CN102516540B - Method for grafting SWNT (single-walled carbon nanotube) into modified PIPD (poly[2,5-dihydroxy-1,4-phenylenepyridinodiimidazole]) - Google Patents
Method for grafting SWNT (single-walled carbon nanotube) into modified PIPD (poly[2,5-dihydroxy-1,4-phenylenepyridinodiimidazole]) Download PDFInfo
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 36
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- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 13
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 235000011150 stannous chloride Nutrition 0.000 claims description 12
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- 238000009413 insulation Methods 0.000 claims description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 6
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- 125000000524 functional group Chemical group 0.000 description 2
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- 238000002329 infrared spectrum Methods 0.000 description 2
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- QXGJCWSBOZXWOV-UHFFFAOYSA-N 3,4-dihydroxyphthalic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1C(O)=O QXGJCWSBOZXWOV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention which relates to a method for grafting modified PIPD concretely relates to a method for grafting SWNT into the PIPD and solves problems of easy agglomeration, difficult dispersion and difficult formation of a stable covalent connection of the SWNT with the PIPD in PIPD matrixes. The method is realized by mixing a methanesulfonic acid solution of the PIPD with a carboxylated SWNT dispersion liquid and reacting. According to the invention, the grafting of the SWNT into the modified PIPD is realized, and a SWNT grafted PIPD copolymer is generated. By utilizing the template effect of the SWNT to the fiber orientation, a PIPD fiber is induced to be further oriented along an axial direction, so mechanical properties are improved. The operation of the method is simple.
Description
Technical field
The present invention relates to the method for a kind of graft modification poly-[2,5-dihydroxy-1,4-pyridobismidazole].
Background technology
High-performance organic fibre has the excellent properties such as low density, high strength, high-modulus, thereby is widely applied in fields such as Aeronautics and Astronautics, weapon armaments.Along with the development of science and technology, people have higher requirement to high-strength high-modulus fibre, and use carbon nanotube enhancing modified organic fibre to obtain people's generally approval, and develop into the study hotspot in this field rapidly.Single Walled Carbon Nanotube (SWNT) strengthens body as the nano level tubulose of rigidity, by with the covalently bound formation nano composite material of polymkeric substance, can solve terminal these serious problems of stress build up of enhancing body in traditional short fiber reinforced composite, the mechanical property of conjugated fibre is greatly improved.In addition, because SWNT has typical nanotube-shaped hollow structure, must reduce the density of gained conjugated fibre, thereby obtain the conjugated fibre of high specific tenacity.
Poly-[2,5-dihydroxy-1,4-pyridobismidazole] is the material scholar carries out molecular designing from structure and property relationship product (PIPD).The PIPD fiber is the highest organic fibre of present over-all properties, and it has high specific strength, high ratio modulus, high impact properties, high surface polarity, good interfacial bond property, thermal insulation, superpower resistance toheat, unique high resistance compressive strength, the good excellent properties such as weathering resistance.Above good characteristic is so that high-performance PIPD fiber is subject to the extensive attention of countries in the world.The research and development of high-performance PIPD fiber and volume production have become the active demand of satisfying national Important Project and leading traditional industry upgrading to regenerate, for accelerating the strategic new industry cultivation of China's novel material and developing significant.The PIPD fibre property is good, but its actual mechanical property still has larger gap than the theoretical mechanics performance.Adopt SWNT enhancing modified PIPD fiber can significantly improve its mechanical property.But, carbon nanotube is added to and unavoidably exists problems such as being easy to reunite, being difficult to dispersion in the PIPD fiber as strengthening body.Simultaneously since the PIPD polymerization system viscosity large, stir difficulty, make be difficult between SWNT and the PIPD to form stable covalently bound.
Summary of the invention
The purpose of this invention is to provide a kind of Single Walled Carbon Nanotube graft modification poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] method, solve Single Walled Carbon Nanotube poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] be easy in the matrix reunite, be difficult to disperse, be difficult to stablize covalently bound problem with poly-[2,5-dihydroxy-1,4-pyridobismidazole] formation.
The method of a kind of Single Walled Carbon Nanotube graft modification of the present invention poly-[2,5-dihydroxy-1,4-pyridobismidazole] realizes by following steps: one, Single Walled Carbon Nanotube is carried out carboxylated processing, get carboxylated Single Walled Carbon Nanotube;
Two, carboxylated Single Walled Carbon Nanotube graft modification gathers [2,5-dihydroxy-1,4-pyridobismidazole]: a, Vanadium Pentoxide in FLAKES is added in the phosphoric acid, and stirring and dissolving gets poly phosphoric acid solution, and wherein the mass ratio of Vanadium Pentoxide in FLAKES and phosphoric acid is 1: 1～2; B, the carboxylated Single Walled Carbon Nanotube that step 1 is obtained add in the poly phosphoric acid solution of a step preparation, stirred 0.5～2 hour, get carboxylated single-walled carbon nanotube dispersion liquid, the mass ratio of the poly phosphoric acid solution of the carboxylated Single Walled Carbon Nanotube that step 1 obtains and the preparation of a step is 1: 50～1000; C, will gather [2,5-dihydroxy-1,4-pyridobismidazole] and methylsulfonic acid mix and blend 4～24 hours, must gather [2,5-dihydroxy-1,4-pyridobismidazole] solution, wherein poly-[2,5-dihydroxy-1,4-pyridobismidazole] is 1: 20～100 with the mass ratio of methylsulfonic acid; D, the carboxylated single-walled carbon nanotube dispersion liquid that the b step is obtained and c step obtain poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] solution is that 1: 1～2 ratio is mixed according to mass ratio, then stirring reaction 12～48 hours under 100 ℃～180 ℃ temperature, get reaction product, with dry after the reaction product washing, get carboxylated Single Walled Carbon Nanotube graft modification poly-[2,5-dihydroxy-1,4-pyridobismidazole].
The method of in the step 1 of the present invention Single Walled Carbon Nanotube being carried out carboxylated processing is to adopt existing open disposal methods to get final product.
Described in the c step in the step 2 of the present invention poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] adopt existing disclosed preparation method to obtain, as to authorize publication number be CN101418073, the patent No. be 200810137342.4 poly-(2, the 5-dihydroxy-1,4-pyridobismidazole) preparation method who puts down in writing in preparation method's the patent.
Phosphoric acid concentration is 85% in a step of step 2 of the present invention.
In the d step of step 2 of the present invention that the reaction product washing is rear dry, method for washing is: reaction product is added to the water, low whipping speed is that 100～1000 rev/mins Water Under was washed 6～36 hours, and the volume ratio of control reaction product and water is 1: 100～1000.
The carboxylated Single Walled Carbon Nanotube that will be easy among the present invention reunite, be difficult to disperse is mixed with dispersion liquid, system viscosity is large, stir poly-[2 of difficulty, 5-dihydroxyl-1, the 4-pyridobismidazole] (PIPD) polymer formulation become solution, then dispersion liquid is mixed with solution, solved Single Walled Carbon Nanotube (SWNT) poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] be easy in the matrix reunite, be difficult to disperse, be difficult to and poly-[2, the 5-dihydroxy-1,4-pyridobismidazole] form and stablize the problems such as covalently bound.Realized that the Single Walled Carbon Nanotube graft modification gathers [2,5-dihydroxy-1,4-pyridobismidazole], has generated SWNT grafting PIPD multipolymer.Simultaneously, utilize SWNT to the template effect of fibre orientation, will induce the PIPD fiber in axial direction further to be orientated, its mechanical property is further improved.
Method of the present invention is simple to operate.
Description of drawings
Fig. 1 is the building-up process schematic diagram of the step 2 of test 1; Fig. 2 is the transmission electron microscope photo of the carboxylated Single Walled Carbon Nanotube that obtains of the treatment process of test 1 step 1; Fig. 3 is the infrared spectrogram of the Single Walled Carbon Nanotube that adopts in the test 1 and the carboxylated Single Walled Carbon Nanotube that obtains after step 1 is processed; Fig. 3 is the infrared spectrogram of the test 4 SWNT graft modification PIPD that prepare; Fig. 5 is the stereoscan photograph of the test 1 SWNT graft modification PIPD for preparing.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment is a kind of Single Walled Carbon Nanotube graft modification poly-[2, the 5-dihydroxy-1,4-pyridobismidazole] method, Single Walled Carbon Nanotube graft modification poly-[2, the 5-dihydroxy-1,4-pyridobismidazole] method realize by following steps:
One, Single Walled Carbon Nanotube is carried out carboxylated processing, get carboxylated Single Walled Carbon Nanotube;
Two, carboxylated Single Walled Carbon Nanotube graft modification gathers [2,5-dihydroxy-1,4-pyridobismidazole]: a, Vanadium Pentoxide in FLAKES is added in the phosphoric acid, and stirring and dissolving gets poly phosphoric acid solution, and wherein the mass ratio of Vanadium Pentoxide in FLAKES and phosphoric acid is 1: 1～2; B, the carboxylated Single Walled Carbon Nanotube that step 1 is obtained add in the poly phosphoric acid solution of a step preparation, stirred 0.5～2 hour, get carboxylated single-walled carbon nanotube dispersion liquid, the mass ratio of the poly phosphoric acid solution of the carboxylated Single Walled Carbon Nanotube that step 1 obtains and the preparation of a step is 1: 50～1000; C, will gather [2,5-dihydroxyl-1, the 4-pyridobismidazole] with methylsulfonic acid (MSA) mix and blend 4～24 hours, must gather [2, the 5-dihydroxy-1,4-pyridobismidazole] solution, wherein gather [2, the 5-dihydroxy-1,4-pyridobismidazole] with the mass ratio of methylsulfonic acid be 1: 20～100; D, the carboxylated single-walled carbon nanotube dispersion liquid that the b step is obtained and c step obtain poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] solution is that 1: 1～2 ratio is mixed according to mass ratio, then stirring reaction 12～48 hours under 100 ℃～180 ℃ temperature, get reaction product, with dry after the reaction product washing, get carboxylated Single Walled Carbon Nanotube graft modification poly-[2,5-dihydroxy-1,4-pyridobismidazole].
The method of in the present embodiment step 1 Single Walled Carbon Nanotube being carried out carboxylated processing is to adopt existing open disposal methods to get final product.
Described in the c step in the present embodiment step 2 poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] adopt existing disclosed preparation method to obtain, as to authorize publication number be CN101418073, the patent No. be 200810137342.4 poly-(2, the 5-dihydroxy-1,4-pyridobismidazole) preparation method who puts down in writing in preparation method's the patent.
The carboxylated Single Walled Carbon Nanotube that will be easy in the present embodiment reunite, be difficult to disperse is mixed with dispersion liquid, system viscosity is large, stir poly-[2 of difficulty, 5-dihydroxyl-1, the 4-pyridobismidazole] (PIPD) polymer formulation become solution, then dispersion liquid is mixed with solution, solved Single Walled Carbon Nanotube (SWNT) poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] be easy in the matrix reunite, be difficult to disperse, be difficult to and poly-[2, the 5-dihydroxy-1,4-pyridobismidazole] form and stablize the problems such as covalently bound.Realized that the Single Walled Carbon Nanotube graft modification gathers [2,5-dihydroxy-1,4-pyridobismidazole], has generated SWNT grafting PIPD multipolymer.Simultaneously, utilize SWNT to the template effect of fibre orientation, will induce the PIPD fiber in axial direction further to be orientated, its mechanical property is further improved.
The method of present embodiment is simple to operate.
The preparation method's of present embodiment step 2 is as follows to the building-up process of step 3:
Embodiment two: what present embodiment and embodiment one were different is to adopt following steps that Single Walled Carbon Nanotube is carried out carboxylated processing in the step 1: one, add Single Walled Carbon Nanotube in nitration mixture, then 100 ℃ of lower stirring reactions 24 hours, cool off to get mixture, wherein, nitration mixture is dense HNO
3With dense H
2SO
4Be 1: 3 by volume, the ratio of Single Walled Carbon Nanotube quality and nitration mixture volume is 1g: 45mL～50mL; Two, add distilled water in the mixture that obtains to step 1, stir after 30 minutes, millipore filtration suction filtration by 0.22 μ m, then use distilled water rinse filter cake, until leaching the pH value of liquid, the strainer lower end is neutral, then with filter cake at 90 ℃ of lower vacuum dryings, obtain carboxylated Single Walled Carbon Nanotube.Other step and parameter are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two is poly-[2 described in the c step of step 2,5-dihydroxyl-1, the 4-pyridobismidazole] the preparation method as follows: a, under nitrogen atmosphere, be to add 2 in the poly phosphoric acid solution (PPA) of 80%～84% Vanadium Pentoxide in FLAKES to massfraction, 5-dihydric para-phthalic acid (DHTA), 2,3,5,6-4-aminopyridine hydrochloride monomer and tindichloride, mixture A stirs to get, then mixture A was reacted 12～36 hours 60 ℃～80 ℃ lower heated and stirred, get mixture B, wherein, 2,5-dihydric para-phthalic acid and 2,3,5, the mol ratio of 6-4-aminopyridine hydrochloride monomer is 1: 1, the mass ratio of tindichloride and 2,5-Dihydroxyterephthalic acid is 0.001～0.01: 1,2, the 5-dihydric para-phthalic acid, 2, the total mass of 3,5,6-4-aminopyridine hydrochloride monomer and tindichloride and the mass ratio of poly phosphoric acid solution are 0.05～0.25: 1; B, the mixture B that a step is obtained are warming up to 100 ℃～120 ℃, then add Vanadium Pentoxide in FLAKES, and the insulated and stirred reaction is 4～8 hours again, get mixture C, wherein, the mol ratio of 2,5-Dihydroxyterephthalic acid is 1: 0.67～1 in the Vanadium Pentoxide in FLAKES of adding and a step; C, the mixture C that the b step is obtained are warming up to 140 ℃～160 ℃, then insulation reaction is 3～5 hours, be warming up to 180 ℃～200 ℃, insulation reaction 3～5 hours gets reaction product again, and then after reaction product is cooled to room temperature, be washed to neutrality, 60～100 ℃ of lower vacuum-dryings 12～48 hours, get poly-[2 again, 5-dihydroxy-1,4-pyridobismidazole].Other step and parameter are identical with embodiment one or two.
The 2,5-Dihydroxyterephthalic acid that adopts in a step of present embodiment and 2,3,5,6-4-aminopyridine hydrochloride monomer all adopt existing public technology to prepare.
Mixture A is 60 ℃～80 ℃ lower heated and stirred reactions 12～36 hours, to remove the hydrogenchloride in 2,3,5, the 6-4-aminopyridine hydrochloride in the present embodiment a step.Add in the b step Vanadium Pentoxide in FLAKES with the massfraction of Vanadium Pentoxide in FLAKES in the polymerization system that guarantees mixture C about 86%.
Embodiment four: present embodiment and embodiment three are different is poly-[2 described in the c step of step 2,5-dihydroxyl-1, the 4-pyridobismidazole] preparation method's a step in the mass ratio of tindichloride and 2,5-Dihydroxyterephthalic acid be 0.002～0.006: 1.Other step and parameter are identical with embodiment three.
The mass ratio of tindichloride and 2,5-Dihydroxyterephthalic acid is preferably 0.003: 1 in the present embodiment.
Embodiment five: present embodiment is different from embodiment three or four is poly-[2 described in the c step of step 2,5-dihydroxyl-1, the 4-pyridobismidazole] preparation method's c step in mixture C that the b step is obtained be warming up to 150 ℃, then insulation reaction is 5 hours, be warming up to again 180 ℃, insulation reaction 5 hours gets reaction product.Other step and parameter are identical with embodiment three or four.
Embodiment six: present embodiment is different from one of embodiment one to five is that phosphoric acid concentration is 85% in a step of step 2.Other step and parameter are identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six be in the d step of step 2 under 120 ℃～150 ℃ temperature stirring reaction 18～32 hours, get reaction product.Other step and parameter are identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to six be in the d step of step 2 under 130 ℃ of temperature stirring reaction 24 hours, get reaction product.Other step and parameter are identical with one of embodiment one to six.
Embodiment nine: present embodiment is different from one of embodiment one to eight is with dry after the reaction product washing in the d step of step 2, method for washing is: reaction product is added to the water, low whipping speed is that 100～1000 rev/mins Water Under was washed 6～36 hours, and the volume ratio of control reaction product and water is 1: 100～1000.Other step and parameter are identical with one of embodiment one to eight.
In order to verify beneficial effect of the present invention, carry out following test:
Test 1: the method for Single Walled Carbon Nanotube graft modification poly-[2,5-dihydroxy-1,4-pyridobismidazole] realizes by following steps:
One, Single Walled Carbon Nanotube is carried out carboxylated processing, concrete steps are as follows: a, filling the dense HNO of 40mL
3With the dense H of 120mL
2SO
4The 1L there-necked flask in, add the Single Walled Carbon Nanotube (SWNT) of 3.420g, 100 ℃ of lower stirring reactions 24 hours, cool off to get mixture; Add 500mL distilled water in b, the mixture that obtains to step 1, stir after 30 minutes, millipore filtration suction filtration by 0.22 μ m, then use distilled water rinse filter cake, until leaching the pH value of liquid, the strainer lower end is neutral, then with filter cake at 90 ℃ of lower vacuum dryings, obtain carboxylated Single Walled Carbon Nanotube;
Two, poly-[2,5-dihydroxy-1,4-pyridobismidazole]: a of carboxylated Single Walled Carbon Nanotube graft modification, the 193.34g Vanadium Pentoxide in FLAKES is added to the 145.55g mass percentage concentration is that stirring and dissolving gets poly phosphoric acid solution in 85% the phosphoric acid; B, the carboxylated Single Walled Carbon Nanotube that the 0.5g step 1 is obtained add in the poly phosphoric acid solution of a step preparation, stir 1 hour, get carboxylated single-walled carbon nanotube dispersion liquid; C, with 10g poly-[2,5-dihydroxy-1,4-pyridobismidazole] and 338.89g methylsulfonic acid mix and blend 12 hours, get poly-[2,5-dihydroxy-1,4-pyridobismidazole] solution; D, the carboxylated single-walled carbon nanotube dispersion liquid that the b step is obtained and c step obtain poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] solution mixes, and then stirring reaction 24 hours under 130 ℃ of temperature gets reaction product, reaction product is added in the 2L water, low whipping speed is that 500 rev/mins Water Under was washed 24 hours, and is dry again, gets carboxylated Single Walled Carbon Nanotube graft modification poly-[2,5-dihydroxy-1,4-pyridobismidazole].
Wherein gather [2 in the c step of step 2,5-dihydroxyl-1, the 4-pyridobismidazole] prepare by following steps: 1., under nitrogen atmosphere, be to add 2 in the poly phosphoric acid solution of 83.7% Vanadium Pentoxide in FLAKES to massfraction, the 5-dihydric para-phthalic acid, 2,3,5,6-4-aminopyridine hydrochloride monomer and tindichloride, mixture A stirs to get, then mixture A was reacted 12～36 hours 60 ℃～80 ℃ lower heated and stirred, get mixture B, wherein, 2,5-dihydric para-phthalic acid and 2,3,5, the mol ratio of 6-4-aminopyridine hydrochloride monomer is 1: 1, the mass ratio of tindichloride and 2,5-Dihydroxyterephthalic acid is 0.003: 1,2, the 5-dihydric para-phthalic acid, 2, the total mass of 3,5,6-4-aminopyridine hydrochloride monomer and tindichloride and the mass ratio of poly phosphoric acid solution are 0.2: 1; 2., mixture B that a step is obtained is warming up to 120 ℃, then adds Vanadium Pentoxide in FLAKES, the insulated and stirred reaction is 6 hours again, gets mixture C, wherein, the mol ratio of 2,5-Dihydroxyterephthalic acid is 1: 0.8 in the Vanadium Pentoxide in FLAKES of adding and a step; 3., the mixture C that the b step is obtained is warming up to 150 ℃, then insulation reaction is 5 hours, be warming up to 180 ℃, insulation reaction 5 hours gets reaction product again, and then after reaction product is cooled to room temperature, be washed to neutrality, 80 ℃ of lower vacuum-dryings 24 hours, get poly-[2 again, 5-dihydroxy-1,4-pyridobismidazole].Wherein step adopt in 1. 2,5-dihydric para-phthalic acid and 2,3,5,6-4-aminopyridine hydrochloride monomer adopts existing open method to prepare, such as 2, the 5-dihydric para-phthalic acid be adopt patent " preparation method of dihydroxy phthalic acid " (Granted publication number: CN101239905B) disclosed method prepares, 2,3,5,6-4-aminopyridine hydrochloride monomer is to adopt patent " a kind ofly to prepare 2,3,5, the method of 6-4-aminopyridine hydrochloride " (applying date: 2008.6.6, application number: 200810064682.7) disclosed method prepares.
The building-up process schematic diagram of the preparation method's of test 1 step 2 as shown in Figure 1.
Adopt the transmission electron microscope photo of the carboxylated Single Walled Carbon Nanotube that the treatment process of the step 1 of test 1 obtains as shown in Figure 2, as seen from Figure 2, Single Walled Carbon Nanotube (SWNT) is through oxide treatment, and its length is prescinded greatly, exists without obvious entanglement phenomenon.The effective purifying of oxidation treatment method SWNT, the impurity of introducing in the SWNT preparation process disappears substantially.Simultaneously, the transmission electron microscope picture also shows, through after the oxide treatment, open the termination of SWNT, and introduced a large amount of activity functional groups at these positions, such as carboxyl, hydroxyl etc.
Test the infrared spectrogram of the Single Walled Carbon Nanotube that adopts in 1 and the carboxylated Single Walled Carbon Nanotube that obtains as shown in Figure 3 after step 1 is processed, as seen from Figure 3, SWNT has two obvious absorption peaks, and one is at 1580cm
-1Near, i.e. C=C stretching vibration; Another is at 1120cm
-1Near, i.e. C-C stretching vibration.In addition, 3400cm
-1There is also strong charateristic avsorption band at the place, is-the OH stretching vibration peak.Be engaged in 1720cm
-1Strong absorption peak also appears in the place, namely in the carboxylic acid-stretching vibration of C=O, show that SWNT has introduced carboxyl functional group on the surface.
The test 1 carboxylated Single Walled Carbon Nanotube graft modification for preparing poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] (SWNT graft modification PIPD) infrared spectrogram as shown in Figure 4, shown poly-[2 among Fig. 4, the 5-dihydroxy-1,4-pyridobismidazole] (PIPD) charateristic avsorption band.As～1620cm
-1C=N ,～1050cm
-1=C-O-C and～3050cm
-1Aromatic ring on C-H.The infrared spectra (Fig. 3) of SWNT graft modification PIPD infrared spectra and carboxylated SWNT is compared, be positioned at～3600cm
-1-the OH charateristic avsorption band obviously weakens after copolyreaction.Because it is comparatively complete that carboxylated SWNT and PIPD copolyreaction are carried out, and causes the hydroxyl characteristic peak to weaken.Be positioned at～3600cm
-1The place faint broad peak might be-OH ,-COOH or-NH
2The association peak that forms also might be the stretching vibration peak of N-H key on the imidazole ring.Fig. 3 shows, copolymerization does not change the molecular structure of PIPD, has generated simultaneously SWNT graft modification PIPD multipolymer.
The test 1 carboxylated Single Walled Carbon Nanotube graft modification for preparing poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] (SWNT graft modification PIPD) stereoscan photograph (SEM) as shown in Figure 4, can find out from SEM figure, SWNT is uniformly dispersed in the PIPD polymeric matrix, does not find to reunite.The PIPD film surface is comparatively smooth.
Claims (9)
1. Single Walled Carbon Nanotube graft modification poly-[2, the 5-dihydroxy-1,4-pyridobismidazole] method, it is characterized in that Single Walled Carbon Nanotube graft modification poly-[2, the 5-dihydroxy-1,4-pyridobismidazole] method realize by following steps:
One, Single Walled Carbon Nanotube is carried out carboxylated processing, get carboxylated Single Walled Carbon Nanotube;
Two, the Single Walled Carbon Nanotube graft modification gathers [2,5-dihydroxy-1,4-pyridobismidazole]: a, Vanadium Pentoxide in FLAKES is added in the phosphoric acid, and stirring and dissolving gets poly phosphoric acid solution, and wherein the mass ratio of Vanadium Pentoxide in FLAKES and phosphoric acid is 1:1～2; B, the carboxylated Single Walled Carbon Nanotube that step 1 is obtained add in the poly phosphoric acid solution of a step preparation, stirred 0.5～2 hour, get carboxylated single-walled carbon nanotube dispersion liquid, the mass ratio of the poly phosphoric acid solution of the carboxylated Single Walled Carbon Nanotube that step 1 obtains and the preparation of a step is 1:50～1000; C, will gather [2,5-dihydroxy-1,4-pyridobismidazole] and methylsulfonic acid mix and blend 4～24 hours, must gather [2,5-dihydroxy-1,4-pyridobismidazole] solution, wherein poly-[2,5-dihydroxy-1,4-pyridobismidazole] is 1:20～100 with the mass ratio of methylsulfonic acid; D, the carboxylated single-walled carbon nanotube dispersion liquid that the b step is obtained and c step obtain poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] solution is that the ratio of 1:1～2 is mixed according to mass ratio, then stirring reaction 12～48 hours under 100 ℃～180 ℃ temperature, get reaction product, with dry after the reaction product washing, get Single Walled Carbon Nanotube graft modification poly-[2,5-dihydroxy-1,4-pyridobismidazole].
2. a kind of Single Walled Carbon Nanotube graft modification according to claim 1 poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] method, it is characterized in that adopting in the step 1 following steps that Single Walled Carbon Nanotube is carried out carboxylated processing: one, in nitration mixture, to add Single Walled Carbon Nanotube, then 100 ℃ of lower stirring reactions 24 hours, cool off to get mixture, wherein, nitration mixture is dense HNO
3With dense H
2SO
4Be 1 ﹕ 3 by volume, the ratio of Single Walled Carbon Nanotube quality and nitration mixture volume is 1g ﹕ 45mL～50mL; Two, add distilled water in the mixture that obtains to step 1, stir after 30 minutes, millipore filtration suction filtration by 0.22 μ m, then use distilled water rinse filter cake, until leaching the pH value of liquid, the strainer lower end is neutral, then with filter cake at 90 ℃ of lower vacuum dryings, obtain carboxylated Single Walled Carbon Nanotube.
3. a kind of Single Walled Carbon Nanotube graft modification according to claim 1 and 2 poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] method, it is characterized in that poly-[2 described in the c step of step 2,5-dihydroxyl-1, the 4-pyridobismidazole] the preparation method as follows: a, under nitrogen atmosphere, be to add 2 in the poly phosphoric acid solution of 80%～84% Vanadium Pentoxide in FLAKES to massfraction, the 5-dihydric para-phthalic acid, 2,3,5,6-4-aminopyridine hydrochloride monomer and tindichloride, mixture A stirs to get, then mixture A was reacted 12～36 hours 60 ℃～80 ℃ lower heated and stirred, get mixture B, wherein, 2,5-Dihydroxyterephthalic acid and 2,3, the mol ratio of 5,6-4-aminopyridine hydrochloride monomer is 1 ﹕ 1, tindichloride and 2,5-dihydric para-phthalic acid's mass ratio is 0.001～0.01 ﹕ 1,2,5-Dihydroxyterephthalic acid, 2,3, the total mass of 5,6-4-aminopyridine hydrochloride monomer and tindichloride and the mass ratio of poly phosphoric acid solution are 0.05～0.25 ﹕ 1; B, the mixture B that a step is obtained are warming up to 100 ℃～120 ℃, then add Vanadium Pentoxide in FLAKES, and the insulated and stirred reaction is 4～8 hours again, get mixture C, wherein, the mol ratio of 2,5-Dihydroxyterephthalic acid is 1:0.67～1 in the Vanadium Pentoxide in FLAKES of adding and a step; C, the mixture C that the b step is obtained are warming up to 140 ℃～160 ℃, then insulation reaction is 3～5 hours, be warming up to 180 ℃～200 ℃, insulation reaction 3～5 hours gets reaction product again, and then after reaction product is cooled to room temperature, be washed to neutrality, 60～100 ℃ of lower vacuum-dryings 12～48 hours, get poly-[2 again, 5-dihydroxy-1,4-pyridobismidazole].
4. a kind of Single Walled Carbon Nanotube graft modification according to claim 3 poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] method, it is characterized in that poly-[2 described in the c step of step 2,5-dihydroxyl-1, the 4-pyridobismidazole] preparation method's a step in the mass ratio of tindichloride and 2,5-Dihydroxyterephthalic acid be 0.002～0.006 ﹕ 1.
5. according to claim 3 or 4 described a kind of Single Walled Carbon Nanotube graft modifications poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] method, it is characterized in that the mixture C that in preparation method's the c step of poly-[2, the 5-dihydroxy-1,4-pyridobismidazole] described in the c step of step 2 the b step is obtained is warming up to 150 ℃, then insulation reaction is 5 hours, be warming up to 180 ℃, insulation reaction 5 hours gets reaction product again.
6. the method for a kind of Single Walled Carbon Nanotube graft modification according to claim 1 and 2 poly-[2,5-dihydroxy-1,4-pyridobismidazole] is characterized in that phosphoric acid concentration is 85% in a step of step 2.
7. a kind of Single Walled Carbon Nanotube graft modification according to claim 1 and 2 poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] method, it is characterized in that in the d step of step 2 under 120 ℃～150 ℃ temperature stirring reaction 18～32 hours, get reaction product.
8. the method for a kind of Single Walled Carbon Nanotube graft modification according to claim 1 and 2 poly-[2,5-dihydroxy-1,4-pyridobismidazole] is characterized in that in the d step of step 2 under 130 ℃ of temperature stirring reaction 24 hours, got reaction product.
9. a kind of Single Walled Carbon Nanotube graft modification according to claim 1 and 2 poly-[2,5-dihydroxyl-1, the 4-pyridobismidazole] method, it is characterized in that in the d step of step 2 dry after the reaction product washing, method for washing is: reaction product is added to the water, low whipping speed is that 100～1000 rev/mins Water Under was washed 6～36 hours, and the volume ratio of control reaction product and water is 1:100～1000.
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