CN106147130A - The preparation method of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite - Google Patents
The preparation method of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite Download PDFInfo
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Abstract
The invention belongs to technical field of nano material, be specifically related to the preparation method of a kind of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite.The present invention by Nano diamond and carbon fiber after surface carboxyl groups, chloride, diamine or polyamine is introduced again on it, modify the Nano diamond being connected to this amino with little molecule aromatic polyvalent anhydride compound, the Nano diamond of anhydride group is carried in preparation.Supersonic oscillations and high-speed stirred, Nano diamond is made to be scattered in epoxy resin-base, use the solidification of organic acid anhydride curing agent, be combined as matrix and carbon fiber using the epoxide resin polymer obtaining containing Nano diamond, form the multi-dimensional hybrid composite structure being connected with covalent bond.The present invention is prepared conveniently；Give the activity that Nano diamond participates in reaction, anhydride group on Nano diamond is chemically crosslinked with the epoxide group in epoxy resin, thus improve Nano diamond dispersion in the epoxy, utilize intensity and the toughness Strengthening and Toughening epoxy resin of Nano diamond, improve the adhesion strength with carbon fiber basal plane, thus improve the overall performance of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite, widen the application of carbon fiber, Nano diamond and epoxy resin.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to the preparation method of a kind of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite.
Background technology
Epoxy resin is a kind of thermoset oligomer, poor performance.In addition to the stabilizer as polyvinyl chloride, there is no direct use value.But after it and curing agent carry out curing reaction formation three-dimensional crosslinked network structure, then present a series of excellent performance.So, curing agent is the basis of epoxy resin application, core with the chemical reactivity of epoxy resin.Epoxy resin behavior in the curing process and Solidified enzyme depend greatly on and interact and reasonable coordination between the performance of curing agent and it and resin, and these depend on the molecular structure of curing agent.Therefore, study the application of epoxy resin ground and study the problem of solidification of epoxy resin to a certain extent exactly.
Recently as the development of nanometer material science, the especially discovery of carbon nanomaterial such as CNT and application, the gradually recognized and application as the novel carbon nanomaterial of another kind of nano level diamond.Due to Nano diamond have excellent biocompatibility, dimensionally stable ' property, electrical insulating property, high temperature resistant, high pressure and chemical stability, at present oneself is through being applied to a lot of aspect, such as the additive of lubricating oil or polymer composite, pharmaceutical carrier and cell marking.But it as in composite, owing to the surface of Nano diamond can be higher, is susceptible to reunite, makes it be difficult in the polymer dispersed.How dispersed Nano diamond strengthen combination between Nano diamond and matrix material interface, is the key improving composite properties.The excellent properties of carbon fibre composite has obtained extensively application in every profession and trade.The mechanical property modified epoxy that carbon fiber and Nano diamond are each excellent can be utilized, prepare carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite, it is anticipated that the prospect of carbon fiber/Nano diamond/epoxy resin hybrid composite will be boundless.
Content of the invention
It is an object of the invention to provide a kind of good dispersion, the preparation method of the firm carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite of interfacial adhesion.
The preparation method of carbon fiber/Nano diamond/epoxy resin multi-dimensional multi-dimensional hybrid composite that the present invention proposes, it is that Nano diamond surface is purified, carboxylated is carried out to the Nano diamond surface purifying, after chloride, introduce diamine or the polyamine with feature structure, obtain the graft type Nano diamond of the active amino in surface, modifying the Nano diamond being connected to this amino with little molecule aromatic polyvalent anhydride compound, the Nano diamond of anhydride group is carried in preparation again.Supersonic oscillations and high-speed stirred, Nano diamond is made to be scattered in epoxy resin-base, use the solidification of organic acid anhydride curing agent, it is combined by certain way using the epoxide resin polymer obtaining containing Nano diamond as matrix and carbon fiber, eventually form the multi-dimensional hybrid composite structure being connected with covalent bond, then carbon fiber and Nano diamond surface will be wound with substantial amounts of polymer.It specifically comprises the following steps that
(1) 1～1 × 10 are weighed2Nano diamond that g is dried and 10g～1 × 103G organic acid mixes, in 1～120kHz ultrasonic wave or 10r/min～106The lower process of centrifugal speed stirring of r/min 1～80 hour, is then heated to 20～180 DEG C, reacts 1～48 hour, and with microfiltration membranes suction filtration, cyclic washing, to neutral, is vacuum dried 1～48 hour at a temperature of 25～150 DEG C, obtains the Nano diamond purifying；
(2) by 1～1 × 102Carbon fiber, step that g is dried obtain purified nanotubes diamond 1～1 × 10 in (1)2G respectively with acid with strong oxidizing property 1～1 × 104ML mixes, process 1～80 hour under 1～120kHz ultrasonic wave, it is then heated to 25～120 DEG C, stirring simultaneously back flow reaction 1～80 hour, ultra porous membranes suction filtration, cyclic washing to solution is neutrality, is vacuum dried 1～48 hour, respectively obtains carbon fiber and the Nano diamond of acidifying at a temperature of 25～200 DEG C；
(3) by carbon fiber and the Nano diamond 1～1 × 10 of the acidifying of step (2) gained2G respectively with acylating reagent 1～1 × 104ML, after processing 0.1～10 hour with 1～120kHz ultrasonic wave, is heated to 25～220 DEG C, stirring simultaneously back flow reaction 0.5～100 hour, and suction filtration cyclic washing remove acylating reagent, respectively obtain carbon fiber and the Nano diamond of acylation；
(4) step (3) gained is acylated carbon fiber and Nano diamond 1～1 × 102G respectively with diamine or polyamine 10～1 × 104G, process 1～100 hour with 1～100kHz ultrasonic wave, then react 0.5～100 hour at a temperature of 25～200 DEG C, suction filtration cyclic washing, it is vacuum dried 1～48 hour at a temperature of 25～200 DEG C, respectively obtain surface with the graft type carbon fiber of active amino and Nano diamond；
(5) by step (4) gained surface with the carbon fiber of active amino and Nano diamond 1～1 × 102The aromatic anhydride compound of g low rate mixing dropping 1～100g in polar organic solvent ice bath, dropping is warming up to 100～150 DEG C and refluxes 3～12 hours after finishing, wash away unreacted aromatic anhydride compound with polar organic solvent, it is vacuum dried 3～12 hours at 40～80 DEG C, obtain the carbon fiber with activity anhydride group and Nano diamond；
(6) by step (5) gained surface with the Nano diamond 1～1 × 10 of activity anhydride group2G and epoxy resin 10～1 × 104G, be warming up to resin matrix melted after, dispersed with stirring uniformly and under vacuum bubble removing, carry out chemical crosslink reaction simultaneously, obtain the epoxide resin polymer containing Nano diamond；
(7) using the epoxide resin polymer 20g-25g containing Nano diamond obtained by step (6) as matrix and carbon fiber 20g-100g with mechanical mixture, at 60～100 DEG C, ultrasonic wave disperses 1～12 hour, add 40～50g organic acid anhydride curing agent, system cured above is poured in mould, bubble removing under vacuum condition, curing molding at 100～250 DEG C, obtain carbon fiber-containing/Nano diamond/epoxy resin multi-dimensional hybrid composite.
In the present invention, Nano diamond described in step (1) uses Detonation Process to obtain, including average grain diameter is 10 nanometers, 30 nanometers, 50 nanometers, 80 nanometers, any one in 100 nanometers.
In the present invention, organic acid described in step (1) be the nitric acid of 1～35% weight acid concentration, the sulfuric acid of 1～55% weight acid concentration or 1～50% weight acid concentration hydrochloric acid in any one or its mixed liquor.
In the present invention, acid with strong oxidizing property described in step (2) is 0.1～70% weight acid concentration nitric acid, 1～100% weight acid concentration sulfuric acid, 1/100～100/1 mol ratio potassium permanganate and sulfuric acid mixed solution, 1/100～100/1 mol ratio nitric acid and sulfuric acid mixed solution, 1/100～100/1 mol ratio potassium permanganate and nitric acid mixed solution, 1/100～100/1 mol ratio hydrogen peroxide and sulfuric acid mixture liquid, 1/100～100/1 mol ratio hydrogen peroxide and hydrochloric acid mixed solution, in 1/100～100/1 mol ratio hydrogen peroxide and nitric acid mixed liquor or 15～95% weight concentration hydrogenperoxide steam generators any one.
In the present invention, acylating reagent described in step (3) is any one in thionyl chloride, phosphorus trichloride or phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide or thionyl bromide.
In the present invention, diamine described in step (4) be ethylenediamine, polyethyene diamine, 1,2-propane diamine, 1,3-propane diamine, 1,2-butanediamine, 1, in 3-butanediamine, hexamethylene diamine, p-phenylenediamine, m-phenylene diamine (MPD), m-xylene diamine, diaminodiphenyl-methane, alkane diamines in the Meng, divinyl propylamine, diaminodiphenyl-methane, chlorination hexamethylene diamine, chlorination nonamethylene diamine, chlorination decamethylene diamine, 12 carbon diamines or 13 carbon diamines any one；Described polyamine is fourth triamine, N-aminoethyl piperazine, dicyandiamide, adipic dihydrazide, N, in N-dimethyl dipropyl triamine, TEPA, diethylenetriamine, triethylene tetramine, TEPA, five hexamine or six ethene seven amine any one.
In the present invention, the Nano diamond of acidifying in step (2) and the quantitative analysis of carboxyl-content in carbon fiber, TGA, XPS or nuclear magnetic resonance method can be used.
In the present invention, the surface that obtains described in step (4) is with the graft type Nano diamond of active amino and carbon fiber, and its amino is diamine or polyamine.
In the present invention, the surface that obtains described in step (5) is with the graft type Nano diamond of activity anhydride group and carbon fiber, and its anhydride group is aromatic anhydride compound.Described aromatic anhydride compound includes the addition product of the addition product of pyromellitic acid anhydride PDMA, pyromellitic acid anhydride and caprolactone, Benzophenone acid dianhydride, Benzophenone acid dianhydride and caprolactone, diphenyl sulfone-3,3 ', 4,4 '-tetracarboxylic dianhydride DSDA, diphenyl sulfone-3,3 ', 4, the addition product of 4 '-tetracarboxylic dianhydride, N, one or more in N '-dicarboxylic anhydride diphenyl methane, mellitic acid three acid anhydride.
In the present invention, the polar organic solvent described in step (5) includes ethanol, methyl alcohol, dimethyl sulfoxide (DMSO), oxolane, acetone or N, one or more mixtures of N '-dimethyl formamide.
In the present invention, the epoxy resin described in step (6) refer to glycidol ethers, glycidol lipid, glycidol amine, alicyclic ring class, epoxidation of olefins class, imide ring epoxy resins or glycolylurea epoxide resin in interior all epoxy resin any one.
In the present invention, obtain described in step (6) containing the linear block polymer of Nano diamond, be the Nano diamond linear block polymer of the block polymer being connected to epoxy resin on the Nano diamond of acid anhydrides.
In the present invention, organic acid anhydride curing agent described in step (7) includes organic acid anhydride type curing agent, such as one or several mixture in phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, adjacent PMDA, phthalic anhydride tetracarboxylic dianhydride, methylcyclohexene tetracarboxylic dianhydride, oxydiphthalic, trimellitic anhydride, poly-azelaic acid acid anhydride.
In the present invention, carbon fiber described in step (7) is any one in unidirectional long fibre cloth, two-way woven cloth, three-phase woven cloth or random chopped fiber.
The preparation method that the present invention provides is simple, and gained is the carbon fiber multi-dimensional hybrid compound that surface is connected to Epoxy/nano diamond.The anhydride group on Nano diamond surface is by producing chemical crosslink reaction with epoxy resin, Nano diamond is made to become a part for epoxy-resin systems, again by being combined in a certain way with the carbon fiber of surface acid anhydridization, froth in vacuum, obtains carbon fiber-containing/Nano diamond/epoxy resin multi-dimensional hybrid composite.Due to the effect of Nano diamond modified epoxy, add the boundary strength between matrix resin and carbon fiber, make composite have good interlaminar shear strength.
The present invention is to have the anhydride group of feature structure at Nano diamond and carbon fiber surface introducing, this structure and epoxy resin is utilized to carry out chemical crosslink reaction, then Nano diamond and carbon fiber surface will be wound with substantial amounts of polymer, owing to polymer has the characteristic of affinity and Nano diamond itself to matrix resin, thus the shortcoming improving the interlaminar shear strength deficiency etc. of carbon fiber, this multi-dimensional hybrid compound has multiple performances such as interfacial adhesion is firm, strength and toughness is good, easy solidification, makes the comprehensive mechanical property of composite be improved significantly.Therefore, the present invention has important science and technology value and actual application value.
Detailed description of the invention
The following examples are to further illustrate the present invention, rather than limit the scope of the present invention.
Embodiment 1: with Nano diamond that average grain diameter prepared by Detonation Process is 10 nanometers and carbon fiber as initial raw material, Nano diamond is through purifying, respectively Nano diamond and carbon fiber are acidified, chloride, after amination, again with after pyromellitic acid anhydride acid anhydrides, Nano diamond and liquid bisphenol A type epoxy resin (E-51) are carried out chemical crosslink reaction, then must arrive surface and be connected to the Nano diamond of liquid bisphenol A type epoxy resin, again it is combined in a certain way with the carbon fiber of pyromellitic acid anhydride acid anhydrides, obtain carbon fiber-containing/Nano diamond/epoxy resin multi-dimensional hybrid composite.
Step (1): in the mono-neck round-bottom flask of the 250mL having been loaded with agitator, add Nano diamond raw material and 100mL, 20% salpeter solution of 1.1g drying, process 10 hours under 120kHz ultrasonic wave, it is then heated to 20 DEG C, react 48 hours, gather inclined tetrafluoroethene microfiltration membranes suction filtration with ψ 0.8 μm, be washed with deionized 3-10 time to neutrality, after being vacuum dried 24 hours at 25 DEG C, obtain the Nano diamond purifying；
Step (2): in two mono-neck round-bottom flasks of 250mL having been loaded with agitator, one of them enters Nano diamond raw material 1g and 100mL of the purifying obtaining in step (1), 60% weight concentration red fuming nitric acid (RFNA), another adds carbon fiber 20g and 100mL of drying, 60% weight concentration red fuming nitric acid (RFNA), two flasks are through following the same terms process: add and be heated to 25 DEG C after processing 1 hour through 60kHz ultrasonic wave, stir and reflux down and react 24 hours, gather inclined tetrafluoroethene milipore filter suction filtration with ψ 1.2 μm, with deionized water cyclic washing 3-10 time to neutral, after 80 DEG C are vacuum dried 48 hours, respectively obtain Carboxylation Nano diamond and carbon fiber；
Step (3): in two 250mL three neck round bottoms having been loaded with agitator, one of them adds the Nano diamond 1g and thionyl chloride 10g of step (2) gained acidifying, another adds the carbon fiber 20g and thionyl chloride 100g of acidifying, two flasks are through following the same terms process: after processing 1 hour with 100Hz ultrasonic wave, it is heated to 80 DEG C, stir and reflux down and react 100 hours, suction filtration cyclic washing remove thionyl chloride, respectively obtain Nano diamond and the carbon fiber of chloride；
Step (4): in two 250mL three neck round bottoms having been loaded with agitator, one of them addition step (3) gained acylated Nano diamond 1g and 12 carbon diamine 10g, another adds acylated carbon fiber 20g and 12 carbon diamine 100g, two flasks are through following the same terms process: after processing 1 hour with 100kHz ultrasonic wave, stirring reaction 0.5 hour at 200 DEG C, suction filtration removes unreacted reactant and byproduct of reaction, after being repeatedly washed with deionized 3-10 time, 80 DEG C are vacuum dried 48 hours, respectively obtain surface with the Nano diamond of amino and carbon fiber；
Step (5): in two 250mL three neck round bottoms having been loaded with agitator; one of them adds the Nano diamond 1g of step (4) gained ammonification to be dissolved in dimethyl sulfoxide (DMSO); another adds the carbon fiber 20g of ammonification to be dissolved in dimethyl sulfoxide (DMSO); two flasks are through following the same terms process: ultrasonic vibration 30min; add 10g pyromellitic acid anhydride; add catalyst concentrated sulfuric acid 10ml; stir at 90 DEG C; nitrogen is protected; magnetic agitation; reaction time is 48 hours, respectively obtains carbon fiber and the Nano diamond that anhydride group is contained on surface.
Step (6): in the 250mL three neck round bottom having been loaded with agitator, add the Nano diamond 1g and liquid bisphenol A type epoxy resin (E-51) 20g of step (5) acid anhydrides, heat and stir, after processing 2 hours with 60kHz ultrasonic wave, react 12 hours at 240 DEG C, surface must be arrived and be connected to the Nano diamond of liquid bisphenol A type epoxy resin (E-51)；
Step (7): take surface and be connected to the Nano diamond compound 20g of liquid bisphenol A type epoxy resin (E-51) and the carbon fiber 20g of step (5) acid anhydrides with compound at 150 DEG C, de-bubble under vacuum, compression molding under 10MPa obtains carbon fiber-containing/Nano diamond/epoxy resin multi-dimensional hybrid composite.
Can show that Nano diamond surface-bound carboxylic content is 7.0% (mol ratio with carbon) from XPS data.Therefore after can calculating process, Nano diamond surface amino groups content is 7.0%.
Embodiment 2: with Nano diamond that average grain diameter prepared by Detonation Process is 30 nanometers as initial raw material, Nano diamond is through purifying, respectively Nano diamond and carbon fiber are acidified, chloride, amination, again with after Benzophenone acid dianhydride acid anhydrides, Nano diamond and liquid bisphenol A type epoxy resin (E-54) are carried out chemical crosslink reaction, then must arrive surface and be connected to the Nano diamond of liquid bisphenol A type epoxy resin (E-54), again it is combined in a certain way with the carbon fiber of Benzophenone acid dianhydride acid anhydrides, obtain carbon fiber-containing/Nano diamond/epoxy resin multi-dimensional hybrid composite
Step (1): in the mono-neck round-bottom flask of the 500mL having been loaded with agitator, add the Nano diamond raw material of 1.1g drying and the sulfuric acid of 100mL, 20% weight concentration, process 12 hours under 120kHz ultrasonic wave, it is then heated to 180 DEG C, react 48 hours, gather inclined tetrafluoroethene microfiltration membranes suction filtration with ψ 0.8 μm, be washed with deionized 3-10 time to neutrality, after being vacuum dried 24 hours at 100 DEG C, obtain the Nano diamond purifying；
Step (2): in two mono-neck round-bottom flasks of 500mL having been loaded with agitator, one of them enters Nano diamond raw material 1g and 200mL of the purifying obtaining in step (1), 98% concentrated sulfuric acid solution, another adds carbon fiber 100g and 200mL of drying, 98% concentrated sulfuric acid solution, two flasks are through following the same terms process: add and be heated to 80 DEG C after processing 2 hours through 70kHz ultrasonic wave, stir and reflux down and react 80 hours, gather inclined tetrafluoroethene milipore filter suction filtration with ψ 1.2 μm, with deionized water cyclic washing 3-10 time to neutral, after 100 DEG C are vacuum dried 24 hours, respectively obtain Carboxylation Nano diamond and carbon fiber；
Step (3): in two 500mL three neck round bottoms having been loaded with agitator, one of them adds the Nano diamond 1g and trichlorine sulfoxide 10g of step (2) gained acidifying, another adds the carbon fiber 100g and three torak 200g of acidifying, two flasks are through following the same terms process: after processing 10 hours with 120Hz ultrasonic wave, it is heated to 25 DEG C, stir and reflux down and react 48 hours, suction filtration cyclic washing remove three toraks, respectively obtain Nano diamond and the carbon fiber of chloride；
Step (4): in two 500mL three neck round bottoms having been loaded with agitator, one of them addition step (3) gained acylated Nano diamond 1g and 12 carbon diamine 10g, another adds acylated carbon fiber 20g and 12 carbon diamine 100g, two flasks are through following the same terms process: after processing 1 hour with 100kHz ultrasonic wave, stirring reaction 0.5 hour at 200 DEG C, suction filtration removes unreacted reactant and byproduct of reaction, after being repeatedly washed with deionized 3-10 time, 80 DEG C are vacuum dried 48 hours, respectively obtain surface with the Nano diamond of amino and carbon fiber；
Step (5): in two 500mL three neck round bottoms having been loaded with agitator; one of them adds the Nano diamond 1g of step (4) gained ammonification to be dissolved in dimethyl sulfoxide (DMSO); another adds the carbon fiber 20g of ammonification to be dissolved in dimethyl sulfoxide (DMSO); two flasks are through following the same terms process: ultrasonic vibration 30min; add the acid of 10g Benzophenone acid dianhydride; add catalyst concentrated sulfuric acid 10ml; stir at 90 DEG C; nitrogen is protected; magnetic agitation; reaction time is 48 hours, respectively obtains carbon fiber and the Nano diamond that anhydride group is contained on surface.
Step (6): in the 500mL three neck round bottom having been loaded with agitator, add the Nano diamond 1g and liquid bisphenol A type epoxy resin (E-54) 20g of step (5) acid anhydrides, heat and stir, after processing 2 hours with 60kHz ultrasonic wave, react 12 hours at 240 DEG C, surface must be arrived and be connected to the Nano diamond of liquid bisphenol A type epoxy resin (E-54)；
Step (7): the carbon fiber 20g taking the Nano diamond compound 20g and step (5) acid anhydrides that surface is connected to liquid bisphenol A type epoxy resin (E-54) is combined at 100 DEG C, de-bubble under vacuum, compression molding under 8MPa obtains carbon fiber-containing/Nano diamond/epoxy resin multi-dimensional hybrid composite.
XPS result shows that carbon fiber and Nano diamond impurity surface anhydride content are 6.5%.
Embodiment 3: with Nano diamond that average grain diameter prepared by Detonation Process is 50 nanometers as initial raw material, Nano diamond is through purifying, respectively by acidified to carbon fiber and Nano diamond, chloride, after amination, use N again, after N '-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydride, Nano diamond and liquid bisphenol A type epoxy resin (E-44) are carried out chemical crosslink reaction, then must arrive surface and be connected to the Nano diamond of liquid bisphenol A type epoxy resin (E-44), again by itself and N, the carbon fiber of N '-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydride is combined in a certain way, obtain carbon fiber-containing/Nano diamond/epoxy resin multi-dimensional hybrid composite.
Step (1): in the mono-neck round-bottom flask of the 500mL having been loaded with agitator, add the Nano diamond raw material of 10g drying and the sulfuric acid of 250mL, 20% weight concentration, process 80 hours under 120kHz ultrasonic wave, then heat and stir at 180 DEG C and reflux, react 48 hours, gather inclined tetrafluoroethene microfiltration membranes suction filtration with ψ 0.8 μm, be washed with deionized 3-10 time to neutrality, after being vacuum dried 24 hours at 100 DEG C, obtain the Nano diamond purifying；
Step (2): in two mono-neck round-bottom flasks of 500mL having been loaded with agitator, one of them enters Nano diamond raw material 9.8g and 250mL of the purifying obtaining in step (1), volume ratio is red fuming nitric acid (RFNA) and the concentrated sulfuric acid mixed liquor of 2: 1, another adds carbon fiber 100g and 250mL of drying, volume ratio is red fuming nitric acid (RFNA) and the concentrated sulfuric acid mixed liquor of 2: 1, two flasks are through following the same terms process: be heated to 25 DEG C after processing 80 hours with 120kHz ultrasonic wave, stir and reflux down and react 80 hours, gather inclined tetrafluoroethene milipore filter suction filtration with ψ 1.2 μm, with deionized water cyclic washing to neutrality, after 25 DEG C are vacuum dried 48 hours, respectively obtain Carboxylation Nano diamond and carbon fiber；
Step (3): at two equipped with in the 500mL three neck round bottom of magnetic agitation rotor, one of them adds the Nano diamond 9.8g and phosphorus pentachloride 100g of step (2) gained acidifying, another adds the carbon fiber 100g and phosphorus pentachloride 200g of acidifying, two flasks are through following the same terms process: after processing 1 hour with 120Hz ultrasonic wave, it is heated to 25 DEG C, stir and reflux down and react 100 hours, suction filtration cyclic washing, except repeatedly removing phosphorus pentachloride, respectively obtain Nano diamond and the carbon fiber of chloride；
Step (4): at two equipped with in the 500mL three neck round bottom of magnetic agitation rotor, one of them adds step (3) gained to be acylated Nano diamond 9.8g and TEPA 50g, another adds the carbon fiber 100g and TEPA 200g of chloride, two flasks are through following the same terms process: after processing 1 hour with 100kHz ultrasonic wave, two flasks react 24 hours at 25 DEG C, suction filtration removes unreacted reactant and byproduct of reaction, after being repeatedly washed with deionized repeatedly, 200 DEG C are vacuum dried 1 hour, respectively obtain surface with the Nano diamond of amino and carbon fiber；
Step (5): in two 500mL three neck round bottoms having been loaded with agitator, one of them adds the Nano diamond 9.8g of step (4) gained ammonification to be dissolved in dimethyl sulfoxide (DMSO), another adds the carbon fiber 100g of ammonification to be dissolved in dimethyl sulfoxide (DMSO), two flasks are through following the same terms process: ultrasonic vibration 30min, add 100gN, N '-dicarboxylic anhydride diphenyl methane, add catalyst concentrated sulfuric acid 10ml, stir at 90 DEG C, nitrogen is protected, magnetic agitation, reaction time is 48 hours, respectively obtain carbon fiber and the Nano diamond that anhydride group is contained on surface.
Step (6): in the 500mL three neck round bottom having been loaded with agitator, add the Nano diamond 9.8g and liquid bisphenol A type epoxy resin (E-44) 100g of step (5) acid anhydrides, heat and stir, after processing 2 hours with 80kHz ultrasonic wave, react 12 hours at 240 DEG C, surface must be arrived and be connected to the Nano diamond of liquid bisphenol A type epoxy resin (E-44)；
Step (7): the carbon fiber 100g taking the Nano diamond compound 25g and step (5) acid anhydrides that surface is connected to liquid bisphenol A type epoxy resin (E-44) is combined at 100 DEG C, de-bubble under vacuum, compression molding under 13MPa obtains carbon fiber-containing/Nano diamond/epoxy resin multi-dimensional hybrid composite.
XPS analysis result shows that carbon fiber and Nano diamond impurity surface anhydride content are 8.0%.
Embodiment 4: with Nano diamond that average grain diameter prepared by Detonation Process is 80 nanometers as initial raw material, Nano diamond is through purifying, respectively by acidified to carbon fiber and Nano diamond, chloride, after amination, use N again, after N '-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydride, Nano diamond and liquid bisphenol A type epoxy resin (E-44) are carried out chemical crosslink reaction, then must arrive surface and be connected to the Nano diamond of liquid bisphenol A type epoxy resin (E-44), again by itself and N, the carbon fiber of N '-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydride is combined in a certain way, obtain carbon fiber-containing/Nano diamond/epoxy resin multi-dimensional hybrid composite.
Step (1): in the mono-neck round-bottom flask of the 500mL having been loaded with agitator, add the Nano diamond raw material of 10g drying and the sulfuric acid of 250mL, 20% weight concentration, process 40 hours under 60kHz ultrasonic wave, then heat and stir at 180 DEG C and reflux, react 48 hours, gather inclined tetrafluoroethene microfiltration membranes suction filtration with ψ 0.8 μm, be washed with deionized 3-10 time to neutrality, after being vacuum dried 24 hours at 100 DEG C, obtain the Nano diamond purifying；
Step (2): in two mono-neck round-bottom flasks of 500mL having been loaded with agitator, one of them enters Nano diamond raw material 9.8g and 250mL of the purifying obtaining in step (1), volume ratio is red fuming nitric acid (RFNA) and the concentrated sulfuric acid mixed liquor of 2: 1, another adds carbon fiber 100g and 250mL of drying, volume ratio is red fuming nitric acid (RFNA) and the concentrated sulfuric acid mixed liquor of 2: 1, two flasks are through following the same terms process: be heated to 25 DEG C after processing 40 hours with 60kHz ultrasonic wave, stir and reflux down and react 80 hours, gather inclined tetrafluoroethene milipore filter suction filtration with ψ 1.2 μm, with deionized water cyclic washing to neutrality, after 25 DEG C are vacuum dried 48 hours, respectively obtain Carboxylation Nano diamond and carbon fiber；
Step (3): at two equipped with in the 500mL three neck round bottom of magnetic agitation rotor, one of them adds the Nano diamond 9.8g and phosphorus pentachloride 100g of step (2) gained acidifying, another adds the carbon fiber 100g and phosphorus pentachloride 200g of acidifying, two flasks are through following the same terms process: after processing 1 hour with 60Hz ultrasonic wave, it is heated to 25 DEG C, stir and reflux down and react 100 hours, suction filtration cyclic washing, except repeatedly removing phosphorus pentachloride, respectively obtain Nano diamond and the carbon fiber of chloride；
Step (4): at two equipped with in the 500mL three neck round bottom of magnetic agitation rotor, one of them adds step (3) gained to be acylated Nano diamond 9.8g and TEPA 50g, another adds the carbon fiber 100g and TEPA 200g of chloride, two flasks are through following the same terms process: after processing 1 hour with 100kHz ultrasonic wave, two flasks react 24 hours at 25 DEG C, suction filtration removes unreacted reactant and byproduct of reaction, after being repeatedly washed with deionized repeatedly, 200 DEG C are vacuum dried 1 hour, respectively obtain surface with the Nano diamond of amino and carbon fiber；
Step (5): in two 500mL three neck round bottoms having been loaded with agitator, one of them adds the Nano diamond 9.8g of step (4) gained ammonification to be dissolved in dimethyl sulfoxide (DMSO), another adds the carbon fiber 100g of ammonification to be dissolved in dimethyl sulfoxide (DMSO), two flasks are through following the same terms process: ultrasonic vibration 30min, add 100gN, N '-dicarboxylic anhydride diphenyl methane, add catalyst concentrated sulfuric acid 10ml, stir at 90 DEG C, nitrogen is protected, magnetic agitation, reaction time is 48 hours, respectively obtain carbon fiber and the Nano diamond that anhydride group is contained on surface.
Step (6): in the 500mL three neck round bottom having been loaded with agitator, add the Nano diamond 9.8g and liquid bisphenol A type epoxy resin (E-44) 100g of step (5) acid anhydrides, heat and stir, after processing 2 hours with 80kHz ultrasonic wave, react 12 hours at 240 DEG C, surface must be arrived and be connected to the Nano diamond of liquid bisphenol A type epoxy resin (E-44)；
Step (7): the carbon fiber 100g taking the Nano diamond compound 25g and step (5) acid anhydrides that surface is connected to liquid bisphenol A type epoxy resin (E-44) is combined at 100 DEG C, de-bubble under vacuum, compression molding under 13MPa obtains carbon fiber-containing/Nano diamond/epoxy resin multi-dimensional hybrid composite.
XPS result shows that carbon fiber and Nano diamond impurity surface anhydride content are 7.4%.
Embodiment 5: with Nano diamond that average grain diameter prepared by Detonation Process is 100 nanometers as initial raw material, Nano diamond is through purifying, respectively by acidified to carbon fiber and Nano diamond, chloride, after amination, use N again, after N '-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydride, Nano diamond and liquid bisphenol A type epoxy resin (E-51) are carried out chemical crosslink reaction, then must arrive surface and be connected to the Nano diamond of liquid bisphenol A type epoxy resin (E-51), again by itself and N, the carbon fiber of N '-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydride is combined in a certain way, obtain carbon fiber-containing/Nano diamond/epoxy resin multi-dimensional hybrid composite.
Step (1): in the mono-neck round-bottom flask of the 500mL having been loaded with agitator, add the Nano diamond raw material of 10g drying and the sulfuric acid of 250mL, 20% weight concentration, process 60 hours under 90kHz ultrasonic wave, then heat and stir at 180 DEG C and reflux, react 48 hours, gather inclined tetrafluoroethene microfiltration membranes suction filtration with ψ 0.8 μm, be washed with deionized 3-10 time to neutrality, after being vacuum dried 24 hours at 100 DEG C, obtain the Nano diamond purifying；
Step (2): in two mono-neck round-bottom flasks of 500mL having been loaded with agitator, one of them enters Nano diamond raw material 9.8g and 250mL of the purifying obtaining in step (1), volume ratio is red fuming nitric acid (RFNA) and the concentrated sulfuric acid mixed liquor of 2: 1, another adds carbon fiber 100g and 250mL of drying, volume ratio is red fuming nitric acid (RFNA) and the concentrated sulfuric acid mixed liquor of 2: 1, two flasks are through following the same terms process: be heated to 25 DEG C after processing 80 hours with 120kHz ultrasonic wave, stir and reflux down and react 80 hours, gather inclined tetrafluoroethene milipore filter suction filtration with ψ 1.2 μm, with deionized water cyclic washing to neutrality, after 25 DEG C are vacuum dried 48 hours, respectively obtain Carboxylation Nano diamond and carbon fiber；
Step (3): at two equipped with in the 500mL three neck round bottom of magnetic agitation rotor, one of them adds the Nano diamond 9.8g and phosphorus pentachloride 100g of step (2) gained acidifying, another adds the carbon fiber 100g and phosphorus pentachloride 200g of acidifying, two flasks are through following the same terms process: after processing 1 hour with 120Hz ultrasonic wave, it is heated to 25 DEG C, stir and reflux down and react 100 hours, suction filtration cyclic washing, except repeatedly removing phosphorus pentachloride, respectively obtain Nano diamond and the carbon fiber of chloride；
Step (4): at two equipped with in the 500mL three neck round bottom of magnetic agitation rotor, one of them adds step (3) gained to be acylated Nano diamond 9.8g and TEPA 50g, another adds the carbon fiber 100g and TEPA 200g of chloride, two flasks are through following the same terms process: after processing 5 hours with 60kHz ultrasonic wave, two flasks react 24 hours at 25 DEG C, suction filtration removes unreacted reactant and byproduct of reaction, after being repeatedly washed with deionized repeatedly, 200 DEG C are vacuum dried 1 hour, respectively obtain surface with the Nano diamond of amino and carbon fiber；
Step (5): in two 500mL three neck round bottoms having been loaded with agitator, one of them adds the Nano diamond 9.8g of step (4) gained ammonification to be dissolved in dimethyl sulfoxide (DMSO), another adds the carbon fiber 100g of ammonification to be dissolved in dimethyl sulfoxide (DMSO), two flasks are through following the same terms process: ultrasonic vibration 30min, add 100gN, N '-dicarboxylic anhydride diphenyl methane, add catalyst concentrated sulfuric acid 10ml, stir at 90 DEG C, nitrogen is protected, magnetic agitation, reaction time is 48 hours, respectively obtain carbon fiber and the Nano diamond that anhydride group is contained on surface.
Step (6): in the 500mL three neck round bottom having been loaded with agitator, add the Nano diamond 9.8g and liquid bisphenol A type epoxy resin (E-51) 100g of step (5) acid anhydrides, heat and stir, after processing 2 hours with 80kHz ultrasonic wave, react 12 hours at 240 DEG C, surface must be arrived and be connected to the Nano diamond of liquid bisphenol A type epoxy resin (E-51)；
Step (7): the carbon fiber 100g taking the Nano diamond compound 25g and step (5) acid anhydrides that surface is connected to liquid bisphenol A type epoxy resin (E-51) is combined at 100 DEG C, de-bubble under vacuum, compression molding under 13MPa obtains carbon fiber-containing/Nano diamond/epoxy resin multi-dimensional hybrid composite.
XPS result shows that carbon fiber and Nano diamond impurity surface anhydride content are 8.3%.
The above-mentioned description to embodiment is to understand for the ease of those skilled in the art and application benzene invention.These embodiments obviously easily can be made various modification by person skilled in the art, and General Principle described herein is applied in other embodiments without through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art are according to the announcement of the present invention, and the improvement making the present invention and modification all should be within protection scope of the present invention.
Claims (11)
1. the preparation method of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite, it is characterised in that specifically comprise the following steps that
(1) 1～1 × 10 are weighed2Nano diamond that g is dried and 10g～1 × 103G organic acid mixes, in 1～120kHz ultrasonic wave or 10r/min～106The lower process of centrifugal speed stirring of r/min 1～80 hour, is then heated to 20～180 DEG C, reacts 1～48 hour, and with microfiltration membranes suction filtration, cyclic washing, to neutral, is vacuum dried 1～48 hour at a temperature of 25～150 DEG C, obtains the Nano diamond purifying；
(2) by 1～1 × 102Carbon fiber, step that g is dried obtain purified nanotubes diamond 1～1 × 10 in (1)2G respectively with acid with strong oxidizing property 1～1 × 104ML mixes, process 1～80 hour under 1～120kHz ultrasonic wave, it is then heated to 25～120 DEG C, stirring simultaneously back flow reaction 1～80 hour, ultra porous membranes suction filtration, cyclic washing to solution is neutrality, is vacuum dried 1～48 hour, respectively obtains carbon fiber and the Nano diamond of acidifying at a temperature of 25～200 DEG C；
(3) by carbon fiber and the Nano diamond 1～1 × 10 of the acidifying of step (2) gained2G respectively with acylating reagent 10～1 × 104G, after processing 0.1～10 hour with 1～120kHz ultrasonic wave, is heated to 25～220 DEG C, stirring simultaneously back flow reaction 0.5～100 hour, and suction filtration cyclic washing remove acylating reagent, respectively obtain carbon fiber and the Nano diamond of acylation；
(4) step (3) gained is acylated carbon fiber and Nano diamond 1～1 × 102G respectively with diamine or polyamine 10～1 × 104G, process 1～100 hour with 1～100kHz ultrasonic wave, then react 0.5～100 hour at a temperature of 25～200 DEG C, suction filtration cyclic washing, it is vacuum dried 1～48 hour at a temperature of 25～200 DEG C, respectively obtain surface with the graft type carbon fiber of active amino and Nano diamond；
(5) by step (4) gained surface with the carbon fiber of active amino and Nano diamond 1～1 × 102The aromatic anhydride compound of g agitation and dropping 1～100g in polar organic solvent ice bath, dropping is warming up to 100～150 DEG C and refluxes 3～12 hours after finishing, wash away unreacted aromatic anhydride compound with polar organic solvent, it is vacuum dried 3～12 hours at 40～80 DEG C, obtain the carbon fiber with activity anhydride group and Nano diamond；
(6) by step (5) gained surface with the Nano diamond 1～1 × 10 of activity anhydride group2G and epoxy resin 10～1 × 104G, be warming up to resin matrix melted after, dispersed with stirring uniformly and under vacuum bubble removing, carry out chemical crosslink reaction simultaneously, obtain the epoxide resin polymer containing Nano diamond；
(7) the epoxide resin polymer 20g-25g of Nano diamond will be contained as matrix and carbon fiber 20g-100g mechanical mixture obtained by step (6), at 60～100 DEG C, ultrasonic wave disperses 1～12 hour, add 40～50g organic acid anhydride curing agent, system cured above is poured in mould, bubble removing under vacuum condition, curing molding at 100～250 DEG C, obtain carbon fiber-containing/Nano diamond/epoxy resin multi-dimensional hybrid composite.
2. the preparation method of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1, it is characterized in that Nano diamond described in step (1) uses Detonation Process to obtain, including average grain diameter is 10 nanometers, 30 nanometers, 50 nanometers, 80 nanometers, any one in 100 nanometers.
3. the preparation method of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1, it is characterised in that organic acid described in step (1) be the nitric acid of 1～35% weight acid concentration, the sulfuric acid of 1～55% weight acid concentration or 1～50% weight acid concentration hydrochloric acid in any one or its mixed liquor.
null4. the preparation method of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1，It is characterized in that acid with strong oxidizing property described in step (2) is 0.1～70% weight acid concentration nitric acid、1～100% weight acid concentration sulfuric acid、1/100～100/1 mol ratio potassium permanganate and sulfuric acid mixed solution、1/100～100/1 mol ratio nitric acid and sulfuric acid mixed solution、1/100～100/1 mol ratio potassium permanganate and nitric acid mixed solution、1/100～100/1 mol ratio hydrogen peroxide and sulfuric acid mixture liquid、1/100～100/1 mol ratio hydrogen peroxide and hydrochloric acid mixed solution、In 1/100～100/1 mol ratio hydrogen peroxide and nitric acid mixed liquor or 15～95% weight concentration hydrogenperoxide steam generators any one.
5. the preparation method of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1, it is characterised in that acylating reagent described in step (3) is any one in thionyl chloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide or thionyl bromide.
6. the preparation method of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1, it is characterized in that described in step (4), diamine is ethylenediamine, polyethyene diamine, 1, 2-propane diamine, 1, 3-propane diamine, 1, 2-butanediamine, 1, 3-butanediamine, hexamethylene diamine, p-phenylenediamine, m-phenylene diamine (MPD), m-xylene diamine, diaminodiphenyl-methane, the Meng alkane diamines, divinyl propylamine, diaminodiphenyl-methane, chlorination hexamethylene diamine, chlorination nonamethylene diamine, chlorination decamethylene diamine, in 12 carbon diamines or 13 carbon diamines any one；Described polyamine is fourth triamine, N-aminoethyl piperazine, dicyandiamide, adipic dihydrazide, N, in N-dimethyl dipropyl triamine, TEPA, diethylenetriamine, triethylene tetramine, TEPA, five hexamine or six ethene seven amine any one.
7. the preparation method of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1, it is characterized in that aromatic anhydride compound described in step (5) includes the addition product of the addition product of pyromellitic acid anhydride PDMA, pyromellitic acid anhydride and caprolactone, Benzophenone acid dianhydride, Benzophenone acid dianhydride and caprolactone, diphenyl sulfone-3,3 ', 4,4 '-tetracarboxylic dianhydride DSDA, diphenyl sulfone-3,3 ', 4, one or more in the addition product of 4 '-tetracarboxylic dianhydride, N, N '-dicarboxylic anhydride diphenyl methane or mellitic acid three acid anhydride.
8. the preparation method of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1, it is characterized in that the polar organic solvent described in step (5) includes ethanol, methyl alcohol, dimethyl sulfoxide (DMSO), oxolane, acetone or N, one or more mixtures of N '-dimethyl formamide.
9. the preparation method of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1, it is characterised in that epoxy resin described in step (6) refers to include any one in glycidol ethers, glycidol lipid, glycidol amine, alicyclic ring class, epoxidation of olefins class, imide ring epoxy resins or glycolylurea epoxide resin.
10. the preparation method of carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1, it is characterized in that described in step (7), organic acid anhydride curing agent is phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, adjacent PMDA, phthalic anhydride tetracarboxylic dianhydride, methylcyclohexene tetracarboxylic dianhydride, oxydiphthalic, one or several mixture in trimellitic anhydride or poly-azelaic acid acid anhydride.
The preparation method of 11. carbon fiber/Nano diamond/epoxy resin multi-dimensional hybrid composites according to claim 1, it is characterised in that carbon fiber described in step (7) is any one in unidirectional long fibre cloth, two-way woven cloth, three-phase woven cloth or random staple fibre cloth.
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