CN102516540A - 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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- CN102516540A CN102516540A CN2011104296345A CN201110429634A CN102516540A CN 102516540 A CN102516540 A CN 102516540A CN 2011104296345 A CN2011104296345 A CN 2011104296345A CN 201110429634 A CN201110429634 A CN 201110429634A CN 102516540 A CN102516540 A CN 102516540A
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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 that a kind of graft modification gathers [2,5-dihydroxyl-1,4-penylene pyrido diimidazole].
Background technology
High-performance organic fibre has excellent properties such as low density, HS, high-modulus, thereby has obtained widespread use in fields such as Aeronautics and Astronautics, weapon armaments.Along with 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 this hot research fields rapidly.SWCN (SWNT) strengthens body as inflexible nano level tubulose; Through 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.
Gathering [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] 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 interface adhesive property, thermal insulation, superpower resistance toheat, unique high incompressible intensity, good excellent properties such as weathering resistance.Above excellent characteristic makes high-performance PIPD fiber receive 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 big 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 big, 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 SWCN graft modification and gather [2; 5-dihydroxyl-1,4-penylene pyrido diimidazole] method, solve SWCN and gathering [2; 5-dihydroxyl-1; 4-penylene pyrido diimidazole] be easy to reunite, be difficult to disperse, be difficult to and gather [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] formation in the matrix and stablize covalently bound problem.
The method that a kind of SWCN graft modification of the present invention gathers [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] realizes through following steps: one, SWCN is carried out carboxylated processing, get carboxylated SWCN;
Two, carboxylated SWCN graft modification gathers [2,5-dihydroxyl-1,4-penylene pyrido diimidazole]: 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 SWCN that step 1 is obtained add in the poly phosphoric acid solution of a step preparation; Stirred 0.5～2 hour; Get carboxylated SWCN dispersion liquid, the mass ratio of the poly phosphoric acid solution of carboxylated SWCN that step 1 obtains and the preparation of a step is 1: 50～1000; C, will gather [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] and mix with methylsulfonic acid and stirred 4～24 hours; Must gather [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] solution; The mass ratio that wherein gathers [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] and methylsulfonic acid is 1: 20～100; D, the carboxylated SWCN dispersion liquid that the b step is obtained and c step obtain, and to gather [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] solution be 1: 1～2 mixed according to mass ratio; Stirring reaction 12～48 hours under 100 ℃～180 ℃ temperature then; Get reaction product, reaction product is washed after drying, get carboxylated SWCN graft modification and gather [2; 5-dihydroxyl-1,4-penylene pyrido diimidazole].
The method of in the step 1 of the present invention SWCN being carried out carboxylated processing is to adopt existing open disposal methods to get final product.
Gather [2 described in the c step in the step 2 of the present invention; 5-dihydroxyl-1; 4-penylene pyrido diimidazole] adopt existing disclosed preparation method to obtain, be CN101418073 as authorizing publication number, the patent No. be 200810137342.4 gather (2; 5-dihydroxyl-1,4-penylene pyrido diimidazole) preparation method who puts down in writing in preparing 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 reaction product is washed after drying; Method for washing is: reaction product is added in the entry; Low whipping speed is to wash 6～36 hours under 100～1000 rev/mins the condition, and the volume ratio of control reaction product and water is 1: 100～1000.
To be easy among the present invention reunite, be difficult to the carboxylated SWCN of dispersive and be mixed with dispersion liquid; System viscosity is big, stir the gathering of difficulty [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] (PIPD) polymer formulation become solution; Then dispersion liquid is mixed with solution; Having solved SWCN (SWNT) is easy in [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] matrix reunite, is difficult to disperse, is difficult to and gather [2 gathering; 5-dihydroxyl-1,4-penylene pyrido diimidazole] form and stablize problems such as covalently bound.Realized that the SWCN graft modification gathers [2,5-dihydroxyl-1,4-penylene pyrido diimidazole], has generated SWNT grafting PIPD multipolymer.Simultaneously, utilize the template effect of SWNT, will induce the PIPD fiber in axial direction further to be orientated, its mechanical property is further improved fibre orientation.
Method of the present invention is simple to operate.
Description of drawings
Fig. 1 is the building-up process synoptic diagram of the step 2 of test 1; Fig. 2 is the transmission electron microscope photo of the carboxylated SWCN that obtains of the treatment process of test 1 step 1; Fig. 3 is the infrared spectrogram of SWCN that adopts in the test 1 and the carboxylated SWCN that after step 1 is handled, obtains; 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 scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: this embodiment is that a kind of SWCN graft modification gathers [2; 5-dihydroxyl-1,4-penylene pyrido diimidazole] method, the SWCN graft modification gathers [2; 5-dihydroxyl-1,4-penylene pyrido diimidazole] method realize through following steps:
One, SWCN is carried out carboxylated processing, get carboxylated SWCN;
Two, carboxylated SWCN graft modification gathers [2,5-dihydroxyl-1,4-penylene pyrido diimidazole]: 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 SWCN that step 1 is obtained add in the poly phosphoric acid solution of a step preparation; Stirred 0.5～2 hour; Get carboxylated SWCN dispersion liquid, the mass ratio of the poly phosphoric acid solution of carboxylated SWCN that step 1 obtains and the preparation of a step is 1: 50～1000; C, will gather [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] and mix with methylsulfonic acid (MSA) and stirred 4～24 hours; Must gather [2; 5-dihydroxyl-1,4-penylene pyrido diimidazole] solution, wherein gather [2; 5-dihydroxyl-1,4-penylene pyrido diimidazole] with the mass ratio of methylsulfonic acid be 1: 20～100; D, the carboxylated SWCN dispersion liquid that the b step is obtained and c step obtain, and to gather [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] solution be 1: 1～2 mixed according to mass ratio; Stirring reaction 12～48 hours under 100 ℃～180 ℃ temperature then; Get reaction product, reaction product is washed after drying, get carboxylated SWCN graft modification and gather [2; 5-dihydroxyl-1,4-penylene pyrido diimidazole].
The method of in this embodiment step 1 SWCN being carried out carboxylated processing is to adopt existing open disposal methods to get final product.
Gather [2 described in the c step in this embodiment step 2; 5-dihydroxyl-1; 4-penylene pyrido diimidazole] adopt existing disclosed preparation method to obtain, be CN101418073 as authorizing publication number, the patent No. be 200810137342.4 gather (2; 5-dihydroxyl-1,4-penylene pyrido diimidazole) preparation method who puts down in writing in preparing method's the patent.
To be easy in this embodiment reunite, be difficult to the carboxylated SWCN of dispersive and be mixed with dispersion liquid; System viscosity is big, stir the gathering of difficulty [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] (PIPD) polymer formulation become solution; Then dispersion liquid is mixed with solution; Having solved SWCN (SWNT) is easy in [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] matrix reunite, is difficult to disperse, is difficult to and gather [2 gathering; 5-dihydroxyl-1,4-penylene pyrido diimidazole] form and stablize problems such as covalently bound.Realized that the SWCN graft modification gathers [2,5-dihydroxyl-1,4-penylene pyrido diimidazole], has generated SWNT grafting PIPD multipolymer.Simultaneously, utilize the template effect of SWNT, will induce the PIPD fiber in axial direction further to be orientated, its mechanical property is further improved fibre orientation.
The method of this embodiment is simple to operate.
The building-up process of the preparing method's of this embodiment step 2 to step 3 is as follows:
Embodiment two: what this embodiment and embodiment one were different is to adopt following steps that SWCN is carried out carboxylated processing in the step 1: one, in nitration mixture, add SWCN; Then 100 ℃ of following stirring reactions 24 hours; Cool off mixture; Wherein, nitration mixture is dense HNO
3With dense H
2SO
4Be 1: 3 by volume, the ratio of SWCN quality and nitration mixture volume is 1g: 45mL～50mL; Two, in the mixture that step 1 obtains, add zero(ppm) water; Stir after 30 minutes; Through the millipore filtration suction filtration of 0.22 μ m, use zero(ppm) water rinse filter cake then, the pH value that leaches liquid until the strainer lower end is neutral; Then with filter cake at 90 ℃ of following vacuum dryings, obtain carboxylated SWCN.Other step and parameter are identical with embodiment one.
Embodiment three: this embodiment is different with embodiment one or two is that the preparation method who gathers [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] described in the c step of step 2 is following: a, under nitrogen atmosphere adds 2 in massfraction is the poly phosphoric acid solution (PPA) of 80%～84% Vanadium Pentoxide in FLAKES; 5-dihydric para-phthalic acid (DHTA), 2,3,5,6-4-aminopyridine hydrochloride monomer and tindichloride; Stir mixture A, then with mixture A 60 ℃～80 ℃ following heated and stirred reactions 12～36 hours, mixture B, wherein; 2,5-dihydric para-phthalic acid and 2,3; 5, the monomeric mol ratio of 6-4-aminopyridine hydrochloride is 1: 1, tindichloride and 2; 5-dihydric para-phthalic acid's mass ratio is 0.001～0.01: 1,2,5-dihydric para-phthalic acid, 2; 3,5, the total mass of 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 ℃, add Vanadium Pentoxide in FLAKES then, and the insulated and stirred reaction is 4～8 hours again; Get mixture C; Wherein, in the Vanadium Pentoxide in FLAKES of adding and a step 2,5-dihydric para-phthalic acid's mol ratio is 1: 0.67～1; C, the mixture C that the b step is obtained are warming up to 140 ℃～160 ℃, and insulation reaction is 3～5 hours then, is warming up to 180 ℃～200 ℃ again; Insulation reaction 3～5 hours, reaction product, and then after reaction product is cooled to room temperature; Washing 60～100 ℃ of following vacuum-dryings 12～48 hours, must gather [2 again to neutral; 5-dihydroxyl-1,4-penylene pyrido diimidazole].Other step and parameter are identical with embodiment one or two.
Adopt in a step of this embodiment 2,5-dihydric para-phthalic acid and 2,3,5,6-4-aminopyridine hydrochloride monomer all adopts existing public technology to prepare.
Mixture A is 60 ℃～80 ℃ following heated and stirred reactions 12～36 hours, to remove 2,3,5, the hydrogenchloride in the 6-4-aminopyridine hydrochloride in this 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: this embodiment and embodiment three are different is to gather [2 described in the c step of step 2; 5-dihydroxyl-1; 4-penylene pyrido diimidazole] preparing method's a step in tindichloride and 2,5-dihydric para-phthalic acid's mass ratio is 0.002～0.006: 1.Other step and parameter are identical with embodiment three.
Tindichloride and 2 in this embodiment, 5-dihydric para-phthalic acid's mass ratio is preferably 0.003: 1.
Embodiment five: this embodiment is different with embodiment three or four is to gather [2 described in the c step of step 2; 5-dihydroxyl-1; 4-penylene pyrido diimidazole] preparing method's c step in mixture C that the b step is obtained be warming up to 150 ℃, insulation reaction is 5 hours then, is warming up to 180 ℃ again; Insulation reaction 5 hours gets reaction product.Other step and parameter are identical with embodiment three or four.
Embodiment six: this embodiment is different with 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: this embodiment is different with one of embodiment one to six be in the d step of step 2 under 120 ℃～150 ℃ temperature stirring reaction 18～32 hours, reaction product.Other step and parameter are identical with one of embodiment one to six.
Embodiment eight: this embodiment is different with one of embodiment one to six be in the d step of step 2 under 130 ℃ of temperature stirring reaction 24 hours, reaction product.Other step and parameter are identical with one of embodiment one to six.
Embodiment nine: this embodiment is different with one of embodiment one to eight is in the d step of step 2 reaction product to be washed after drying; Method for washing is: reaction product is added in the entry; Low whipping speed is to wash 6～36 hours under 100～1000 rev/mins the condition, 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, test as follows:
Test 1: the method that the SWCN graft modification gathers [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] realizes through following steps:
One, SWCN is carried out carboxylated processing, concrete steps are following: a, filling the dense HNO of 40mL
3With the dense H of 120mL
2SO
4The 1L there-necked flask in, add the SWCN (SWNT) of 3.420g, 100 ℃ of following stirring reactions 24 hours, cool off mixture; B, in the mixture that step 1 obtains, add 500mL zero(ppm) water; Stir after 30 minutes; Through the millipore filtration suction filtration of 0.22 μ m, use zero(ppm) water rinse filter cake then, the pH value that leaches liquid until the strainer lower end is neutral; Then with filter cake at 90 ℃ of following vacuum dryings, obtain carboxylated SWCN;
Two, to gather [2,5-dihydroxyl-1,4-penylene pyrido diimidazole]: a, the 193.34g Vanadium Pentoxide in FLAKES is added to the 145.55g mass percentage concentration be that stirring and dissolving gets poly phosphoric acid solution in 85% the phosphoric acid in carboxylated SWCN graft modification; B, the carboxylated SWCN that the 0.5g step 1 is obtained add in the poly phosphoric acid solution of a step preparation, stir 1 hour, get carboxylated SWCN dispersion liquid; C, 10g is gathered [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] and mix with the 338.89g methylsulfonic acid and stirred 12 hours, must gather [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] solution; [2,5-dihydroxyl-1, the 4-penylene pyrido diimidazole] solution that gathers that d, the carboxylated SWCN dispersion liquid that the b step is obtained and c step obtain mixes; Stirring reaction 24 hours under 130 ℃ of temperature then, reaction product, reaction product is added in the 2L water; Low whipping speed is washing 24 hours under 500 rev/mins the condition, and is dry again, carboxylated SWCN graft modification gather [2; 5-dihydroxyl-1,4-penylene pyrido diimidazole].
1., under nitrogen atmosphere wherein gathering [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] in the c step of step 2 prepares through following steps:, in massfraction is the poly phosphoric acid solution of 83.7% Vanadium Pentoxide in FLAKES, add 2; 5-dihydric para-phthalic acid, 2,3,5,6-4-aminopyridine hydrochloride monomer and tindichloride; Stir mixture A, then with mixture A 60 ℃～80 ℃ following heated and stirred reactions 12～36 hours, mixture B, wherein; 2,5-dihydric para-phthalic acid and 2,3; 5, the monomeric mol ratio of 6-4-aminopyridine hydrochloride is 1: 1, tindichloride and 2; 5-dihydric para-phthalic acid's mass ratio is 0.003: 1,2, and 5-dihydric para-phthalic acid, 2; 3,5, the total mass of 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 ℃, adds Vanadium Pentoxide in FLAKES then, the insulated and stirred reaction is 6 hours again, mixture C, wherein, in the Vanadium Pentoxide in FLAKES of adding and a step 2,5-dihydric para-phthalic acid's mol ratio is 1: 0.8; 3., mixture C that the b step is obtained is warming up to 150 ℃, insulation reaction is 5 hours then, is warming up to 180 ℃ again; Insulation reaction 5 hours, reaction product, and then after reaction product is cooled to room temperature; Washing 80 ℃ of following vacuum-dryings 24 hours, must gather [2 again to neutral; 5-dihydroxyl-1,4-penylene pyrido diimidazole].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, 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 of preparation 2,3; 5, the method for 6-4-aminopyridine hydrochloride " (applying date: 2008.6.6, application number: 200810064682.7) disclosed method prepares.
The building-up process synoptic diagram of the preparing method's of test 1 step 2 is as shown in Figure 1.
The transmission electron microscope photo of the carboxylated SWCN that the treatment process of the step 1 of employing test 1 obtains is as shown in Figure 2, and visible by Fig. 2, SWCN (SWNT) is through oxide treatment, and its length is prescinded greatly, does not have tangible entanglement phenomenon and exists.The effective purifying of oxidation treatment method SWNT, prepare the impurity of introducing in the process at SWNT and disappear basically.Simultaneously, the transmission electron microscope picture shows that also through after the oxide treatment, open the termination of SWNT, and introduced a large amount of activity functional groups at these positions, like carboxyl, hydroxyl etc.
The infrared spectrogram of testing SWCN that adopts in 1 and the carboxylated SWCN that after step 1 is handled, obtains is as shown in Figure 3, and is visible by Fig. 3, and SWNT has two tangible 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, promptly in the carboxylic acid-stretching vibration of C=O, show that SWNT has introduced carboxyl functional group on the surface.
The carboxylated SWCN graft modification that test 1 prepares gathers [2; 5-dihydroxyl-1; 4-penylene pyrido diimidazole] infrared spectrogram of (SWNT graft modification PIPD) is as shown in Figure 4; Shown among Fig. 4 and gathered [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] charateristic avsorption band (PIPD).As～1620cm
-1C=N ,～1050cm
-1=C-O-C and～3050cm
-1Aromatic ring on C-H.The ir spectra (Fig. 3) of SWNT graft modification PIPD ir 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 that copolymerization does not change the molecular structure of PIPD, has generated SWNT graft modification PIPD multipolymer simultaneously.
The carboxylated SWCN graft modification that test 1 prepares gathers [2; 5-dihydroxyl-1; 4-penylene pyrido diimidazole] stereoscan photograph (SEM) of (SWNT graft modification PIPD) is as shown in Figure 4; Can find out that from SEM figure SWNT is uniformly dispersed in the PIPD polymeric matrix, not find to reunite.The PIPD film surface is comparatively smooth.
Claims (9)
1. a SWCN graft modification gathers [2; 5-dihydroxyl-1,4-penylene pyrido diimidazole] method, it is characterized in that the SWCN graft modification gathers [2; 5-dihydroxyl-1,4-penylene pyrido diimidazole] method realize through following steps:
One, SWCN is carried out carboxylated processing, get carboxylated SWCN;
Two, carboxylated SWCN graft modification gathers [2,5-dihydroxyl-1,4-penylene pyrido diimidazole]: 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 SWCN that step 1 is obtained add in the poly phosphoric acid solution of a step preparation; Stirred 0.5～2 hour; Get carboxylated SWCN dispersion liquid, the mass ratio of the poly phosphoric acid solution of carboxylated SWCN that step 1 obtains and the preparation of a step is 1: 50～1000; C, will gather [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] and mix with methylsulfonic acid and stirred 4～24 hours; Must gather [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] solution; The mass ratio that wherein gathers [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] and methylsulfonic acid is 1: 20～100; D, the carboxylated SWCN dispersion liquid that the b step is obtained and c step obtain, and to gather [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] solution be 1: 1～2 mixed according to mass ratio; Stirring reaction 12～48 hours under 100 ℃～180 ℃ temperature then; Get reaction product, reaction product is washed after drying, get carboxylated SWCN graft modification and gather [2; 5-dihydroxyl-1,4-penylene pyrido diimidazole].
2. a kind of SWCN graft modification according to claim 1 gathers [2; 5-dihydroxyl-1,4-penylene pyrido diimidazole] method, it is characterized in that adopting in the step 1 following steps that SWCN is carried out carboxylated processing: one, in nitration mixture, to add SWCN; Then 100 ℃ of following stirring reactions 24 hours; Cool off mixture, wherein, nitration mixture is dense HNO
3With dense H
2SO
4Be 1: 3 by volume, the ratio of SWCN quality and nitration mixture volume is 1g: 45mL～50mL; Two, in the mixture that step 1 obtains, add zero(ppm) water; Stir after 30 minutes; Through the millipore filtration suction filtration of 0.22 μ m, use zero(ppm) water rinse filter cake then, the pH value that leaches liquid until the strainer lower end is neutral; Then with filter cake at 90 ℃ of following vacuum dryings, obtain carboxylated SWCN.
3. a kind of SWCN graft modification according to claim 1 and 2 gathers the method for [2,5-dihydroxyl-1,4-penylene pyrido diimidazole], it is characterized in that gathering [2 described in the c step of step 2; 5-dihydroxyl-1,4-penylene pyrido diimidazole] the preparation method following: a, under nitrogen atmosphere adds 2,5-dihydric para-phthalic acid, 2 in massfraction is the poly phosphoric acid solution of 80%～84% Vanadium Pentoxide in FLAKES; 3,5,6-4-aminopyridine hydrochloride monomer and tindichloride, stir mixture A; Then mixture A was reacted 12～36 hours 60 ℃～80 ℃ following heated and stirred, get mixture B, wherein; 2,5-dihydric para-phthalic acid and 2,3; 5, the monomeric mol ratio of 6-4-aminopyridine hydrochloride is 1: 1, tindichloride and 2; 5-dihydric para-phthalic acid's mass ratio is 0.001～0.01: 1,2,5-dihydric para-phthalic acid, 2; 3,5, the total mass of 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 ℃, add Vanadium Pentoxide in FLAKES then, and the insulated and stirred reaction is 4～8 hours again; Get mixture C; Wherein, in the Vanadium Pentoxide in FLAKES of adding and a step 2,5-dihydric para-phthalic acid's mol ratio is 1: 0.67～1; C, the mixture C that the b step is obtained are warming up to 140 ℃～160 ℃, and insulation reaction is 3～5 hours then, is warming up to 180 ℃～200 ℃ again; Insulation reaction 3～5 hours, reaction product, and then after reaction product is cooled to room temperature; Washing 60～100 ℃ of following vacuum-dryings 12～48 hours, must gather [2 again to neutral; 5-dihydroxyl-1,4-penylene pyrido diimidazole].
4. a kind of SWCN graft modification according to claim 3 gathers [2; 5-dihydroxyl-1; 4-penylene pyrido diimidazole] method, it is characterized in that gathering described in the c step of step 2 [2,5-dihydroxyl-1; 4-penylene pyrido diimidazole] preparing method's a step in tindichloride and 2,5-dihydric para-phthalic acid's mass ratio is 0.002～0.006: 1.
5. the method for gathering [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] according to claim 3 or 4 described a kind of SWCN graft modifications; It is characterized in that the mixture C that in the preparing method's who gathers [2,5-dihydroxyl-1,4-penylene pyrido diimidazole] described in the c step of step 2 the c step b step is obtained is warming up to 150 ℃; Insulation reaction is 5 hours then; Be warming up to 180 ℃ again, insulation reaction 5 hours gets reaction product.
6. a kind of SWCN graft modification according to claim 1 and 2 gathers the method for [2,5-dihydroxyl-1,4-penylene pyrido diimidazole], it is characterized in that phosphoric acid concentration is 85% in a step of step 2.
7. a kind of SWCN graft modification according to claim 1 and 2 gathers [2; 5-dihydroxyl-1; 4-penylene pyrido diimidazole] method, it is characterized in that in the d step of step 2 under 120 ℃～150 ℃ temperature stirring reaction 18～32 hours, reaction product.
8. a kind of SWCN graft modification according to claim 1 and 2 gathers the method for [2,5-dihydroxyl-1,4-penylene pyrido diimidazole], it is characterized in that in the d step of step 2 under 130 ℃ of temperature stirring reaction 24 hours, reaction product.
9. a kind of SWCN graft modification according to claim 1 and 2 gathers [2; 5-dihydroxyl-1; 4-penylene pyrido diimidazole] method, it is characterized in that in the d step of step 2 reaction product being washed after drying, method for washing is: reaction product is added in the entry; Low whipping speed is to wash 6～36 hours under 100～1000 rev/mins the condition, and the volume ratio of control reaction product and water is 1: 100～1000.
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| CN104818611A (en) * | 2015-05-07 | 2015-08-05 | 哈尔滨工业大学 | Method of improving anti-ultraviolet performance of M5 fiber with tubular titanium dioxide |
| CN114805799A (en) * | 2022-05-18 | 2022-07-29 | 哈尔滨工业大学 | Preparation method and application of PIPD-SWCNT (polymer dispersed particle nano tube-single-walled carbon nanotube) copolymer |
| CN114835436A (en) * | 2022-06-06 | 2022-08-02 | 安徽飞鹰汽车零部件股份有限公司 | Water passing groove wear-resistant drum brake pad with mineral wool as filler and preparation method thereof |
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