CN103788395A - Preparation method of graphene/polyparaphenylene benzobisoxazole composite copolymer film - Google Patents
Preparation method of graphene/polyparaphenylene benzobisoxazole composite copolymer film Download PDFInfo
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Abstract
The invention discloses a preparation method of a graphene/polyparaphenylene benzobisoxazole (PBO) composite copolymer film, relating to a preparation method of a graphene high molecular composite copolymer film and solving the problems that a PBO composite film is hard to prepare, graphene is easy to agglomerate, hard to disperse, liable to migrate to the surface of the film and relatively low in activity of reaction with PBO in a PBO base body. The method comprises the following steps: 1, preparing graphite oxide; 2, preparing aminated graphene; 3, preparing a graphene/PBO copolymer; 4, preparing the film. According to the method, graphene has good dispersity in the PBO base body, hardly agglomerate, and is stable in phase structure, unlikely to migrate to the surface of the film and relatively high in activity of reaction with the PBO. The method is used for preparing the graphene/PBO composite copolymer film.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene polymer composite copolymerization film.
Background technology
Polyparaphenylene's benzo-dioxazole (PBO) is pioneer and the representative of high strength of new generation, high-modulus, high temperature polymeric materials, is the ideal material of preparing high-strength and high-modulus film or fiber.PBO is a kind of full hetero-aromatic ring liquid crystal polymer, have the extremely strong linear extended-chain configuration of rigidity, its link angle is that the angle between the ring external key on stiff backbone unit is 180 °, can not interiorly rotate, molecular chain is rigidity, therefore has good mechanical property, thermal characteristics and flame retardant properties.PBO is usually used to prepare high-performance fiber, and PBO laminated film is difficult to preparation.Graphene, as a kind of flexible layer nano material, has excellent mechanics, optics, magnetics and electric property, has therefore caused people's extensive concern in high-performance polymer modification field.Due to Graphene have high surface can, with the compound process of PBO in, inevitably can produce agglomeration, thereby cause the phase structure of blend extremely unstable, be easy to, to material surface migration, modified effect sharply be declined.Meanwhile, Graphene reactive behavior is conventionally poor, is difficult to form the covalently bound molecular composite material of preparing with PBO, and then makes Graphene very limited for the modifying function of PBO.
Summary of the invention
The object of the invention is to be difficult to preparation in order to solve PBO laminated film, Graphene is easy to reunite, is difficult to disperse, be easy to the problem on the low side to film surface migration, Graphene and PBO reactive behavior in PBO matrix, and a kind of preparation method of Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film is provided.
The preparation method of Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film of the present invention, realizes by following steps:
One, the preparation of graphite oxide: by the dense H of 200～2000mL
2sO
4dense H with 20～200mL
3pO
4mix, then add 1～5g nano-graphite and 3～100g KMnO
4then be to mix under 0 ℃～50 ℃ conditions in temperature, continue again to stir 24～72 hours, after cooling, add again 0.5～10L distilled water, stir 0.5～3 hour, then by the millipore filtration suction filtration of 0.22 μ m, and with distilled water rinse filter cake, be neutral until strainer lower end leaches the pH value of liquid, then will after filter cake lyophilize, obtain graphite oxide;
Two, the preparation of amination Graphene: take the graphite oxide powder that 0.1～1g step 1 obtains, the amino-complex of 10～100g, the N of 5～40mL, the N of N'-dimethyl formamide, 0.5～10g, the DMAP of N'-dicyclohexylcarbodiimide and 0.05～1g, ultrasonic dispersion 1～6 hour after mixing, under 40 ℃～100 ℃ lasting agitation conditions, react 18～72 hours again, obtain mixture, mixture is passed through to the millipore filtration suction filtration of 0.22 μ m, and with DMF washing 3～8 times, then amination Graphene will be obtained after filter cake lyophilize;
Three, the preparation of Graphene/PBO multipolymer: the amination Graphene that 0.5～5g step 2 is obtained joins in the phosphoric acid that the quality percentage composition of 30～200g is 80%～90%, ultrasonic 5～10h obtains the phosphoric acid solution of amination Graphene, then the Vanadium Pentoxide in FLAKES of 50～300g is divided and joined for 3～5 times in the phosphoric acid solution of amination Graphene under agitation condition, at 60 ℃～100 ℃, stir 1～5h and obtain mixture A, at nitrogen atmosphere, under 110 ℃～130 ℃ conditions, the terephthalic acid of 5～20g is added in mixture A, and stirring reaction obtains mixture B for 8～24 hours, get 4 of 20～150g, the tindichloride of 6-diamino resorcin dihydrochloride and 1～10g joins in mixture B, heated and stirred 12～36 hours at 60 ℃～100 ℃, obtain mixture C, 10～75g terephthalic acid is joined in mixture C, be warming up to 140 ℃～160 ℃, react after 3～5 hours, temperature is risen to 180 ℃～200 ℃, divide the Vanadium Pentoxide in FLAKES that adds 30～200g for 1～5 time, react 3～5 hours, obtain mixture D,
Four, the preparation of Graphene/PBO composite copolymerization film: the mixture D that step 3 is obtained is poured on the super flat stainless steel plate with polytetrafluoroethylene film, stainless steel plate is placed on thermocompressor, parameter is set to: temperature is that 120 ℃～240 ℃, pressure are that 5～300MPa, film formation time are 0.2～2h, after moulding, the film obtaining is placed in to quality percentage composition and is 0～30% phosphoric acid solution and soak 8～48 hours, then after drying at room temperature, obtain Graphene/PBO composite copolymerization film.
Beneficial effect of the present invention:
1, the present invention carries out amination modification to Graphene, and then by copolycondensation, Graphene is incorporated in the molecular chain of PBO polymkeric substance, and Graphene is connected with PBO molecular chain covalency, finally prepares PBO laminated film;
2, in the present invention, Graphene is dispersed better in PBO matrix, difficult reunion, phase structure are stablized, are not easy to film surface migration, Graphene and PBO reactive behavior higher, approximately improve 30%～80%, and the mechanical property of laminated film, resistance toheat are improved.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of present embodiment Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film, carries out according to the following steps:
One, the preparation of graphite oxide: by the dense H of 200～2000mL
2sO
4dense H with 20～200mL
3pO
4mix, then add 1～5g nano-graphite and 3～100g KMnO
4then be to mix under 0 ℃～50 ℃ conditions in temperature, continue again to stir 24～72 hours, after cooling, add again 0.5～10L distilled water, stir 0.5～3 hour, then by the millipore filtration suction filtration of 0.22 μ m, and with distilled water rinse filter cake, be neutral until strainer lower end leaches the pH value of liquid, then will after filter cake lyophilize, obtain graphite oxide;
Two, the preparation of amination Graphene: take the graphite oxide powder that 0.1～1g step 1 obtains, the amino-complex of 10～100g, the N of 5～40mL, the N of N'-dimethyl formamide, 0.5～10g, the DMAP of N'-dicyclohexylcarbodiimide and 0.05～1g, ultrasonic dispersion 1～6 hour after mixing, under 40 ℃～100 ℃ lasting agitation conditions, react 18～72 hours again, obtain mixture, mixture is passed through to the millipore filtration suction filtration of 0.22 μ m, and with DMF washing 3～8 times, then amination Graphene will be obtained after filter cake lyophilize;
Three, the preparation of Graphene/PBO multipolymer: the amination Graphene that 0.5～5g step 2 is obtained joins in the phosphoric acid that the quality percentage composition of 30～200g is 80%～90%, ultrasonic 5～10h obtains the phosphoric acid solution of amination Graphene, then the Vanadium Pentoxide in FLAKES of 50～300g is divided and joined for 3～5 times in the phosphoric acid solution of amination Graphene under agitation condition, at 60 ℃～100 ℃, stir 1～5h and obtain mixture A, at nitrogen atmosphere, under 110 ℃～130 ℃ conditions, the terephthalic acid of 5～20g is added in mixture A, and stirring reaction obtains mixture B for 8～24 hours, get 4 of 20～150g, the tindichloride of 6-diamino resorcin dihydrochloride and 1～10g joins in mixture B, heated and stirred 12～36 hours at 60 ℃～100 ℃, obtain mixture C, 10～75g terephthalic acid is joined in mixture C, be warming up to 140 ℃～160 ℃, react after 3～5 hours, temperature is risen to 180 ℃～200 ℃, divide the Vanadium Pentoxide in FLAKES that adds 30～200g for 1～5 time, react 3～5 hours, obtain mixture D,
Four, the preparation of Graphene/PBO composite copolymerization film: the mixture D that step 3 is obtained is poured on the super flat stainless steel plate with polytetrafluoroethylene film, stainless steel plate is placed on thermocompressor, parameter is set to: temperature is that 120 ℃～240 ℃, pressure are that 5～300MPa, film formation time are 0.2～2h, after moulding, the film obtaining is placed in to quality percentage composition and is 0～30% phosphoric acid solution and soak 8～48 hours, then after drying at room temperature, obtain Graphene/PBO composite copolymerization film.
The beneficial effect of present embodiment:
1, present embodiment is carried out amination modification to Graphene, and then by copolycondensation, Graphene is incorporated in the molecular chain of PBO polymkeric substance, and Graphene is connected with PBO molecular chain covalency, finally prepares PBO laminated film;
2, in present embodiment, Graphene is dispersed better in PBO matrix, difficult reunion, phase structure are stablized, are not easy to film surface migration, Graphene and PBO reactive behavior higher, approximately improve 30%～80%, and the mechanical property of laminated film, resistance toheat are improved.
Embodiment two: present embodiment is different from embodiment one: the dense H described in step 1
2sO
4volume be 400mL, dense H
3pO
4volume be 50mL.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: the quality of the nano-graphite described in step 1 is 2g.Other is identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: the KMnO described in step 1
4quality be 22g.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: the volume that adds distilled water described in step 1 is 2L.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five: the amino-complex described in step 2 is quadrol, 1,2-propylene diamine, 1, one or more in 3-propylene diamine, Putriscine, hexanediamine, Ursol D, mphenylenediamine, O-Phenylene Diamine are by any combination.Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six: be warming up to 150 ℃ described in step 3, react after 4 hours, temperature is risen to 190 ℃, divide the Vanadium Pentoxide in FLAKES that adds 39g for 3 times, react 4 hours, obtain mixture D.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven: the parameter described in step 4 is set to: temperature is that 160 ℃, pressure are that 10MPa, film formation time are 15min.Other is identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight: after the moulding described in step 4, the film obtaining is placed in to quality percentage composition and is 10% phosphoric acid solution and soak 36 hours.Other is identical with one of embodiment one to eight.
Embodiment ten: present embodiment is different from one of embodiment one to nine: after the moulding described in step 4, the film obtaining is placed in to pure water and soaks 36 hours.Other is identical with one of embodiment one to nine.
Verify beneficial effect of the present invention by following examples:
Embodiment mono-:
The preparation method of the present embodiment Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film, carries out according to the following steps:
One, the preparation of graphite oxide: filling the dense H of 400mL
2sO
4and the dense H of 50mL
3pO
41L there-necked flask in, add 2g nano-graphite and 22g KMnO
4at 50 ℃, continue to stir 24 hours, reacted and cooling after, mixing solutions proceeds in the beaker of 3L, adds 2L distilled water, stirs after 2 hours, by the millipore filtration suction filtration of 0.22 μ m, and with a large amount of distilled water rinse filter cakes, be neutral until strainer lower end leaches the pH value of liquid, will after filter cake lyophilize, obtain graphite oxide;
Two, the preparation of amination Graphene: get the graphite oxide of 0.2g prepared by step 1, the quadrol of 50mL, the N of 10mL, the N of N'-dimethyl formamide, 1g, the DMAP of N'-dicyclohexylcarbodiimide, 0.1g is placed in single port flask, after ultrasonic dispersion 4h, continue to react 48 hours under stirring at 80 ℃, obtain a homogeneous mixture, this uniform mixture is passed through to the millipore filtration suction filtration of 0.22 μ m, and with DMF washing 5 times, amination Graphene will be obtained after filter cake lyophilize;
Three, the preparation of Graphene/PBO multipolymer: 0.5g amination Graphene prepared by step 2 is added in the phosphoric acid that the quality percentage composition of 43g is 85%, ultrasonic 10h is dispersed in phosphoric acid to amination Graphene, 54g Vanadium Pentoxide in FLAKES is under agitation divided in the phosphoric acid solution that joins above-mentioned amination Graphene for 3 times, at 80 ℃, stir 3h and obtain mixture A, at nitrogen atmosphere, at 120 ℃, 6g terephthalic acid is added in mixture A, and stirring reaction obtains mixture B for 24 hours at this temperature, get 4 of 21.31g, 6-diamino resorcin dihydrochloride and 1g tindichloride are added in mixture B, at 80 ℃, heated and stirred 24 hours is to remove 4, hydrogenchloride in 6-diamino resorcin dihydrochloride, obtain mixture C, other 10.6g terephthalic acid is added in mixture C, when being warming up to 150 ℃, polymerization system reacts after 4 hours, temperature rises to 190 ℃, divide the Vanadium Pentoxide in FLAKES that adds 39g for 3 times, react 4 hours, obtain mixture D,
Four, the preparation of Graphene/PBO composite copolymerization film: mixture D prepared by step 3 is poured on the super flat stainless steel plate with polytetrafluoroethylene film, stainless steel plate is placed on thermocompressor, parameter is set to: 160 ℃ of temperature, pressure 10MPa, film formation time 15min, after moulding, the film obtaining is placed in to quality percentage composition and is 10% phosphoric acid solution and soak 36 hours, after drying at room temperature, obtain Graphene/PBO composite copolymerization film.
Graphene/PBO composite copolymerization the film that adopts standard GB/T/T1040.3-2006 to prepare embodiment mono-carries out tensile property test, adopt in thermogravimetric analyzer test Graphene/PBO composite copolymerization film air atmosphere and carry out thermal weight loss, mensuration temperature range is room temperature～750 ℃, temperature rise rate is 10 ℃/10min, and composite membrane consumption is 25mg.From test result, tensile strength and the modulus of the Graphene/PBO composite copolymerization film being prepared by the present embodiment are respectively 1.96GPa and 103.6GPa, and the purer PBO film of tensile strength and modulus has increased respectively 47% and 57%; The initial decomposition temperature (T5%) of Graphene/PBO composite copolymerization film is 556.8 ℃, exceeds 102 ℃ than the initial decomposition temperature of pure PBO film, has illustrated that composite copolymerization film has better resistance toheat than PBO film.
Embodiment bis-:
The preparation method of the present embodiment Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film, carries out according to the following steps:
One, the preparation of graphite oxide: filling the dense H of 480mL
2sO
4and the dense H of 54mL
3pO
41L there-necked flask in, add 4g nano-graphite and 24g KMnO
4at 40 ℃, continue to stir 48 hours, reacted and cooling after, mixing solutions proceeds in the beaker of 3L, adds 0.72L distilled water, stirs after 3 hours, by the millipore filtration suction filtration of 0.22 μ m, and with a large amount of distilled water rinse filter cakes, be neutral until strainer lower end leaches the pH value of liquid, will after filter cake lyophilize, obtain graphite oxide;
Two, the preparation of amination Graphene: take the graphite oxide powder that 0.2g step 1 obtains, the quadrol of 50mL, the N of 10mL, the N of N'-dimethyl formamide, 1g, the DMAP of N'-dicyclohexylcarbodiimide and 0.1g, ultrasonic dispersion 6 hours after mixing, under 90 ℃ of lasting agitation conditions, react 72 hours again, obtain mixture, mixture is passed through to the millipore filtration suction filtration of 0.22 μ m, and with DMF washing 6 times, then amination Graphene will be obtained after filter cake lyophilize;
Three, the preparation of Graphene/PBO multipolymer: the amination Graphene that 0.5g step 2 is obtained joins in the phosphoric acid that the quality percentage composition of 50g is 90%, ultrasonic 8h obtains the phosphoric acid solution of amination Graphene, then the Vanadium Pentoxide in FLAKES of 60g is divided and joined for 5 times in the phosphoric acid solution of amination Graphene under agitation condition, at 90 ℃, stir 5h and obtain mixture A, at nitrogen atmosphere, under 130 ℃ of conditions, the terephthalic acid of 7g is added in mixture A, and stirring reaction obtains mixture B for 24 hours, get 4 of 25g, the tindichloride of 6-diamino resorcin dihydrochloride and 1.2g joins in mixture B, heated and stirred 36 hours at 90 ℃, obtain mixture C, 12g terephthalic acid is joined in mixture C, be warming up to 160 ℃, react after 3 hours, temperature is risen to 200 ℃, divide the Vanadium Pentoxide in FLAKES that adds 50g for 4 times, react 5 hours, obtain mixture D,
Four, the preparation of Graphene/PBO composite copolymerization film: the mixture D that step 3 is obtained is poured on the super flat stainless steel plate with polytetrafluoroethylene film, stainless steel plate is placed on thermocompressor, parameter is set to: temperature is that 180 ℃, pressure are that 30MPa, film formation time are 0.5h, after moulding, the film obtaining is placed in to pure water and soaks 36 hours, more obtain Graphene after drying at room temperature/PBO composite copolymerization film.
Above-described embodiment carries out amination modification to Graphene, and then by copolycondensation, Graphene is incorporated in the molecular chain of PBO polymkeric substance, and Graphene is connected with PBO molecular chain covalency, finally prepares PBO laminated film.
In above-described embodiment, Graphene is dispersed better in PBO matrix, difficult reunion, phase structure are stablized, are not easy to film surface migration, Graphene and PBO reactive behavior higher, approximately improve 30%～80%, and the mechanical property of laminated film, resistance toheat are improved.
Claims (10)
1. a preparation method for Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film, is characterized in that it comprises the following steps:
One, the preparation of graphite oxide: by the dense H of 200～2000mL
2sO
4dense H with 20～200mL
3pO
4mix, then add 1～5g nano-graphite and 3～100g KMnO
4then be to mix under 0 ℃～50 ℃ conditions in temperature, continue again to stir 24～72 hours, after cooling, add again 0.5～10L distilled water, stir 0.5～3 hour, then by the millipore filtration suction filtration of 0.22 μ m, and with distilled water rinse filter cake, be neutral until strainer lower end leaches the pH value of liquid, then will after filter cake lyophilize, obtain graphite oxide;
Two, the preparation of amination Graphene: take the graphite oxide powder that 0.1～1g step 1 obtains, the amino-complex of 10～100g, the N of 5～40mL, the N of N'-dimethyl formamide, 0.5～10g, the DMAP of N'-dicyclohexylcarbodiimide and 0.05～1g, ultrasonic dispersion 1～6 hour after mixing, under 40 ℃～100 ℃ lasting agitation conditions, react 18～72 hours again, obtain mixture, mixture is passed through to the millipore filtration suction filtration of 0.22 μ m, and with DMF washing 3～8 times, then amination Graphene will be obtained after filter cake lyophilize;
Three, the preparation of Graphene/PBO multipolymer: the amination Graphene that 0.5～5g step 2 is obtained joins in the phosphoric acid that the quality percentage composition of 30～200g is 80%～90%, ultrasonic 5～10h obtains the phosphoric acid solution of amination Graphene, then the Vanadium Pentoxide in FLAKES of 50～300g is divided and joined for 3～5 times in the phosphoric acid solution of amination Graphene under agitation condition, at 60 ℃～100 ℃, stir 1～5h and obtain mixture A, at nitrogen atmosphere, under 110 ℃～130 ℃ conditions, the terephthalic acid of 5～20g is added in mixture A, and stirring reaction obtains mixture B for 8～24 hours, get 4 of 20～150g, the tindichloride of 6-diamino resorcin dihydrochloride and 1～10g joins in mixture B, heated and stirred 12～36 hours at 60 ℃～100 ℃, obtain mixture C, 10～75g terephthalic acid is joined in mixture C, be warming up to 140 ℃～160 ℃, react after 3～5 hours, temperature is risen to 180 ℃～200 ℃, divide the Vanadium Pentoxide in FLAKES that adds 30～200g for 1～5 time, react 3～5 hours, obtain mixture D,
Four, the preparation of Graphene/PBO composite copolymerization film: the mixture D that step 3 is obtained is poured on the super flat stainless steel plate with polytetrafluoroethylene film, stainless steel plate is placed on thermocompressor, parameter is set to: temperature is that 120 ℃～240 ℃, pressure are that 5～300MPa, film formation time are 0.2～2h, after moulding, the film obtaining is placed in to quality percentage composition and is 0～30% phosphoric acid solution and soak 8～48 hours, then after drying at room temperature, obtain Graphene/PBO composite copolymerization film.
2. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film according to claim 1, is characterized in that the dense H described in step 1
2sO
4volume be 400mL, dense H
3pO
4volume be 50mL.
3. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film according to claim 1, the quality that it is characterized in that the nano-graphite described in step 1 is 2g.
4. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film according to claim 1, is characterized in that the KMnO described in step 1
4quality be 22g.
5. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film according to claim 1, is characterized in that the volume that adds distilled water described in step 1 is 2L.
6. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film according to claim 1, it is characterized in that the amino-complex described in step 2 is quadrol, 1,2-propylene diamine, 1, one or more in 3-propylene diamine, Putriscine, hexanediamine, Ursol D, mphenylenediamine, O-Phenylene Diamine are by any combination.
7. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film according to claim 1, it is characterized in that be warming up to 150 ℃ described in step 3, react after 4 hours, temperature is risen to 190 ℃, divide the Vanadium Pentoxide in FLAKES that adds 39g for 3 times, react 4 hours, obtain mixture D.
8. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film according to claim 1, is characterized in that the parameter described in step 4 is set to: temperature is that 160 ℃, pressure are that 10MPa, film formation time are 15min.
9. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film according to claim 1, is characterized in that the film obtaining being placed in after the moulding described in step 4 quality percentage composition and is 10% phosphoric acid solution and soak 36 hours.
10. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite copolymerization film according to claim 1, is characterized in that the film obtaining being placed in to pure water after the moulding described in step 4 soaks 36 hours.
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| CN107603107A (en) * | 2017-09-27 | 2018-01-19 | 上海航天精密机械研究所 | Poly- 2 isopropenyl benzo oxazole nano composite material and preparation method thereof |
| CN107603107B (en) * | 2017-09-27 | 2019-09-17 | 上海航天精密机械研究所 | Poly- 2- isopropenyl benzo oxazole nanocomposite and preparation method thereof |
| CN115368683A (en) * | 2022-08-22 | 2022-11-22 | 浙江顺豪新材料有限公司 | Lining rubber material for electromagnetic flowmeter and preparation method thereof |
| CN115368683B (en) * | 2022-08-22 | 2023-11-17 | 浙江顺豪新材料有限公司 | Lining rubber material for electromagnetic flowmeter and preparation method thereof |
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