CN1730743A - Modification method of interface between carbon fiber and non-polar resin - Google Patents
Modification method of interface between carbon fiber and non-polar resin Download PDFInfo
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Abstract
The present invention is modification method for the combination interface between carbon fiber and non-polar resin, relates to the interface modification method for polymer-base composite material, and aims at raising the intralaminar shearing strength of composite comprising carbon fiber and non-polar resin through surface activation. The method of the present invention includes the following steps: pre-treatment, preparing coating solution; activating carbon fiber; introducing coating solution; and post-treatment. The carbon fiber and polyaryl acetylene silicon resin thus treated may be molded into composite material with resin content of 35 wt%, and this composite material has intralaminar shearing strength at room temperature up to 38-52 MPa and lowered to 32.5-37.5 MPa after high temperature oxidation.
Description
Technical field:
The present invention relates to the composite material interface modification technology, be specifically related to a kind of method that is used for the polymer matrix composite interface modification.
Background technology:
Advanced polymer matrix composite plays an important role in fields such as Aeronautics and Astronautics, military affairs, buildings, and the interface is a composite distinctive, extremely important part, performance to material plays important or even conclusive effect, has been acknowledged as the research topic that runs through composite development basic and general character all the time.The interface directly influences Stress Transfer and the dispersion between composite fiber and the matrix, thereby influences the off-axis performance of composite; Interfacial characteristics also has influence on the damage accumulation of composite inner and the course of crack propagation, thereby influences the fracture toughness of composite; In addition, the interface also influences the anti-environmental stability of composite.
Proved already,, reached desirable composite effect by regulating interfacial phenomenon, can make the coupling that has the best between fiber and matrix composite material interface microcell (being generally several nanometers) to hundreds of nanometers.Therefore, the correct microstructure information of understanding the interface is carried out the research of interfacial property, as required composite material interface is carried out chemical modification, for fiber reasonable in design-polymeric matrix interface microstructure, realize that the control of composite overall performance is significant.
But owing to strengthen the popularity of body, polymeric matrix, reasons such as the diversity of composite material process planning have caused the complexity of polymer matrix composite interface problem.At present, people do not obtain unified understanding as yet to interface interaction mechanism, especially to the related not fine as yet establishment between characteristics such as its interfacial chemical reaction, interfacial stress, interface phase microstructure, interface micro-property and the composite macroscopic view overall performance, there are many problems of clarifying and solving demanded urgently.This mainly is to lack controlled, stable method for activating surface, and then cause dispersiveness, randomness and the randomness of formed fiber surface functional group (comprising impurity) quantity and distribution, the complexity of various functional groups, surface topography, interface interaction (comprising chemical reaction), thus make material in use can not reach desirable estimated performance.For example, the composite interlaminar shear strength at room temperature that carbon current fiber and nonpolar poly-aryl ethane resin constitute is generally 34Mpa, after the high temperature thermal oxidation burin-in process, interlaminar shear strength drops to 29～32Mpa, therefore, can not satisfy the needs of the application scenario that composite property is had relatively high expectations.
Summary of the invention:
The objective of the invention is to cause the low problem of composite interlayer shear strength of carbon fiber and non-polar resin formation, thereby a kind of method of modifying that is used for carbon fiber and non-polar resin combination interface is provided for the processing that solves existing composite material interface lacks method for activating surface.
Method of the present invention is carried out according to the following steps: one, preliminary treatment: use acetone or alcohol that the original coating of carbon fiber surface is removed; Two, preparation coating solution: coating solution is formulated by vinyl silsesquioxane and oxolane, and the quality of described vinyl silsesquioxane accounts for 1%～2% of described coating solution gross mass; Three, activated carbon fiber: use the cold plasma of air activated carbon fiber under the power of 150～200W, make carbon fiber surface produce a large amount of spikes; Four, introduce coating solution: under the condition that keeps vacuum, coating solution is introduced, made carbon fiber in described coating solution, soak 5～35min, make the carbon fiber of surface active and described vinyl silsesquioxane react; Five, post processing: from plasma apparatus, take out carbon fiber, and oven dry in a vacuum, can obtain the carbon fiber after the surface modification.
The present invention adopts to contain the modifier of active function groups organic inorganic hybridization silsesquioxane as carbon fiber surface, simultaneously in conjunction with the cold plasma activation carbon fiber surface of air, thereby connects the functional group that is complementary with resin structure on fiber surface.Through after the plasma activation, carbon and oxygen isoreactivity kind on carbon fiber surface, have been introduced, cause the reaction of the silsesquioxane and the carbon fiber that contain active function groups, thereby on carbon fiber surface, introduce the single single functional group that is complementary with resin, thereby carbon fiber after feasible processing the and the bonding enhancing between the resin, the interface performance of the composite of preparation improves greatly, at high temperature still has good interface performance.
The present invention is applicable to the interface modification processing of carbon fiber and nonpolar poly-aryl ethane resin system.Adopt carbon fiber and poly-aryl ethane silicones after the present invention handles can be prepared into the composite that resin content is 35mass% by mold pressing, and this composite interlaminar shear strength at room temperature can reach 38～52MPa, compare with the composite that untreated carbon fiber forms, interlaminar shear strength has improved 12～53%, and above-mentioned composite is behind high-temperature oxydation, and interlaminar shear strength only drops to 32.5～37.5Mpa.
Description of drawings:
Fig. 1 is influence the as a result figure of ionic medium processing time of the present invention to composite interlayer shear strength, Fig. 2 contains processing time of coating solution of vinyl silsesquioxane of 2% (mass ratio) to the figure as a result that influences of composite interlayer shear strength among the present invention, Fig. 3 contains processing time of coating solution of vinyl silsesquioxane of 1% (mass ratio) to the figure as a result that influences of composite interlayer shear strength among the present invention, Fig. 4 is the Fourier infrared spectrum figure of the collosol and gel hydrolytie polycondensation product vinyl silsesquioxane for preparing of the present invention, Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of the vinyl silsesquioxane for preparing of the present invention, Fig. 6 is the nuclear magnetic resonance of carbon spectrogram of the vinyl silsesquioxane for preparing of the present invention, Fig. 7 is the silicon nmr spectrum of the vinyl silsesquioxane for preparing of the present invention, and Fig. 8 is the ground substance assistant laser desorption ionization flight time mass spectrum figure of the vinyl silsesquioxane for preparing of the present invention.
The specific embodiment:
The specific embodiment one: this specific embodiment is carried out according to the following steps: one, preliminary treatment: use acetone or alcohol that the original coating of carbon fiber surface is removed; Two, preparation coating solution: coating solution is formulated by vinyl silsesquioxane and oxolane, and the quality of described vinyl silsesquioxane accounts for 1%～2% of described coating solution gross mass; Three, activated carbon fiber: use the cold plasma of air activated carbon fiber under the power of 150～200W, make carbon fiber surface produce a large amount of spikes; Four, introduce coating solution: under the condition that keeps vacuum, coating solution is introduced, made carbon fiber in described coating solution, soak 5～35min, make the carbon fiber of surface active and described vinyl silsesquioxane react; Five, post processing: from plasma apparatus, take out carbon fiber, and oven dry in a vacuum, can obtain the carbon fiber after the surface modification.
The temperature of drying in a vacuum in the 5th step of this specific embodiment is 50～60 ℃.Using the time of the cold plasma treatment carbon fiber of air in the 3rd step of this specific embodiment is 5～15min.When the power of plasma apparatus immobilized, the time that can regulate the cold plasma treatment carbon fiber of air was controlled the activation effect to fiber, and it is more convenient, easy to operate to control activated carbon fiber like this.As shown in Figure 1, the broken line of band point adopts the raising rate and the corresponding relation of plasma treatment time of the interlaminar shear strength of the composite after the plasma treatment when being illustrated in 175W, the cylindricality frame table of band oblique line adopts the interlaminar shear strength and the corresponding relation of plasma treatment time of the composite after the plasma treatment when being shown in 175W, the vertical line among the figure above the cylindricality frame of each band oblique line is represented the Measurement Variance of the interlaminar shear strength of described composite.
The specific embodiment two: this specific embodiment with the difference of the specific embodiment one is: the vinyl silsesquioxane contains 2g in the coating solution of second step preparation, and oxolane contains 198g; The 3rd step was used the cold plasma of air activated carbon fiber 10min under the power of 175W; The 4th step made carbon fiber soak 15min in described coating solution; The 5th step made carbon fiber 50 ℃ of oven dry down.Other steps are identical with the specific embodiment one.This specific embodiment makes and occurs a large amount of unsaturated double-bonds that are complementary with poly-aryl ethane nonpolar structure on the fiber surface.Adopt the carbon fiber of the silsesquioxane modification that this specific embodiment prepares and poly-aryl ethane silicones can reach 49.2MPa by the composite interlaminar shear strength at room temperature of mold pressing preparation, compare with the composite that untreated carbon fiber forms, interlaminar shear strength has improved 45%.Behind the oxidation 30min, interlaminar shear strength drops to 35.0MPa to above-mentioned composite in 350 ℃ air, mass loss 1.0%; Compare with the composite that untreated carbon fiber forms, after thermo-oxidative ageing was handled under similarity condition, interlaminar shear strength dropped to 31.4MPa, mass loss 1.7%.As seen the carbon fiber after handling through the present invention and the surperficial associativity of nonpolar poly-aryl ethane resin are better, and the composite interlayer shear strength of the two formation is stronger.As shown in Figure 3, the broken line of band point represents to use the corresponding relation of raising rate and soak time in coating solution of the interlaminar shear strength of the composite after the coating solution of the vinyl silsesquioxane that contains 1% (mass ratio) is handled, the cylindricality frame table of band oblique line shows the interlaminar shear strength of the composite after the coating solution that uses the vinyl silsesquioxane that contains 1% (mass ratio) is handled and the corresponding relation of the soak time in coating solution, and the vertical line among the figure above the cylindricality frame of each band oblique line is represented the Measurement Variance of the interlaminar shear strength of described composite.
The specific embodiment three: this specific embodiment with the difference of the specific embodiment two is: the vinyl silsesquioxane contains 4g in the coating solution of second step preparation, and oxolane contains 196g; The 4th step made carbon fiber soak 20min in described coating solution.Other steps are identical with the specific embodiment two.Adopt the carbon fiber of the silsesquioxane modification that this specific embodiment makes and poly-aryl ethane silicones can reach 41.7MPa by the composite interlaminar shear strength at room temperature of mold pressing preparation, compare with the composite that untreated carbon fiber forms, interlaminar shear strength has improved 22%.As shown in Figure 2, the broken line of band point represents to use the corresponding relation of raising rate and soak time in coating solution of the interlaminar shear strength of the composite after the coating solution of the vinyl silsesquioxane that contains 2% (mass ratio) is handled, the cylindricality frame table of band oblique line shows the interlaminar shear strength of the composite after the coating solution that uses the vinyl silsesquioxane that contains 2% (mass ratio) is handled and the corresponding relation of the soak time in coating solution, and the vertical line among the figure above the cylindricality frame of each band oblique line is represented the Measurement Variance of the interlaminar shear strength of described composite.
The specific embodiment four: the difference of this specific embodiment and the specific embodiment two is: in the coating solution of second step preparation vinyl silsesquioxane quality account for 1.5% of described coating solution gross mass.Other steps are identical with the specific embodiment two.Adopt the carbon fiber of the silsesquioxane modification that this specific embodiment makes and poly-aryl ethane silicones can reach 45Mpa by the composite interlaminar shear strength at room temperature of mold pressing preparation.
The specific embodiment five: this specific embodiment with the difference of the specific embodiment two is: the 3rd step was used the cold plasma of air activated carbon fiber 7min under the power of 100W; The 4th step made carbon fiber soak 5min in described coating solution.Other steps are identical with the specific embodiment two.Adopt the carbon fiber of the silsesquioxane modification that this specific embodiment makes and poly-aryl ethane silicones can reach 39.5MPa by the composite interlaminar shear strength at room temperature of mold pressing preparation, compare with the composite that untreated carbon fiber forms, interlaminar shear strength has improved 14%.This specific embodiment is compared with the specific embodiment three with the specific embodiment two, and the composite that the carbon fiber after handling through the specific embodiment two forms has interlaminar shear strength relatively preferably.
The specific embodiment six: this specific embodiment with the difference of the specific embodiment two is: the 3rd step was used the cold plasma of air activated carbon fiber 7min under the power of 150W, and the temperature at vacuum drying in the 5th step is 60 ℃.Other steps are identical with the specific embodiment two.Adopt the carbon fiber of the silsesquioxane modification that this specific embodiment makes and poly-aryl ethane silicones can reach 38.8Mpa by the composite interlaminar shear strength at room temperature of mold pressing preparation.
The specific embodiment seven: this specific embodiment with the difference of the specific embodiment two is: the 3rd step was used the cold plasma of air activated carbon fiber 5min under the power of 200W, and the temperature at vacuum drying in the 5th step is 55 ℃.Other steps are identical with the specific embodiment two.Adopt the carbon fiber of the silsesquioxane modification that this specific embodiment makes and poly-aryl ethane silicones can reach 45.235Mpa by the composite interlaminar shear strength at room temperature of mold pressing preparation.
The specific embodiment eight: in this specific embodiment, the preparation method of vinyl silsesquioxane carries out according to the following steps described in the coating solution of the second step preparation: (I), vinyltrimethoxy silane, absolute alcohol kind solvent and water are put in the reaction vessels, the consumption mol ratio of wherein said vinyltrimethoxy silane and described water is 1: 3～1: 4, and the consumption mol ratio of described vinyltrimethoxy silane and described absolute alcohol kind solvent is 1: 2～1: 3; (II), in described reaction vessels, drip catalyst after, use magnetic stirring apparatus that the material in the described reaction vessels is stirred, the consumption mol ratio of wherein said catalyst and described vinyltrimethoxy silane is 1: 2～1: 3; (III), the material in the described reaction vessels after will stirring again is placed under 30～40 ℃ and is hydrolyzed and polycondensation reaction.Among the preparation method of the described vinyl silsesquioxane of this specific embodiment, the absolute alcohol kind solvent comprises a kind of in absolute ethyl alcohol, methyl alcohol or the acetone.Among the preparation method of the described vinyl silsesquioxane of this specific embodiment, catalyst is acidity or base catalyst, comprises a kind of in formic acid, hydrochloric acid or the NaOH.When adopting this specific embodiment, preparation technology is simple, and is easy to operate.Adopting the silsesquioxane of this specific embodiment preparation is the mixture of free structure, trapezium structure, half cagelike structure and cagelike structure, as Fig. 4, Fig. 5, Fig. 6, Fig. 7 and shown in Figure 8, figure among Fig. 4 (2) is the Fourier infrared spectrum figure of the collosol and gel hydrolytie polycondensation product vinyl silsesquioxane of the present invention's preparation, Fig. 5, Fig. 6 and Fig. 7 are the nmr spectrum of the vinyl silsesquioxane of the present invention's preparation, and Fig. 8 is the ground substance assistant laser desorption ionization flight time mass spectrum figure of the vinyl silsesquioxane of the present invention's preparation.
In this specific embodiment, the consumption mol ratio of described vinyltrimethoxy silane and described water is less than 1: 3 o'clock, the hypovolia in the system, thickness very soon becomes, greater than 1: 4 o'clock, the hypervolia in the reaction system makes the hydrolysis condensation reaction process very very long; The consumption mol ratio of described vinyltrimethoxy silane and described absolute alcohol kind solvent is less than 1: 2 o'clock, having observed droplet in system suspends, illustrate that organic facies is with inorganic miscible inhomogeneous between mutually, greater than 3: 1 o'clock, the time of gel is longer, and main cause may be that the content of absolute alcohol kind solvent too much causes the hydrolysis condensation reaction speed of polysiloxane precursor body to reduce; The consumption mol ratio of described catalyst and described vinyltrimethoxy silane is very fast greater than the speed of 1: 2 o'clock hydrolysis condensation reaction, reaching the required time of gel state shortens, the micromolecule that makes in the system some have neither part nor lot in reaction is wrapped in wherein, can not volatilize, cause the target product productive rate very low, impurity is more.During at the system of other fiber reinforced polymer matrix composites, synthetic required active function groups changes, and the parameter in the process conditions will change accordingly, can explore optimised process by orthogonal test method.
The specific embodiment nine: this specific embodiment with the difference of the specific embodiment eight is: hydrolysis and polycondensation reaction are carried out according to the following steps in (III) step of the preparation method of the described vinyl silsesquioxane of this specific embodiment: earlier the material in the described reaction vessels is placed under the complete air-proof condition, floccule occurs in described reaction vessels; The material in the described reaction vessels is placed under the semitight condition, the material in described reaction vessels presents thick again; At last the material in the described reaction vessels is placed under the condition of opening wide, the material in described reaction vessels reaches till the viscoelastic state gel.Other steps are identical with the specific embodiment eight.The course of reaction of this specific embodiment all can detect by an unaided eye: floccule occurs in described reaction vessels, can see having the byssaceous material of picture to occur in original clear solutions; When the material in the described reaction vessels presents when thick, pick up described reaction vessels rotation and can find that the flow of matter in the vessel is slow.
The specific embodiment ten: this specific embodiment with the difference of the specific embodiment nine is: in (III) step of the preparation method of described vinyl silsesquioxane, when hydrolysis and polycondensation reaction, air-proof condition is meant with film described reaction vessels is sealed fully, the semitight condition is meant pricks several pin holes with described film, and unlimited condition is meant takes described film away.Other steps are identical with the specific embodiment nine.Utilize film to realize that the reaction condition of hydrolysis and polycondensation reaction is the easiest mode.
The specific embodiment 11: the difference of this specific embodiment and the specific embodiment eight is that the preparation method of vinyl silsesquioxane described in its coating solution of second step preparation carries out according to the following steps: (I), vinyltrimethoxy silane, absolute ethyl alcohol and water are put in the beaker of 50ml, the consumption mol ratio of wherein said vinyltrimethoxy silane and described water is 1: 3, and the consumption mol ratio of described vinyltrimethoxy silane and described absolute ethyl alcohol is 1: 3; (II), in described beaker, drip formic acid, the consumption mol ratio of described formic acid and described vinyltrimethoxy silane is 1: 2; (III), the described beaker diaphragm seal after will stirring earlier, and be placed in 35 ℃ the water-bath and heat, react and floccule occurs in the described beaker after five days, again described film is pricked several pin holes, and to keep bath temperature be 35 ℃, continue heating after two days the material in the beaker present thick, at last described film is removed, and to continue to keep bath temperature be 35 ℃, and the material in described beaker reaches till the viscoelastic state, and gel total time is eight days.Other steps are identical with the specific embodiment eight.The vinyl silsesquioxane synthetic through this specific embodiment is gel state at last, is the mixture of trapezium structure and cagelike structure, and the scope of its molecular weight of ground substance assistant laser desorption ionization flight time mass spectrum test shows is at m/z=487～1608Da.
The specific embodiment 12: the difference of this specific embodiment and the specific embodiment 11 is that the preparation method of vinyl silsesquioxane described in its coating solution of second step preparation carries out according to the following steps: (I), the consumption mol ratio of described vinyltrimethoxy silane and described water is 1: 4; (II), the consumption mol ratio of described formic acid and described vinyltrimethoxy silane is 1: 3; (III), the material in the described beaker is hydrolyzed and polycondensation reaction under 35 ℃, gel total time is the Ninth Heaven.Other steps are identical with the specific embodiment 11.
The specific embodiment 13: the difference of this specific embodiment and the specific embodiment 11 is that the preparation method of vinyl silsesquioxane described in its coating solution of second step preparation carries out according to the following steps: (I), the consumption mol ratio of described vinyltrimethoxy silane and described water is 1: 4, the consumption mol ratio of described vinyltrimethoxy silane and described absolute ethyl alcohol is 1: 2; (II), the consumption mol ratio of described formic acid and described vinyltrimethoxy silane is 1: 2.5; (III), the material in the described beaker is hydrolyzed and polycondensation reaction under 45 ℃, gel total time is five days.Adopting the synthetic vinyl silsesquioxane of this specific embodiment is cross-linked network product simple in structure, the free mechanism of small-molecular weight.Other steps are identical with the specific embodiment 11.
The specific embodiment 14: this specific embodiment is when the described vinyl silsesquioxane of preparation, and adopting methyl alcohol is the absolute alcohol kind solvent.When adopting this specific embodiment, methyl alcohol is toxic, and is bad to environment.
The specific embodiment 15: this specific embodiment is when the described vinyl silsesquioxane of preparation, and adopting acetone is the absolute alcohol kind solvent.When adopting this specific embodiment, the reaction time is long.
The specific embodiment 16: this specific embodiment is when the described vinyl silsesquioxane of preparation, and employing hydrochloric acid is catalyst.When adopting this specific embodiment, reaction speed is fast.
The specific embodiment 17: this specific embodiment is when the described vinyl silsesquioxane of preparation, and employing NaOH is catalyst.When adopting this specific embodiment, introduced sodium ion, can cause the suction effect of carbon fiber like this on the surface of carbon fiber.
The present invention can select for use different active function groups silane to prepare coating solution at different fibers and resin system to be used to handle the composite fiber surface, for example in carbon fiber and nonpolar poly-aryl ethane resin system, select the vinyl silanes that contains nonpolar unsaturated double-bond for use; In systems such as carbon fiber and polar resin such as epoxy, phenolic aldehyde, unsaturated polyester (UP), select the silane that contains amino, hydroxyl, ester group, epoxy radicals isopolarity functional group for use; Strengthen body at other, in the polymeric system as enhancings such as glass fibres, can select according to the characteristic of fiber and resin.So, select different functional groups silane to prepare coating solution according to the characteristic of fiber and resin, and described coating solution be used to handle carbon fiber after the plasma activation, also in protection scope of the present invention.
Claims (10)
1, a kind of method of modifying that is used for carbon fiber and non-polar resin combination interface, it carries out according to the following steps: one, preliminary treatment: use acetone or alcohol that the original coating of carbon fiber surface is removed; It is characterized in that: two, preparation coating solution: coating solution is formulated by vinyl silsesquioxane and oxolane, and the quality of described vinyl silsesquioxane accounts for 1%～2% of described coating solution gross mass; Three, activated carbon fiber: use the cold plasma of air activated carbon fiber under the power of 150～200W, make carbon fiber surface produce a large amount of spikes; Four, introduce coating solution: under the condition that keeps vacuum, coating solution is introduced, made carbon fiber in described coating solution, soak 5～35min, make the carbon fiber of surface active and described vinyl silsesquioxane react; Five, post processing: from plasma apparatus, take out carbon fiber, and oven dry in a vacuum, can obtain the carbon fiber after the surface modification.
2, a kind of method of modifying that is used for carbon fiber and non-polar resin combination interface according to claim 1 is characterized in that the temperature of drying in a vacuum in its 5th step is 50～60 ℃.
3, a kind of method of modifying that is used for carbon fiber and non-polar resin combination interface according to claim 1 is characterized in that using the time of the cold plasma treatment carbon fiber of air in its 3rd step is 5～15min.
4,, it is characterized in that the quality of vinyl silsesquioxane accounts for 1% of described coating solution gross mass described in its second step according to claim 1,2 or 3 described a kind of method of modifying that are used for carbon fiber and non-polar resin combination interface; The 3rd step was used the cold plasma of air activated carbon fiber 10min under the power of 175W; The 4th step made carbon fiber soak 15min in described coating solution; The 5th step made carbon fiber 50 ℃ of oven dry down.
5, a kind of method of modifying that is used for carbon fiber and non-polar resin combination interface according to claim 1, the preparation method who it is characterized in that vinyl silsesquioxane described in its coating solution of the second step preparation carries out according to the following steps: (I), vinyltrimethoxy silane, absolute alcohol kind solvent and water are put in the reaction vessels, the consumption mol ratio of wherein said vinyltrimethoxy silane and described water is 1: 3～1: 4, and the consumption mol ratio of described vinyltrimethoxy silane and described absolute alcohol kind solvent is 1: 2～1: 3; (II), in described reaction vessels, drip catalyst after, use magnetic stirring apparatus that the material in the described reaction vessels is stirred, the consumption mol ratio of wherein said catalyst and described vinyltrimethoxy silane is 1: 2～1: 3; (III), the material in the described reaction vessels after will stirring again is placed under 30～40 ℃ and is hydrolyzed and polycondensation reaction.
6, a kind of method of modifying that is used for carbon fiber and non-polar resin combination interface according to claim 5 is characterized in that among the preparation method of described vinyl silsesquioxane, and the absolute alcohol kind solvent comprises a kind of in absolute ethyl alcohol, methyl alcohol or the acetone.
7, a kind of method of modifying that is used for carbon fiber and non-polar resin combination interface according to claim 5, it is characterized in that among the preparation method of described vinyl silsesquioxane, catalyst is acidity or base catalyst, comprises a kind of in formic acid, hydrochloric acid or the NaOH.
8, a kind of method of modifying that is used for carbon fiber and non-polar resin combination interface according to claim 5, it is characterized in that hydrolysis and polycondensation reaction are carried out according to the following steps in (III) step of preparation method of described vinyl silsesquioxane: earlier the material in the described reaction vessels is placed under the complete air-proof condition, in described reaction vessels, floccule occurs; The material in the described reaction vessels is placed under the semitight condition, the material in described reaction vessels presents thick again; At last the material in the described reaction vessels is placed under the condition of opening wide, the material in described reaction vessels reaches till the viscoelastic state gel.
9, a kind of method of modifying that is used for carbon fiber and non-polar resin combination interface according to claim 8, when it is characterized in that in (III) step of preparation method of described vinyl silsesquioxane hydrolysis and polycondensation reaction, air-proof condition is meant with film described reaction vessels is sealed fully, the semitight condition is meant pricks several pin holes with described film, and unlimited condition is meant takes described film away.
10, according to claim 5,6 or 7 described a kind of method of modifying that are used for carbon fiber and non-polar resin combination interface, the preparation method who it is characterized in that vinyl silsesquioxane described in its coating solution of the second step preparation carries out according to the following steps: (I), vinyltrimethoxy silane, absolute ethyl alcohol and water are put in the beaker of 50ml, the consumption mol ratio of wherein said vinyltrimethoxy silane and described water is 1: 3, and the consumption mol ratio of described vinyltrimethoxy silane and described absolute ethyl alcohol is 1: 3; (II), in described beaker, drip formic acid, the consumption mol ratio of described formic acid and described vinyltrimethoxy silane is 1: 2; (III), the described beaker after will stirring is placed on to heat in 35 ℃ the water-bath and is hydrolyzed and polycondensation reaction, gel total time is eight days.
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