CN103788647A - Preparation method of graphene/poly(p-phenylene benzobisthiazole) composite membrane - Google Patents
Preparation method of graphene/poly(p-phenylene benzobisthiazole) composite membrane Download PDFInfo
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Abstract
The invention discloses a preparation method of a graphene/poly(p-phenylene benzobisthiazole) (PBO) composite membrane, and relates to a preparation method of a graphene high polymer composite membrane. The preparation method of the graphene/PBO composite membrane is used for solving the problem that the PBO composite membranes prepared by the existing methods are bad in heat resistance and bad in mechanical property. The graphene/PBO composite membrane comprises the steps: (1) preparing graphite oxide, (2) weighing, (3) preparing a graphene/PBO compound, and (4) preparing the membrane. According to the preparation method, the prepared composite membrane has better heat resistance and mechanical property than the PBO membrane. The preparation method is used for preparing the graphene/PBO composite membrane.
Description
Technical field
The present invention relates to the preparation method of Graphene polymer compound film.
Background technology
High-performance liquid crystalline polymers has the advantages such as mechanical property is high, resistance toheat is stable, is widely used in the key areas such as aerospace, weapon armament.Polyparaphenylene's benzo-dioxazole (PBO) is a kind of typical aromatic liquid-crystalline polymkeric substance, has high strength, high-modulus, high impact properties, super-hydrophobicity and thermal insulation, the superpower excellent properties such as resistance toheat, good weathering resistance.PBO is usually used to prepare high-performance fiber, and PBO laminated film is difficult to preparation.Along with scientific and technical progress, people have higher requirement to PBO, obtained people's generally approval, and develop into the study hotspot in this field rapidly and use Graphene to carry out modification to it.Graphene is as a kind of nano level sheet modification body of flexibility, by forming nano composite material with PBO covalency or composite, prepare Graphene/PBO composite membrane and can significantly improve mechanical strength and the resistance toheat of film by being hot pressed into membrane process, can improve the specific conductivity of PBO film, give the functions such as film wave-absorbing and camouflage, electromagnetic shielding simultaneously.But, the preparation method of existing Graphene PBO composite membrane still exists Graphene and is easy to reunite, is difficult to disperse, is easy to the problem of film surface migration, thereby cause Graphene PBO composite membrane poor heat resistance, the poor mechanical property prepared, affect it and further develop.
Summary of the invention
The present invention will solve PBO laminated film prepared by existing method and have the problem of poor heat resistance, poor mechanical property, and a kind of preparation method of Graphene/polyparaphenylene benzo-dioxazole composite membrane is provided.
A preparation method for Graphene/polyparaphenylene benzo-dioxazole composite membrane, specifically carries out according to following steps:
One, by the dense H of 200mL～1500mL
2sO
4dense H with 20mL～100mL
3pO
4mix, then add 1g～10g nano-graphite and 6g～50g KMnO
4then be to mix under 0～50 ℃ of condition in temperature, continue again to stir 12～48 hours, then cooling, then add 0.5L～5L distilled water, stir 0.5～2 hour, again 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, take the Vanadium Pentoxide in FLAKES of graphite oxide that 0.5～6 part of step 1 obtains, phosphoric acid that 202 parts of mass concentrations are 85%, the Vanadium Pentoxide in FLAKES of 253 parts, 100 parts of 4,6-diaminoresorcinol dihydrochlorides, 1～10 part of tindichloride, 78 parts of terephthalic acids and 183 parts according to mass fraction;
Three, the graphite oxide that step 2 is taken joins in phosphoric acid, ultrasonic dispersion 5～10h, point Vanadium Pentoxide in FLAKES of 253 parts that adds for 3～5 times step 2 to take under agitation condition again, then controlling temperature is 60 ℃～100 ℃, stir 1～5h, again under nitrogen atmosphere, add that step 2 takes 4, 6-diamino resorcin dihydrochloride and tindichloride, then controlling temperature is 60 ℃～100 ℃, stir 12～36 hours, be warming up to again 120 ℃, keep 8～24 hours, then be under 120 ℃ of conditions in temperature, the terephthalic acid that adds step 2 to take, and stir 4～8 hours, being warming up to temperature is 140 ℃～160 ℃ again, keep 3～5 hours, being warming up to temperature is 180 ℃～200 ℃ again, dividing adds for 3 times the Vanadium Pentoxide in FLAKES of 183 parts that step 2 takes to react, controlling the reaction times is 3～5 hours, obtain Graphene/PBO mixture,
Four, Graphene/PBO mixture step 3 being prepared into is poured on the super flat stainless steel plate with polytetrafluoroethylene film, then stainless steel plate is placed on thermocompressor, be arranged to shape parameter: 120 ℃～240 ℃ of temperature, pressure 5MPa～300MPa, film formation time 0.2～2h, after moulding, it is that 0～30% phosphoric acid solution soaks 8～48 hours that the film obtaining is put into mass concentration, then drying at room temperature, obtains Graphene/polyparaphenylene benzo-dioxazole composite membrane.
The invention has the beneficial effects as follows: tensile strength and the modulus of Graphene/polyparaphenylene benzo-dioxazole composite membrane that the present invention prepares are respectively 1.52GPa and 87.9GPa, and the purer PBO film of tensile strength and modulus has increased respectively 14% and 33%.The initial decomposition temperature (T5%) of Graphene/polyparaphenylene benzo-dioxazole composite membrane is 543.2 ℃, exceed 88.4 ℃ than the initial decomposition temperature of pure PBO film, illustrated that the composite membrane that the present invention prepares has better resistance toheat and mechanical property than PBO film.
The present invention is for the preparation of Graphene/polyparaphenylene benzo-dioxazole composite membrane.
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 a kind of Graphene/polyparaphenylene of present embodiment benzo-dioxazole composite membrane, specifically carries out according to following steps:
One, by the dense H of 200mL～1500mL
2sO
4dense H with 20mL～100mL
3pO
4mix, then add 1g～10g nano-graphite and 6g～50g KMnO
4then be to mix under 0～50 ℃ of condition in temperature, continue again to stir 12～48 hours, then cooling, then add 0.5L～5L distilled water, stir 0.5～2 hour, again 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, take the Vanadium Pentoxide in FLAKES of phosphoric acid that graphite oxide that 0.5～6 part of step 1 obtains, 202 parts of mass concentrations are 85%, 253 parts of Vanadium Pentoxide in FLAKESs, 100 parts of 4,6-diaminoresorcinol dihydrochlorides, 1～10 part of tindichloride, 78 parts of terephthalic acids and 183 parts according to mass fraction;
Three, the graphite oxide that step 2 is taken joins in phosphoric acid, ultrasonic dispersion 5～10h, point 253 parts of Vanadium Pentoxide in FLAKESs that add for 3～5 times step 2 to take under agitation condition again, then controlling temperature is 60 ℃～100 ℃, stir 1～5h, again under nitrogen atmosphere, add that step 2 takes 4, 6-diamino resorcin dihydrochloride and tindichloride, then controlling temperature is 60 ℃～100 ℃, stir 12～36 hours, be warming up to again 120 ℃, keep 8～24 hours, then be under 120 ℃ of conditions in temperature, the terephthalic acid that adds step 2 to take, and stir 4～8 hours, being warming up to temperature is 140 ℃～160 ℃ again, keep 3～5 hours, being warming up to temperature is 180 ℃～200 ℃ again, dividing adds for 3 times the Vanadium Pentoxide in FLAKES of 183 parts that step 2 takes to react, controlling the reaction times is 3～5 hours, obtain Graphene/PBO mixture,
Four, Graphene/PBO mixture step 3 being prepared into is poured on the super flat stainless steel plate with polytetrafluoroethylene film, then stainless steel plate is placed on thermocompressor, be arranged to shape parameter: 120 ℃～240 ℃ of temperature, pressure 5MPa～300MPa, film formation time 0.2～2h, after moulding, it is that 0～30% phosphoric acid solution soaks 8～48 hours that the film obtaining is put into mass concentration, then drying at room temperature, obtains Graphene/polyparaphenylene benzo-dioxazole composite membrane.
Embodiment two: present embodiment is different from embodiment one: dense H in step 1
2sO
4volume be .360mL, dense H
3pO
4volume be 40mL.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one: the volume that adds distilled water in step 1 is 0.8L～3L.Other is identical with embodiment one.
Embodiment four: present embodiment is different from one of embodiment one to three: the volume that adds distilled water in step 1 is 1L.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different from embodiment one: in step 1, the quality of nano-graphite is 3g.Other is identical with embodiment one.
Embodiment six: present embodiment is different from embodiment one: KMnO in step 1
4quality be 18g.Other is identical with embodiment one.
Embodiment seven: present embodiment is different from embodiment one: ultrasonic dispersion 8h in step 3.Other is identical with embodiment one.
Embodiment eight: present embodiment is different from embodiment one: be arranged to shape parameter in step 4: 180 ℃ of temperature, pressure 10MPa, film formation time 30min.Other is identical with embodiment one.
Embodiment nine: present embodiment is different from embodiment one: in step 4, the film obtaining is put into pure water and soaked 24 hours.Other is identical with embodiment one.
Embodiment ten: present embodiment is different from embodiment one: in step 4, the film obtaining is put into mass concentration and be 20% phosphoric acid solution and soak 24 hours.Other is identical with embodiment one.
Adopt following examples and contrast experiment to verify beneficial effect of the present invention:
Embodiment mono-:
The preparation method of a kind of Graphene/polyparaphenylene of the present embodiment benzo-dioxazole composite membrane, specifically carries out according to following steps:
One, by the dense H of 360mL
2sO
4dense H with 40mL
3pO
4mix, then add 3 nano-graphites and 18g KMnO
4then be to mix under 50 ℃ of conditions in temperature, continue again to stir 24 hours, then cooling, then add 1L distilled water, stir 1 hour, again 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, take the graphite oxide that 0.448g step 1 obtains, the phosphoric acid that 43g mass concentration is 85%, the Vanadium Pentoxide in FLAKES of 54g, the 4,6-diaminoresorcinol dihydrochloride of 21.31g, tindichloride, the terephthalic acid of 16.6g and the Vanadium Pentoxide in FLAKES of 39g of 0.5g;
Three, the graphite oxide that step 2 is taken joins in phosphoric acid, ultrasonic dispersion 8h, under agitation condition, point add again the Vanadium Pentoxide in FLAKES of the 54g that step 2 takes for 3 times, then controlling temperature is 80 ℃, stir 3, again under nitrogen atmosphere, add that step 2 takes 4, 6-diamino resorcin dihydrochloride and tindichloride, then controlling temperature is 80 ℃, stir 24 hours, be warming up to again 120 ℃, keep 24 hours, then be under 120 ℃ of conditions in temperature, the terephthalic acid that adds step 2 to take, and stir 6 hours, being warming up to temperature is 150 ℃ again, keep 4 hours, being warming up to temperature is 190 ℃ again, point add for 3 times the Vanadium Pentoxide in FLAKES of the 39g that step 2 takes to react, controlling the reaction times is 4 hours, obtain Graphene/PBO mixture,
Four, Graphene/PBO mixture step 3 being prepared into is poured on the super flat stainless steel plate with polytetrafluoroethylene film, then stainless steel plate is placed on thermocompressor, be arranged to shape parameter: 180 ℃ of temperature, pressure 10MPa, film formation time 30min, after moulding, the film obtaining is put into pure water to be soaked 24 hours, then drying at room temperature, obtains Graphene/polyparaphenylene benzo-dioxazole composite membrane.
Adopt standard GB/T/T1040.3-2006 to carry out tensile property test to the Graphene/polyparaphenylene benzo-dioxazole composite membrane making, adopt in thermogravimetric analyzer test Graphene/polyparaphenylene benzo-dioxazole composite membrane air atmosphere and carry out thermal weight loss, measure temperature range: room temperature～750 ℃; 10 ℃/10min of temperature rise rate, composite membrane consumption: 25mg.From test result, tensile strength and the modulus of the Graphene/polyparaphenylene benzo-dioxazole composite membrane being prepared by this experiment are respectively 1.52GPa and 87.9GPa, and the purer PBO film of tensile strength and modulus has increased respectively 14% and 33%.The initial decomposition temperature (T5%) of Graphene/polyparaphenylene benzo-dioxazole composite membrane is 543.2 ℃, exceeds 88.4 ℃ than the initial decomposition temperature of pure PBO film, has illustrated that composite membrane has better resistance toheat and mechanical property than PBO film.
Embodiment bis-:
The preparation method of a kind of Graphene/polyparaphenylene of the present embodiment benzo-dioxazole composite membrane, specifically carries out according to following steps:
One, by the dense H of 360mL
2sO
4dense H with 40mL
3pO
4mix, then add 3 nano-graphites and 18g KMnO
4then be to mix under 50 ℃ of conditions in temperature, continue again to stir 24 hours, then cooling, then add 1L distilled water, stir 1 hour, again 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, take the graphite oxide that 0.448g step 1 obtains, the phosphoric acid that 43g mass concentration is 85%, the Vanadium Pentoxide in FLAKES of 54g, the 4,6-diaminoresorcinol dihydrochloride of 21.31g, tindichloride, the terephthalic acid of 16.6g and the Vanadium Pentoxide in FLAKES of 39g of 0.5g;
Three, the graphite oxide that step 2 is taken joins in phosphoric acid, ultrasonic dispersion 8h, under agitation condition, point add again the Vanadium Pentoxide in FLAKES of the 54g that step 2 takes for 3 times, then controlling temperature is 80 ℃, stir 3, again under nitrogen atmosphere, add that step 2 takes 4, 6-diamino resorcin dihydrochloride and tindichloride, then controlling temperature is 80 ℃, stir 24 hours, be warming up to again 120 ℃, keep 24 hours, then be under 120 ℃ of conditions in temperature, the terephthalic acid that adds step 2 to take, and stir 6 hours, being warming up to temperature is 150 ℃ again, keep 4 hours, being warming up to temperature is 190 ℃ again, point add for 3 times the Vanadium Pentoxide in FLAKES of the 39g that step 2 takes to react, controlling the reaction times is 4 hours, obtain Graphene/PBO mixture,
Four, Graphene/PBO mixture step 3 being prepared into is poured on the super flat stainless steel plate with polytetrafluoroethylene film, then stainless steel plate is placed on thermocompressor, be arranged to shape parameter: 180 ℃ of temperature, pressure 10MPa, film formation time 30min, after moulding, it is that 20% phosphoric acid solution soaks 24 hours that the film obtaining is put into mass concentration, then drying at room temperature, obtains Graphene/polyparaphenylene benzo-dioxazole composite membrane.
Claims (10)
1. a preparation method for Graphene/polyparaphenylene benzo-dioxazole composite membrane, is characterized in that what this preparation method specifically carried out according to following steps:
One, by the dense H of 200mL～1500mL
2sO
4dense H with 20mL～100mL
3pO
4mix, then add 1g～10g nano-graphite and 6g～50g KMnO
4then be to mix under 0～50 ℃ of condition in temperature, continue again to stir 12～48 hours, then cooling, then add 0.5L～5L distilled water, stir 0.5～2 hour, again 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, take the Vanadium Pentoxide in FLAKES of graphite oxide that 0.5～6 part of step 1 obtains, phosphoric acid that 202 parts of mass concentrations are 85%, the Vanadium Pentoxide in FLAKES of 253 parts, 100 parts of 4,6-diaminoresorcinol dihydrochlorides, 1～10 part of tindichloride, 78 parts of terephthalic acids and 183 parts according to mass fraction;
Three, the graphite oxide that step 2 is taken joins in phosphoric acid, ultrasonic dispersion 5～10h, point Vanadium Pentoxide in FLAKES of 253 parts that adds for 3～5 times step 2 to take under agitation condition again, then controlling temperature is 60 ℃～100 ℃, stir 1～5h, again under nitrogen atmosphere, add that step 2 takes 4, 6-diamino resorcin dihydrochloride and tindichloride, then controlling temperature is 60 ℃～100 ℃, stir 12～36 hours, be warming up to again 120 ℃, keep 8～24 hours, then be under 120 ℃ of conditions in temperature, the terephthalic acid that adds step 2 to take, and stir 4～8 hours, being warming up to temperature is 140 ℃～160 ℃ again, keep 3～5 hours, being warming up to temperature is 180 ℃～200 ℃ again, dividing adds for 3 times the Vanadium Pentoxide in FLAKES of 183 parts that step 2 takes to react, controlling the reaction times is 3～5 hours, obtain Graphene/PBO mixture,
Four, Graphene/PBO mixture step 3 being prepared into is poured on the super flat stainless steel plate with polytetrafluoroethylene film, then stainless steel plate is placed on thermocompressor, be arranged to shape parameter: 120 ℃～240 ℃ of temperature, pressure 5MPa～300MPa, film formation time 0.2～2h, after moulding, it is that 0～30% phosphoric acid solution soaks 8～48 hours that the film obtaining is put into mass concentration, then drying at room temperature, obtains Graphene/polyparaphenylene benzo-dioxazole composite membrane.
2. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite membrane according to claim 1, is characterized in that dense H in step 1
2sO
4volume be .360mL, dense H
3pO
4volume be 40mL.
3. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite membrane according to claim 1, is characterized in that in step 1, adding the volume of distilled water is 0.8L～3L.
4. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite membrane according to claim 3, is characterized in that in step 1, adding the volume of distilled water is 1L.
5. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite membrane according to claim 1, the quality that it is characterized in that nano-graphite in step 1 is 3g.
6. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite membrane according to claim 1, is characterized in that KMnO in step 1
4quality be 18g.
7. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite membrane according to claim 1, is characterized in that ultrasonic dispersion 8h in step 3.
8. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite membrane according to claim 1, is characterized in that being arranged in step 4 shape parameter: 180 ℃ of temperature, pressure 10MPa, film formation time 30min.
9. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite membrane according to claim 1, is characterized in that in step 4, the film obtaining being put into pure water soaks 24 hours.
10. the preparation method of a kind of Graphene/polyparaphenylene benzo-dioxazole composite membrane according to claim 1, is characterized in that in step 4, the film obtaining being put into mass concentration and is 20% phosphoric acid solution and soak 24 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115926164A (en) * | 2023-01-31 | 2023-04-07 | 润华(江苏)新材料有限公司 | PBO polymerization liquid, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4876077A (en) * | 1985-05-30 | 1989-10-24 | Research Development Corp. Of Japan | Process for producing graphite |
| JPH04310569A (en) * | 1991-04-09 | 1992-11-02 | Matsushita Electric Ind Co Ltd | Production of graphite film |
| CN103013113A (en) * | 2012-12-12 | 2013-04-03 | 哈尔滨工业大学 | Preparation method of graphene/PBO polymer |
-
2014
- 2014-02-19 CN CN201410056446.6A patent/CN103788647A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4876077A (en) * | 1985-05-30 | 1989-10-24 | Research Development Corp. Of Japan | Process for producing graphite |
| JPH04310569A (en) * | 1991-04-09 | 1992-11-02 | Matsushita Electric Ind Co Ltd | Production of graphite film |
| CN103013113A (en) * | 2012-12-12 | 2013-04-03 | 哈尔滨工业大学 | Preparation method of graphene/PBO polymer |
Non-Patent Citations (3)
| Title |
|---|
| MARCANO D C, ET AL.: "Improved synthesis of graphene oxide", 《ACS NANO》 * |
| Y.W. LI,ET AL.: "Interfacial microstructure and properties of poly (phenylene benzobisoxazole) fiber grafted with graphene oxide via solvothermal method", 《APPLIED SURFACE SCIENCE》 * |
| YI CHEN, ET AL.: "Preparation of thermostable PBO/graphene nanocomposites with high dielectric constant", 《NANOTECHNOLOGY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115926164A (en) * | 2023-01-31 | 2023-04-07 | 润华(江苏)新材料有限公司 | PBO polymerization liquid, preparation method and application thereof |
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