer of equimolar amount is dissolved in NaOH solution, and at N
2under protection, be progressively titrated in the aqueous solution of 4,6-diaminoresorcinol hydrochloride; After dropwising, be warming up to 90 ℃ of reaction 5-10 minute; White solid to be separated out, in N
2under atmosphere, filter, wash, vacuum-drying, obtains DAR-TA composite salt, takes out sample and preserves under vacuum condition;
(2) in reactor, add polyphosphoric acid, P
2o
5and glass putty, logical N after mix and blend
2displace air logical N
2protection, then add the DAR-TA composite salt of preparing in step (1); Heating, after stopped reaction, washing, dry, is prepared into PBO polymkeric substance.
Reactant, except 4,6-diaminoresorcinol hydrochloride and the second dicarboxylic acid monomer, also comprises terephthalic acid, terephthalic acid and the second dicarboxylic acid monomer is dissolved in NaOH solution and forms mixing acid, and at N
2under protection, be progressively titrated in the aqueous solution with the 4,6-diaminoresorcinol hydrochloride of mixing acid equimolar amount.Terephthalic acid mixes with arbitrary proportion with the second dicarboxylic acid monomer, and the molar weight sum of the two equals the molar weight of 4,6-diaminoresorcinol hydrochloride.
The second described dicarboxylic acid monomer is 2,6-dicarboxyl pyridine.
Adopt 2,6-dicarboxyl pyridine as modified monomer, to make the PBO multipolymer of modification by copolymerization, result shows the PBO multipolymer that a small amount of the second dicarboxylic acid monomer's modification by copolymerization makes, and its thermal stability is improved to some extent.
In addition, the invention allows for and adopt polyamines salt monomer as modified monomer, to make the PBO multipolymer of modification by copolymerization, comprise the steps:
(1) polyamines salt monomer is dissolved in deionized water; To be dissolved in NaOH solution with the terephthalic acid of polyamines salt monomer equimolar amount, and at N
2under protection, be progressively titrated in the aqueous solution of polyamines salt monomer; After dropwising, be warming up to 90 ℃ of reaction 5-10 minute; White solid to be separated out, in N
2under atmosphere, filter, wash, vacuum-drying obtains DAR-TA composite salt, takes out sample and preserves under vacuum condition;
(2) in reactor, add polyphosphoric acid, P
2o
5and glass putty, logical N after mix and blend
2displace air logical N
2protection, then add the DAR-TA composite salt of preparing in step (1); Heating, after stopped reaction, washing, dry, is prepared into PBO polymkeric substance.
Reactant is except polyamines salt monomer and terephthalic acid, also comprise 4,6-diamino resorcin hydrochlorate, 4,6-diaminoresorcinol hydrochloride and polyamines salt monomer are dissolved in deionized water, form mixed solution, 4,6-diamino resorcin hydrochlorate mixes with arbitrary proportion with polyamines salt monomer, the terephthalic acid with mixed solution equimolar amount is dissolved in NaOH solution, and at N
2under protection, be progressively titrated in mixed solution.
Described polyamines salt monomer is 4-aminopyridine hydrochloride.Result shows the PBO multipolymer that adds modification by copolymerization to make of a small amount of polyamines salt monomer, and its thermal stability is improved to some extent.
By adding, a small amount of the 3rd monomer---the PBO multipolymer that the second dicarboxylic acid monomer or polyamines salt monomer modification by copolymerization make, its thermal stability is improved to some extent in the present invention.
Two kinds of technical schemes of the present invention are mainly based on prior art, with 4, 6-diamino resorcin hydrochlorate and terephthalic acid are raw material, preparation 4, 6-diamino resorcin-terephthalate (TA salt), take polyphosphoric acid as medium again, the polycondensation of TA salt is obtained having on the basis of PBO of viscosity higher, by adding the 3rd monomer (the second dicarboxylic acid monomer, polyamines salt monomer) PBO is carried out to copolycondensation modification and make PBO multipolymer, the resistance to elevated temperatures of finding the monomer copolymerization modified PBO multipolymer making of certain proportion the 3rd has significant raising, also find that thus modification by copolymerization is to improve the better method of the thermostability of multipolymer.
figure of description
The existing TA salt of Fig. 1 legal system is for the reaction schematic diagram of PBO homopolymer
Fig. 2 prepares the reaction schematic diagram of PBO multipolymer containing the mixing salt polymerization of 2,6-dicarboxyl pyridine
Fig. 3 prepares the reaction schematic diagram of PBO multipolymer containing the mixing salt polymerization of 4-aminopyridine
Fig. 42, the PBO multipolymer thermogravimetric analysis spectrogram of 6-dicarboxyl pyridine modification
The PBO multipolymer thermogravimetric analysis spectrogram of Fig. 5 4-aminopyridine modification.
Embodiment
At 1,90 ℃ of embodiment, DAR-TA salt method is prepared PBO homopolymer (as shown in Figure 1)
(1) 3.20g 4,6-diaminoresorcinol hydrochloride (0.015mol) is dissolved in containing 0.01gSnCl
2deionized water solution in; 2.50g terephthalic acid (0.015mol) is dissolved in to 300mlNaOH(1.20g, 0.03mol) in solution, at N
2under protection, be progressively added dropwise in the aqueous solution of aforementioned 4,6-diaminoresorcinol hydrochloride.After dropwising, be warming up to
90 ℃react 10 minutes.White solid to be separated out, in N
2under atmosphere, filter, after washing, be positioned in the vacuum drying oven of 60 ℃ dry 48 hours, obtain 4,6-diaminoresorcinol-terephthalate (DAR-TA composite salt), take out sample and preserve under vacuum condition.
(2) in reactor, be added into polyphosphoric acid 15.22g, P
2o
56.35g, glass putty 0.02g, logical N after mix and blend
2displace air logical N
2protection, then add the DAR-TA composite salt 3.06g preparing in step (1).Under 80 ℃ of conditions, react after 2 hours, be warming up to 120 ℃ of reactions 2 hours, and then rising temperature to 140 ℃ reaction 6 hours, the temperature to 170 that raises subsequently ℃ reaction 8 hours is then reacted 2 hours under 190 ℃ of conditions; Stopped reaction, washing, dry, be prepared into PBO homopolymer.
(1) 2.13g 4,6-diaminoresorcinol hydrochloride (0.010mol) is dissolved in to the SnCl containing 0.01g
2deionized water solution in; By 1.58g terephthalic acid (0.0095mol) and 0.08g 2,200mlNaOH(0.80g, 0.02mol that 6-dicarboxyl pyridine (0.0005mol) is dissolved in) in solution, at N
2under protection, be progressively added dropwise in the aforementioned DAR aqueous solution.After dropwising, be warming up to 90 ℃ of reactions 10 minutes.White solid to be separated out, in N
2under atmosphere, filter, after washing, be positioned in the vacuum drying oven of 60 ℃ dry 48 hours, obtain 4,6-diaminoresorcinol-2 containing 5%, the DAR-TA composite salt of 6-dicarboxyl pyridinium salt, takes out sample and preserves under vacuum condition.
(2) in reactor, be added into polyphosphoric acid 9.44g, P
2o
53.97g and glass putty 0.01g, logical N after mix and blend
2protection, adds the DAR-TA composite salt 1.90g making in step (1).Under 80 ℃ of conditions, react 2 hours, then be warming up to 120 ℃ of reactions 2 hours, continue rising temperature to 140 ℃ reaction 10 hours, the temperature to 170 that raises subsequently ℃ reaction 8 hours is then reacted 2 hours under 190 ℃ of conditions; Stopped reaction, washing, dry, make the PBO multipolymer containing 5% dicarboxyl pyridine.
(1) 2.13g 4,6-diaminoresorcinol hydrochloride (0.010mol) is dissolved in to the SnCl containing 0.01g
2deionized water solution in; By 1.50g terephthalic acid (0.0090mol) and 0.16g 2,6-dicarboxyl pyridine (0.0010mol) is dissolved in 200mLNaOH(0.80g, 0.02mol) in solution, at N
2under protection, be progressively added dropwise in the aforementioned DAR aqueous solution.After dropwising, be warming up to 90 ℃ of reactions 5 minutes.White solid to be separated out, in N
2under atmosphere, filter, after washing, be positioned in the vacuum drying oven of 60 ℃ dry 48 hours, obtain containing 10%4,6-diamino resorcin-2, the DAR-TA composite salt of 6-dicarboxyl pyridinium salt, takes out sample and preserves under vacuum condition.
(2) in reactor, be added into polyphosphoric acid 9.94g, P
2o
54.18g and glass putty 0.01g, logical N after mix and blend
2protection, and add the DAR-TA composite salt 2.00g making in step (1), under 80 ℃ of conditions, react 2 hours, be warming up to 120 ℃ of reactions 2 hours, continue rising temperature to 140 ℃ reaction 6 hours, the temperature to 170 that raises subsequently ℃ reaction 8 hours is then reacted 2 hours under 190 ℃ of conditions; Stopped reaction, washing, dry, make the PBO multipolymer containing 10% dicarboxyl pyridine.
Embodiment 4,50% 2, the preparation (as shown in Figure 2) of the PBO multipolymer of 6-dicarboxyl pyridine modification
(1) 2.13g 4,6-diaminoresorcinol hydrochloride (0.010mol) is dissolved in to the SnCl containing 0.01g
2deionized water solution in; By 0.83g terephthalic acid (0.0050mol) and 0.84g 2,6-dicarboxyl pyridine (0.005mol) is dissolved in 200mLNaOH(0.80g, 0.02mol) in solution, at N
2under protection, be progressively added dropwise in the aforementioned DAR aqueous solution.After dropwising, be warming up to 90 ℃ of reactions 10 minutes.White solid to be separated out, in N
2under atmosphere, filter, after washing, be positioned in the vacuum drying oven of 60 ℃ dry 48 hours, obtain containing 10%4,6-diamino resorcin-2, the DAR-TA composite salt of 6-dicarboxyl pyridinium salt, takes out sample and preserves under vacuum condition.
(2) in reactor, be added into polyphosphoric acid 9.94g, P
2o
54.18g and glass putty 0.01g, logical N after mix and blend
2protection, and add the DAR-TA composite salt 2.00g making in step (1), under 80 ℃ of conditions, react 2 hours, be warming up to 120 ℃ of reactions 2 hours, continue rising temperature to 140 ℃ reaction 6 hours, the temperature to 170 that raises subsequently ℃ reaction 8 hours is then reacted 2 hours under 190 ℃ of conditions; Stopped reaction, washing, dry, make the PBO multipolymer containing 50% dicarboxyl pyridine.
(1) 2.13g 4,6-diaminoresorcinol hydrochloride (0.010mol) is dissolved in to the SnCl containing 0.01g
2deionized water solution in; By 0.08g terephthalic acid (0.0005mol) and 1.58g 2,6-dicarboxyl pyridine (0.0095mol) is dissolved in 200mLNaOH(0.8g, 0.02mol) in solution, at N
2under protection, be progressively added dropwise in the aforementioned DAR aqueous solution.After dropwising, be warming up to 90 ℃ of reactions 10 minutes.White solid to be separated out, in N
2under atmosphere, filter, after washing, be positioned in the vacuum drying oven of 60 ℃ dry 48 hours, obtain containing 10%4,6-diamino resorcin-2, the DAR-TA composite salt of 6-dicarboxyl pyridinium salt, takes out sample and preserves under vacuum condition.
(2) in reactor, be added into polyphosphoric acid 9.94g, P
2o
54.18g and glass putty 0.01g, logical N after mix and blend
2protection, and add the DAR-TA composite salt 2.00g making in step (1), under 80 ℃ of conditions, react 2 hours, be warming up to 120 ℃ of reactions 2 hours, continue rising temperature to 140 ℃ reaction 6 hours, the temperature to 170 that raises subsequently ℃ reaction 8 hours is then reacted 2 hours under 190 ℃ of conditions; Stopped reaction, washing, dry, make the PBO multipolymer containing 95% dicarboxyl pyridine.
Embodiment 6,100% 2, the preparation of the PBO multipolymer of 6-dicarboxyl pyridine modification
(1) 2.56g 4,6-diaminoresorcinol hydrochloride (0.012mol) is dissolved in to the SnCl containing 0.01g
2deionized water solution in; By 2.00g 2, (0.012mol) of 6-dicarboxyl pyridine is dissolved in NaOH(0.96g, the 0.024mol of 240mL) in the aqueous solution, at N
2under protection, be progressively added dropwise in the aforementioned DAR aqueous solution.After dropwising, be warming up to 90 ℃ of reactions 10 minutes.White solid to be separated out, in N
2under atmosphere, filter, after washing, be positioned in the vacuum drying oven of 60 ℃ dry 48 hours, obtain 4,6-diaminoresorcinol-2,6-dicarboxyl pyridinium salt composite salt, takes out sample and preserves under vacuum condition.
(2) in reactor, be added into polyphosphoric acid 13.70g, P
2o
55.74g and glass putty 0.01g, logical N after mix and blend
2protection, and add the composite salt 2.76g making in step (1).Under 80 ℃ of conditions, react 2 hours, be warming up to 120 ℃ of reactions 2 hours, continue rising temperature to 140 ℃ reaction 6 hours, the temperature to 170 that raises subsequently ℃ reaction 8 hours is then reacted 2 hours under 190 ℃ of conditions; Stopped reaction, washing, dry, prepare pyridine structure oxazole polymkeric substance.
The preparation (as shown in Figure 3) of the PBO multipolymer of embodiment 7,2% 4-aminopyridine modification
(1) 4.18g 4,6-diaminoresorcinol hydrochloride (0.0196mol) and 0.10g 4-aminopyridine hydrochloride (0.0004mol) are dissolved in to the SnCl containing 0.01g
2deionized water solution in; 3.32g terephthalic acid (0.020mol) is dissolved in to 406mLNaOH(1.62g, 0.0406mol) in the aqueous solution, at N
2under protection, be progressively added dropwise in the aforementioned DAR aqueous solution.After dropwising, be warming up to 90 ℃ of reactions 10 minutes.White solid to be separated out, in N
2under atmosphere, filter, after washing, be positioned in the vacuum drying oven of 60 ℃ dry 48 hours, obtain the DAR-TA monomer composite salt of 4-aminopyridine-terephthalate of 2%, take out sample and preserve under vacuum condition.
(2) in reactor, be added into polyphosphoric acid 15.22g, P
2o
56.35g and glass putty 0.01g, mix and blend logical N
2protection, and add the DAR-TA monomer composite salt 3.06g in step (1), under 80 ℃ of conditions, react 2 hours, be warming up to 120 ℃ of reactions 2 hours, continue rising temperature to 140 ℃ reaction 6 hours, the temperature to 170 that raises subsequently ℃ reaction 8 hours is then reacted 2 hours under 190 ℃ of conditions; Stopped reaction, washing, dry, be prepared into the PBO multipolymer of 2% 4-aminopyridine modification.
The preparation (as shown in Figure 3) of the PBO multipolymer of embodiment 8,5% 4-aminopyridine modification
(1) 4.04g 4,6-diaminoresorcinol hydrochloride (0.0190mol) and 0.26g 4-aminopyridine hydrochloride (0.0010mol) are dissolved in to the SnCl containing 0.01g
2deionized water solution in; 3.32g terephthalic acid (0.020mol) is dissolved in to NaOH(1.64g, the 0.0410mol of 410mL) in the aqueous solution, at N
2under protection, be progressively added dropwise in the aforementioned DAR aqueous solution.After dropwising, be warming up to 90 ℃ of reactions 10 minutes.White solid to be separated out, in N
2under atmosphere, filter, after washing, be positioned in the vacuum drying oven of 60 ℃ dry 48 hours, obtain the DAR-TA monomer composite salt of 4-aminopyridine-terephthalate of 5%, take out sample and preserve under vacuum condition.
(2) in reactor, be added into polyphosphoric acid 15.22g, P
2o
56.35g and glass putty 0.01g, mix and blend logical N
2protection, and add the DAR-TA monomer composite salt 3.06g in step (1), under 80 ℃ of conditions, react 2 hours, be warming up to 120 ℃ of reactions 2 hours, continue rising temperature to 140 ℃ reaction 6 hours, the temperature to 170 that raises subsequently ℃ reaction 8 hours is then reacted 2 hours under 190 ℃ of conditions; Stopped reaction, washing, is dried, and is prepared into the PBO multipolymer of 5% 4-aminopyridine modification.
The preparation (as shown in Figure 3) of the PBO multipolymer of embodiment 9,10% 4-aminopyridine modification
(1) 3.84g 4,6-diaminoresorcinol hydrochloride (0.0180mol) and 0.52g 4-aminopyridine hydrochloride (0.0020mol) are dissolved in to the SnCl containing 0.01g
2deionized water solution in; 3.32g terephthalic acid (0.020mol) is dissolved in to NaOH(1.68g, the 0.0420mol of 420mL) in the aqueous solution, at N
2under protection, be progressively added dropwise in the aforementioned DAR aqueous solution.After dropwising, be warming up to 90 ℃ of reactions 5 minutes.White solid to be separated out, in N
2under atmosphere, filter, after washing, be positioned in the vacuum drying oven of 60 ℃ dry 48 hours, obtain the DAR-TA monomer composite salt containing 10% 4-aminopyridine-terephthalate, take out sample and preserve under vacuum condition.
(2) in reactor, be added into polyphosphoric acid 15.22g, P
2o
56.35g and glass putty 0.01g, mix and blend logical N
2protection, and add the DAR-TA monomer composite salt 3.06g in step (1), under 80 ℃ of conditions, react 2 hours, be warming up to 120 ℃ of reactions 2 hours, continue rising temperature to 140 ℃ reaction 6 hours, the temperature to 170 that raises subsequently ℃ reaction 8 hours is then reacted 2 hours under 190 ℃ of conditions; Stopped reaction, washing, dry, be prepared into the PBO multipolymer of 10% 4-aminopyridine modification.
The preparation (as shown in Figure 3) of the PBO multipolymer of embodiment 10,50% 4-aminopyridine modification
(1) 2.13g 4,6-diaminoresorcinol hydrochloride (0.0100mol) and 2.67g 4-aminopyridine hydrochloride (0.0100mol) are dissolved in to the SnCl containing 0.01g
2deionized water solution in; 3.32g terephthalic acid (0.020mol) is dissolved in to NaOH(2.00g, the 0.0500mol of 500mL) in the aqueous solution, at N
2under protection, be progressively added dropwise in the aforementioned DAR aqueous solution.After dropwising, be warming up to 90 ℃ of reactions 10 minutes.White solid to be separated out, in N
2under atmosphere, filter, after washing, be positioned in the vacuum drying oven of 60 ℃ dry 48 hours, obtain the DAR-TA monomer composite salt containing 10% 4-aminopyridine-terephthalate, take out sample and preserve under vacuum condition.
(2) in reactor, be added into polyphosphoric acid 15.22g, P
2o
56.35g and glass putty 0.01g, mix and blend logical N
2protection, and add the DAR-TA monomer composite salt 3.06g in step (1), under 80 ℃ of conditions, react 2 hours, be warming up to 120 ℃ of reactions 2 hours, continue rising temperature to 140 ℃ reaction 6 hours, the temperature to 170 that raises subsequently ℃ reaction 8 hours is then reacted 2 hours under 190 ℃ of conditions; Stopped reaction, washing, dry, be prepared into the PBO multipolymer of 50% 4-aminopyridine modification.
The preparation (as shown in Figure 3) of the PBO multipolymer of embodiment 11,98% 4-aminopyridine modification
(1) 0.09g 4,6-diaminoresorcinol hydrochloride (0.0004mol) and 5.22g 4-aminopyridine hydrochloride (0.0196mol) are dissolved in to the SnCl containing 0.01g
2deionized water solution in; 3.32g terephthalic acid (0.020mol) is dissolved in to NaOH(2.40g, the 0.0600mol of 600mL) in the aqueous solution, at N
2under protection, be progressively added dropwise in the aforementioned DAR aqueous solution.After dropwising, be warming up to 90 ℃ of reactions 10 minutes.White solid to be separated out, in N
2under atmosphere, filter, after washing, be positioned in the vacuum drying oven of 60 ℃ dry 48 hours, obtain the DAR-TA monomer composite salt containing 10% 4-aminopyridine-terephthalate, take out sample and preserve under vacuum condition.
(2) in reactor, be added into polyphosphoric acid 15.22g, P
2o
56.35g and glass putty 0.01g, mix and blend logical N
2protection, and add the DAR-TA monomer composite salt 3.05g in step (1), under 80 ℃ of conditions, react 2 hours, be warming up to 120 ℃ of reactions 2 hours, continue rising temperature to 140 ℃ reaction 6 hours, the temperature to 170 that raises subsequently ℃ reaction 8 hours is then reacted 2 hours under 190 ℃ of conditions; Stopped reaction, washing, dry, be prepared into the PBO multipolymer of 98% 4-aminopyridine modification.
The preparation of the PBO multipolymer of embodiment 12,100% 4-aminopyridine
(1) 2.6g 4-aminopyridine hydrochloride (0.010mol) is dissolved in to the SnCl containing 0.01g
2deionized water solution in; 1.66g terephthalic acid (0.010mol) is dissolved in to NaOH(0.84g, the 0.0210mol of 210mL) in the aqueous solution, at N
2under protection, be progressively added dropwise in the aforementioned DAR aqueous solution.After dropwising, be warming up to 90 ℃ of reactions 10 minutes.White solid to be separated out, in N
2under atmosphere, filter, after washing, be positioned in the vacuum drying oven of 60 ℃ dry 48 hours, obtain the DAR-TA monomer composite salt containing 100% 4-aminopyridine-terephthalate, take out sample and preserve under vacuum condition.
(2) in reactor, be added into polyphosphoric acid 15.22g, P
2o
56.35g and glass putty 0.01g, mix and blend logical N
2protection, and add the DAR-TA monomer composite salt 3.06g in step (1), under 80 ℃ of conditions, react 2 hours, be warming up to 120 ℃ of reactions 2 hours, continue rising temperature to 140 ℃ reaction 6 hours, the temperature to 170 that raises subsequently ℃ reaction 8 hours is then reacted 2 hours under 190 ℃ of conditions; Stopped reaction, washing, dry, be prepared into the PBO multipolymer of 100% 4-aminopyridine modification.
Embodiment 13, performance analysis
Fig. 4 is 2 of different ratios, the thermogravimetric analysis spectrogram of PBO multipolymer prepared by 6-dicarboxyl pyridine, the content of the pyridine dicarboxylic acid that corresponding each copolymerization is used respectively of percentage ratio shown in figure.As can be seen from the figure, the thermal weight loss temperature of PBO homopolymer (be in embodiment 1 0% pyridine dicarboxylic acid modification) is 650 ℃; And the thermal weight loss temperature of the PBO base polymer of 5%, 10% pyridine dicarboxylic acid copolymerization is more approaching, approach 680 ℃; By 100% pyridine dicarboxylic acid, replace the thermal weight loss temperature of terephthalic acid resulting polymers to be 550 ℃.This shows, 5% and 10% 2, the heat decomposition temperature of the PBO multipolymer of dipicolimic acid 2 modification is than 30 ℃ of left and right of the raising of PBO homopolymer.
Fig. 5 is the thermogravimetric analysis spectrogram of the PBO multipolymer prepared of the 4-aminopyridine of different ratios, the content of the 4-aminopyridine that corresponding each copolymerization is used respectively of percentage ratio shown in figure.Because the thermal weight loss temperature of PBO homopolymer is 650 ℃; The thermal weight loss of the PBO base polymer of 2% 4-aminopyridine copolymerization has obvious raising, and the heat decomposition temperature of the PBO multipolymer of 5% or 10% 4-aminopyridine modification is compared slightly raising with PBO homopolymer.
Claims (6)
1.PBO copolycondensation method of modifying, comprises the steps:
(1) 4,6-diaminoresorcinol hydrochloride is dissolved in deionized water; The second dicarboxylic acid monomer of equimolar amount is dissolved in NaOH solution, and at N
2under protection, be progressively titrated in the aqueous solution of 4,6-diaminoresorcinol hydrochloride; After dropwising, be warming up to 90 ℃ of reaction 5-10 minute; White solid to be separated out, in N
2under atmosphere, filter, wash, vacuum-drying, obtains DAR-TA composite salt, takes out sample and preserves under vacuum condition;
(2) in reactor, add polyphosphoric acid, P
2o
5and glass putty, logical N after mix and blend
2displace air logical N
2protection, then add the DAR-TA composite salt of preparing in step (1); Heating, after stopped reaction, washing, dry, is prepared into PBO polymkeric substance.
2. PBO copolycondensation method of modifying as claimed in claim 1, it is characterized in that, reactant also comprises terephthalic acid, and terephthalic acid and the second dicarboxylic acid monomer are dissolved in NaOH solution and form mixing acid, terephthalic acid mixes with arbitrary proportion with the second dicarboxylic acid monomer, at N
2under protection, be progressively titrated in the aqueous solution with the 4,6-diaminoresorcinol hydrochloride of mixing acid equimolar amount.
3. PBO copolycondensation method of modifying as claimed in claim 1 or 2, is characterized in that, the second described dicarboxylic acid monomer is 2,6-dicarboxyl pyridine.
4.PBO copolycondensation method of modifying, comprises the steps:
(1) polyamines salt monomer is dissolved in deionized water; To be dissolved in NaOH solution with the terephthalic acid of polyamines salt monomer equimolar amount, and at N
2under protection, be progressively titrated in the aqueous solution of polyamines salt monomer; After dropwising, be warming up to 90 ℃ of reaction 5-10 minute; White solid to be separated out, in N
2under atmosphere, filter, wash, vacuum-drying obtains DAR-TA composite salt, takes out sample and preserves under vacuum condition;
(2) in reactor, add polyphosphoric acid, P
2o
5and glass putty, logical N after mix and blend
2displace air logical N
2protection, then add the DAR-TA composite salt of preparing in step (1); Heating, after stopped reaction, washing, dry, is prepared into PBO polymkeric substance.
5. PBO copolycondensation method of modifying as claimed in claim 4, it is characterized in that, reactant also comprises 4,6-diaminoresorcinol hydrochloride, by 4,6-diamino resorcin hydrochlorate and polyamines salt monomer are dissolved in deionized water, form mixed solution, 4,6-diaminoresorcinol hydrochloride mixes with arbitrary proportion with polyamines salt monomer, terephthalic acid with mixed solution equimolar amount is dissolved in NaOH solution, and at N
2under protection, be progressively titrated in mixed solution.
6. the PBO copolycondensation method of modifying as described in claim 4 or 5, is characterized in that, described polyamines salt monomer is 4-aminopyridine hydrochloride.
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