CN104497641A - Preparation method of nano-silica with surface grafted with polystearylmethacrylate - Google Patents

Abstract

The invention relates to a preparation method of nano-silica with the surface grafted with polystearylmethacrylate, belonging to the field of surface grafting and modification of nano-particles. The preparation method comprises the following steps of firstly grafting amino silane to the surface of nano-silica in a high polar solvent by virtue of a reversible addition-fragmentation chain transfer polymerization method; then grafting a chain transfer agent to the surfaces of nano-particles through amino silane by virtue of the combination between thiol ester functional groups and amino functional groups on the chain transfer agent; finally providing free radicals by an initiator, and polymerizing monomers of polystearylmethacrylate to the tail end of the chain transfer agent. According to the polystearylmethacrylate-grafted nano-silica nano-particles prepared by virtue of the preparation method, the dispersity of nano-silica in low density polyethylene and a crosslinked polyethylene matrix is improved. According to the preparation method, a firm foundation is laid for the further improvement of mechanical and electrical properties of polyvinyl nano-composite materials.

Description

The preparation method of surface grafting Polystearylmethacrylate nano silicon

Technical field

The present invention relates to a kind of preparation method of surface grafting Polystearylmethacrylate nano silicon, belong to nano grain surface graft modification field.

Background technology

Since entering 21 century, the application of nanotechnology gets more and more, and it does not allow to despise to the pushing effect of material industry especially.Each industrialized country all at input substantial contribution research nano-macromolecule material, to adapt to growing industrial requirement, and forms an international competition gradually.

It is the important embodiment of nanotechnology to material industry pushing effect that nano particle adds the performance boost of macromolecular material, and suitable nano particle adds the performance can improving the aspect such as mechanics, optics, electricity, biology of macromolecular material well.But, nano particle has the large feature of the little and surface energy of volume, usually and high molecular polymerization matrix incompatible, and due to mutual magnetism, cause nano particle easily to be reunited, thus coexist with the form of micron-scale reunion and nano particle and distribute in complex media.From nano-dispersibility angle, above-mentioned complex media can not be called nano-filled composite truly, and existing research also shows that nano-dispersibility is the key factor affecting nano-filled composite performance.Therefore, before nano particle adds high molecular polymer matrix to, often need to carry out modification to it, namely with certain material decorated nanometer particle surface, change mi-crochemistry and the physical properties at interface between nano particle and polymeric matrix, thus improve the dispersiveness of nano particle in polymeric matrix, give full play of the characteristic of nano particle excellence.

Nano grain surface graft modification has two class methods usually, i.e. physically modified and chemical modification.The former refers to and carries out modification by absorption, coating, the physical means such as coated to particle surface; The latter refers to, by modifier molecule and nano grain surface atom or special functional group, chemical reaction occurs, thus realizes grafting and fix.Wherein, the nanoparticulate dispersed after chemical modification process is better, obtains in actual applications and promotes in large quantities.

Chemical modification comprises surfactant method and surface grafting polymerization method: the tensio-active agent that (1) is commonly used has: silane coupling agent, stearic acid and organosilicon etc., this method is simple to operate, it is the most frequently used chemical modification method, but because tensio-active agent is not macromolecular material, with the molecular structure of polymeric matrix and molecular weight difference very large, cannot interpenetrate with polymer chain, thus unsatisfactory to the improvement effect of nanoparticulate dispersed; (2) surface grafting polymerization method has become the important means of modified by nano particles, and graft polymerization species is many, and controllability is good.And controllable free-radical polymerisation method is topmost class methods in surface grafting polymerization method at present.

Controllable free-radical polymerisation method utilizes the balance between Propagating Radical and all kinds of dormancy kind, control the Raolical polymerizable of the molecular weight of polymkeric substance, molecular weight distribution and terminated functional, comprise oxygen nitrogen stable free radical polymerization method, Transfer Radical Polymerization and reversible addition ~ chain rupture transfer polymerization method.Relative to the method for other polymer brush surface graft modification nano particle, the suitable monomers kind of reversible addition ~ chain rupture transfer polymerization method is more, and reaction conditions requires lower, and the molecular weight distribution of graftomer is narrower, aftertreatment is simple, is applicable to the multiple system such as solution, suspension polymerization.Due to these advantages, reversible addition ~ chain rupture transfer polymerization method becomes the important method of nano grain surface graft modification, is widely used in the preparation of nano-filled composite.

In Polymer Material Industry, the advantages such as polyethylene is good, cheap with its chemical stability, mature preparation process, good insulation preformance, first of the output having occupied general synthetic resin, be widely used in agricultural, packaging, electric, mechanical, the aspect such as automobile, daily use Sundry goods.Polyethylene comprises Low Density Polyethylene, high density polyethylene(HDPE), crosslinked polyethylene etc., and along with emerging in large numbers of new technology, poly performance is in continuous improvement, and cost is in lasting reduction, and the competition of high-performance polyethylene technical field simultaneously is also growing more intense.Add the focus that nano particle is undoubtedly high-performance polyethylene based composite dielectric research direction.

Summary of the invention

The object of the invention is the preparation method proposing a kind of surface grafting Polystearylmethacrylate nano silicon, to improve the dispersiveness of nano silicon in polyethylene, thus provide maximum likelihood for preparing high-performance polyethylene base nano-filled composite.

The preparation method of the surface grafting Polystearylmethacrylate nano silicon that the present invention proposes, comprises the following steps:

(1) be first scattered in intensive polar solvent by silicon-dioxide, obtain the silicon dioxde solution that mass percent concentration is 10% ~ 40%, described intensive polar solvent is: methyl alcohol, ethanol, methylethylketone, trichloromethane, tetrahydrofuran (THF) or toluene; Aminosilane is joined in silicon dioxde solution, the volumetric molar concentration of aminosilane in silicon dioxde solution is made to be 1 ~ 10mol/L, and at nitrogen atmosphere, reflux 5 ~ 24 hours at 50 ~ 120 DEG C, obtain the first mixed solution, described aminosilane is APTES, 3-TSL 8330,3-dimethyl methoxy silane or 4-ammobutyltriethoxysilane; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=(5 ~ 15): 1, after waiting for that solid precipitates completely, centrifugation is carried out to this mixture, and isolated solid is dissolved in above-mentioned intensive polar solvent, obtain the solution that mass body volume concentrations is 0.01 ~ 0.4g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) chain-transfer agent is added step (1) described intensive polar solvent, obtain the chain-transfer agent solution that mass body volume concentrations is 1 ~ 5g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: chain-transfer agent: the first solution=1:(0.5 ~ 2), at room temperature stir 6 ~ 12 hours, obtain the second mixed solution, described chain-transfer agent is dithiobenzoic acid isopropyl phenyl ester, trithiocarbonate, 4-cyano group-4-(thiobenzoyl) valeric acid, dithio benzoyl or the withered ester of dithiobenzoic acid; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=(2 ~ 6): 1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=(5 ~ 15): 1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the intensive polar solvent of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.01 ~ 0.4g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of surface grafting chain-transfer agent, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the intensive polar solvent of step (1), obtain the solution that mass body volume concentrations is 2 ~ 10g/mL, be designated as the second solution; Second solution is mixed with stearyl methacrylate and initiator, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:(0.5 ~ 2), second solution: initiator=1:(0.005 ~ 0.05), obtain the 3rd mixed solution, described initiator is any one in benzoyl peroxide, diacetyl peroxide, dioctanoyl peroxide, 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester, isopropyl benzene hydroperoxide, tertbutyl peroxide or peroxy dicarbonate diisobutyl ester; Above-mentioned 3rd mixed solution is heated to 50 ~ 120 DEG C, and the reaction times is 8 ~ 24 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: the 4th mixed solution=(5 ~ 15): 1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the intensive polar solvent centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.01 ~ 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in intensive polar solvent of surface grafting Polystearylmethacrylate.

The preparation method of the surface grafting Polystearylmethacrylate nano silicon that the present invention proposes, its advantage is:

Polystearylmethacrylate grafted silica nano particle prepared by the inventive method, first reversible addition ~ fracture chain transfer polymerization method is incorporated in polyethylene based composition system, the acting in conjunction result of the Van der Waals force be mutually wound around due to Polystearylmethacrylate and polyethylene backbone and attract each other between screen nano particle, improve the dispersiveness of nano silicon in low density in polyethylene, then, after low density polyethylene cross-linked, the dispersiveness of nano silicon in crosslinked polyethylene matrix is also significantly improved.The nano grain surface grafting method that the present invention proposes is that the performance such as mechanics, electricity improving polyvinyl nano composite material has further established solid basis.In terms of mechanics, the storage modulus of polyvinyl nano composite material, Young's modulus and hardness modulus can be improved; In calorifics, its glass transition temperature can be improved; In optics, the transmissivity of light can be improved, and improve material to ultraviolet and ultrared shield effectiveness; In electricity, its voltage breakdown can be improved, and suppress space charge.

The nano-silica surface grafting method adopted in the present invention has universality, is specially adapted to the nano particle that surface has oh group.

Accompanying drawing explanation

Fig. 1 is the thermogravimetic analysis (TGA) result of the nano silicon of non-grafting and grafting Polystearylmethacrylate in embodiment 1;

Fig. 2 is the infrared spectra of the nano silicon of non-grafting and grafting Polystearylmethacrylate in embodiment 1;

Fig. 3 is the scanning electron microscope (SEM) photograph of non-engrafted nanometer silicon-dioxide compound crosslinked polyethylene in embodiment 1;

Fig. 4 is the scanning electron microscope (SEM) photograph of the nano silicon compound crosslinked polyethylene of grafting Polystearylmethacrylate in embodiment 1.

Embodiment

The preparation method of the surface grafting Polystearylmethacrylate nano silicon that the present invention proposes, comprises the following steps:

(1) be first scattered in intensive polar solvent by silicon-dioxide, obtain the silicon dioxde solution that mass percent concentration is 10% ~ 40%, described intensive polar solvent is: methyl alcohol, ethanol, methylethylketone, trichloromethane, tetrahydrofuran (THF) or toluene; Aminosilane is joined in silicon dioxde solution, the volumetric molar concentration of aminosilane in silicon dioxde solution is made to be 1 ~ 10mol/L, and at nitrogen atmosphere, reflux 5 ~ 24 hours at 50 ~ 120 DEG C, obtain the first mixed solution, described aminosilane is APTES, 3-TSL 8330,3-dimethyl methoxy silane or 4-ammobutyltriethoxysilane; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=(5 ~ 15): 1, after waiting for that solid precipitates completely, centrifugation is carried out to this mixture, and isolated solid is dissolved in above-mentioned intensive polar solvent, obtain the solution that mass body volume concentrations is 0.01 ~ 0.4g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) chain-transfer agent is added step (1) described intensive polar solvent, obtain the chain-transfer agent solution that mass body volume concentrations is 1 ~ 5g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: chain-transfer agent: the first solution=1:(0.5 ~ 2), at room temperature stir 6 ~ 12 hours, obtain the second mixed solution, described chain-transfer agent is dithiobenzoic acid isopropyl phenyl ester, trithiocarbonate, 4-cyano group-4-(thiobenzoyl) valeric acid, dithio benzoyl or the withered ester of dithiobenzoic acid; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=(2 ~ 6): 1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=(5 ~ 15): 1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the intensive polar solvent of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.01 ~ 0.4g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of surface grafting chain-transfer agent, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the intensive polar solvent of step (1), obtain the solution that mass body volume concentrations is 2 ~ 10g/mL, be designated as the second solution; Second solution is mixed with stearyl methacrylate and initiator, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:(0.5 ~ 2), second solution: initiator=1:(0.005 ~ 0.05), obtain the 3rd mixed solution, described initiator is any one in benzoyl peroxide, diacetyl peroxide, dioctanoyl peroxide, 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester, isopropyl benzene hydroperoxide, tertbutyl peroxide or peroxy dicarbonate diisobutyl ester; Above-mentioned 3rd mixed solution is heated to 50 ~ 120 DEG C, and the reaction times is 8 ~ 24 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: the 4th mixed solution=(5 ~ 15): 1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the intensive polar solvent centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.01 ~ 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in intensive polar solvent of surface grafting Polystearylmethacrylate.

Below introduce the embodiment of the inventive method:

Embodiment 1

(1) first silicon-dioxide is scattered in methyl alcohol, obtains the silicon dioxde solution that mass percent concentration is 30%; APTES is joined in silicon dioxde solution, make the volumetric molar concentration of APTES in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned methyl alcohol, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) dithiobenzoic acid isopropyl phenyl ester is added step (1) described methyl alcohol, obtain the dithiobenzoic acid isopropyl benzene ester solution that mass body volume concentrations is 3g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the methyl alcohol of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of surface grafting dithiobenzoic acid isopropyl phenyl ester, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the methyl alcohol of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and benzoyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the centrifugal product obtained is joined the dissolve with methanol of step (1), obtain the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in methyl alcohol of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Thermogravimetic analysis (TGA): Fig. 1 is the thermogravimetic analysis (TGA) test result of nano particle, and ordinate zou represents residual mass percentage, X-coordinate representation temperature.See from figure, nano particle residual mass per-cent 800 DEG C time of non-grafting is 97.4%, and the quality of loss comprises oh group and the tensio-active agent of nano grain surface.Polystearylmethacrylate engrafted nanometer silicon-dioxide quality 800 DEG C time also remains 50.4%, and Polystearylmethacrylate almost accounts for nano particle total mass half.

FTIR spectrum: Fig. 2 is the Fourier infrared spectrum of nano particle, and X-coordinate represents wave number, and ordinate zou represents transmissivity.Very strong absorption peak has been there is in the nano particle of Polystearylmethacrylate grafting in 2855 and 2924cm ~ 1 place, corresponding to hydrocarbyl functional group (as shown in Figure 1) corresponding on Polystearylmethacrylate molecule, wherein the absorption peak at 2957cm ~ 1 place is probably flooded by adjacent strong absorption peak.

Thermogravimetic analysis (TGA) and Fourier infrared spectrum analysis all indicate Polystearylmethacrylate and have been grafted on nano particle.

Respectively by the nano particle of non-grafting and grafted polymer brushes and polyethylene melt blending on close formula mixing roll, preparation compound Low Density Polyethylene, and make can for the sample of scanning electron microscopic observation.Adopt the microscopic appearance of scanning electron microscope observation bi-material section, find that nano particle dispersion effect in Low Density Polyethylene of graftomer is better.

After crosslinked to the hot pressing of two kinds of nano combined Low Density Polyethylenes employing linking agents, make nano combined crosslinked polyethylene, Fig. 3 and Fig. 4 that same employing scanning electron microscope obtains, observe its microscopic appearance, find that the dispersion effect of the nano particle of surface grafting Polystearylmethacrylate in crosslinked polyethylene is good, maximum particle size is 200 ran.

Embodiment 2

(1) first silicon-dioxide is scattered in ethanol, obtains the silicon dioxde solution that mass percent concentration is 30%; APTES is joined in silicon dioxde solution, make the volumetric molar concentration of APTES in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned ethanol, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) dithiobenzoic acid isopropyl phenyl ester is added step (1) described ethanol, obtain the dithiobenzoic acid isopropyl benzene ester solution that mass body volume concentrations is 3g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the ethanol of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of surface grafting dithiobenzoic acid isopropyl phenyl ester, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the ethanol of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and benzoyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the centrifugal product obtained is joined the dissolve with ethanol of step (1), obtain the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the nano silicon solution in ethanol of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 3

(1) first silicon-dioxide is scattered in methylethylketone, obtains the silicon dioxde solution that mass percent concentration is 30%; APTES is joined in silicon dioxde solution, make the volumetric molar concentration of APTES in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned methylethylketone, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) dithiobenzoic acid isopropyl phenyl ester is added step (1) described methylethylketone, obtain the dithiobenzoic acid isopropyl benzene ester solution that mass body volume concentrations is 3g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the methylethylketone of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of surface grafting dithiobenzoic acid isopropyl phenyl ester, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the methylethylketone of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and benzoyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the methylethylketone centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in methylethylketone of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 4

(1) first silicon-dioxide is scattered in trichloromethane, obtains the silicon dioxde solution that mass percent concentration is 30%; APTES is joined in silicon dioxde solution, make the volumetric molar concentration of APTES in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 55 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned trichloromethane, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) dithiobenzoic acid isopropyl phenyl ester is added step (1) described trichloromethane, obtain the dithiobenzoic acid isopropyl benzene ester solution that mass body volume concentrations is 3g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the trichloromethane of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of surface grafting dithiobenzoic acid isopropyl phenyl ester, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the trichloromethane of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and benzoyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 55 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the trichloromethane centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in trichloromethane of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 5

(1) first silicon-dioxide is scattered in tetrahydrofuran (THF), obtains the silicon dioxde solution that mass percent concentration is 30%; APTES is joined in silicon dioxde solution, make the volumetric molar concentration of APTES in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned tetrahydrofuran (THF), obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) dithiobenzoic acid isopropyl phenyl ester is added step (1) described tetrahydrofuran (THF), obtain the dithiobenzoic acid isopropyl benzene ester solution that mass body volume concentrations is 3g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the tetrahydrofuran (THF) of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of surface grafting dithiobenzoic acid isopropyl phenyl ester, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the tetrahydrofuran (THF) of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and benzoyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the tetrahydrofuran (THF) centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in tetrahydrofuran (THF) of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 6

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; APTES is joined in silicon dioxde solution, make the volumetric molar concentration of APTES in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) dithiobenzoic acid isopropyl phenyl ester is added step (1) described toluene, obtain the dithiobenzoic acid isopropyl benzene ester solution that mass body volume concentrations is 3g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of surface grafting dithiobenzoic acid isopropyl phenyl ester, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and benzoyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 7

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 3-TSL 8330 is joined in silicon dioxde solution, makes the volumetric molar concentration of 3-TSL 8330 in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) dithiobenzoic acid isopropyl phenyl ester is added step (1) described toluene, obtain the dithiobenzoic acid isopropyl benzene ester solution that mass body volume concentrations is 3g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of surface grafting dithiobenzoic acid isopropyl phenyl ester, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and benzoyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 8

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 3-dimethyl methoxy silane is joined in silicon dioxde solution, makes the volumetric molar concentration of 3-dimethyl methoxy silane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) dithiobenzoic acid isopropyl phenyl ester is added step (1) described toluene, obtain the dithiobenzoic acid isopropyl benzene ester solution that mass body volume concentrations is 3g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of surface grafting dithiobenzoic acid isopropyl phenyl ester, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and benzoyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 9

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 4-ammobutyltriethoxysilane is joined in silicon dioxde solution, makes the volumetric molar concentration of 4-ammobutyltriethoxysilane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) dithiobenzoic acid isopropyl phenyl ester is added step (1) described toluene, obtain the dithiobenzoic acid isopropyl benzene ester solution that mass body volume concentrations is 3g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of surface grafting dithiobenzoic acid isopropyl phenyl ester, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and benzoyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 10

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 4-ammobutyltriethoxysilane is joined in silicon dioxde solution, makes the volumetric molar concentration of 4-ammobutyltriethoxysilane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) trithiocarbonate is added step (1) described toluene, obtain the trithiocarbonic acid ester solution that mass body volume concentrations is 3g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: trithiocarbonate: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of surface grafting trithiocarbonate, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and benzoyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 11

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 4-ammobutyltriethoxysilane is joined in silicon dioxde solution, makes the volumetric molar concentration of 4-ammobutyltriethoxysilane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) 4-cyano group-4-(thiobenzoyl) valeric acid is added step (1) described toluene, obtain 4-cyano group-4-(thiobenzoyl) the valeric acid solution that mass body volume concentrations is 3g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: 4-cyano group-4-(thiobenzoyl) valeric acid: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtain the nano silicon of surface grafting 4-cyano group-4-(thiobenzoyl) valeric acid, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and benzoyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 12

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 4-ammobutyltriethoxysilane is joined in silicon dioxde solution, makes the volumetric molar concentration of 4-ammobutyltriethoxysilane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) dithio benzoyl is added step (1) described toluene, obtain the dithio benzoyl solution that mass body volume concentrations is 3g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: dithio benzoyl: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of surface grafting dithio benzoyl, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and benzoyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 13

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 4-ammobutyltriethoxysilane is joined in silicon dioxde solution, makes the volumetric molar concentration of 4-ammobutyltriethoxysilane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) withered for dithiobenzoic acid ester is added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's or the withered ester solution of dithiobenzoic acid; Dropwise add described first solution of step (1) wherein, the volume ratio added is: the withered ester of dithiobenzoic acid: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of the withered ester of surface grafting dithiobenzoic acid, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and benzoyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 14

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 4-ammobutyltriethoxysilane is joined in silicon dioxde solution, makes the volumetric molar concentration of 4-ammobutyltriethoxysilane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) withered for dithiobenzoic acid ester is added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's or the withered ester solution of dithiobenzoic acid; Dropwise add described first solution of step (1) wherein, the volume ratio added is: the withered ester of dithiobenzoic acid: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of the withered ester of surface grafting dithiobenzoic acid, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and diacetyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: diacetyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 15

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 4-ammobutyltriethoxysilane is joined in silicon dioxde solution, makes the volumetric molar concentration of 4-ammobutyltriethoxysilane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) withered for dithiobenzoic acid ester is added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's or the withered ester solution of dithiobenzoic acid; Dropwise add described first solution of step (1) wherein, the volume ratio added is: the withered ester of dithiobenzoic acid: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of the withered ester of surface grafting dithiobenzoic acid, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and dioctanoyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: dioctanoyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 16

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 4-ammobutyltriethoxysilane is joined in silicon dioxde solution, makes the volumetric molar concentration of 4-ammobutyltriethoxysilane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) withered for dithiobenzoic acid ester is added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's or the withered ester solution of dithiobenzoic acid; Dropwise add described first solution of step (1) wherein, the volume ratio added is: the withered ester of dithiobenzoic acid: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of the withered ester of surface grafting dithiobenzoic acid, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and 2,2'-Azobis(2,4-dimethylvaleronitrile) by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: 2,2'-Azobis(2,4-dimethylvaleronitrile)=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 17

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 4-ammobutyltriethoxysilane is joined in silicon dioxde solution, makes the volumetric molar concentration of 4-ammobutyltriethoxysilane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) withered for dithiobenzoic acid ester is added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's or the withered ester solution of dithiobenzoic acid; Dropwise add described first solution of step (1) wherein, the volume ratio added is: the withered ester of dithiobenzoic acid: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of the withered ester of surface grafting dithiobenzoic acid, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and Diisopropyl azodicarboxylate by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: Diisopropyl azodicarboxylate=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 18

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 4-ammobutyltriethoxysilane is joined in silicon dioxde solution, makes the volumetric molar concentration of 4-ammobutyltriethoxysilane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) withered for dithiobenzoic acid ester is added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's or the withered ester solution of dithiobenzoic acid; Dropwise add described first solution of step (1) wherein, the volume ratio added is: the withered ester of dithiobenzoic acid: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of the withered ester of surface grafting dithiobenzoic acid, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and peroxidized t-butyl perbenzoate by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: peroxidized t-butyl perbenzoate=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 19

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 4-ammobutyltriethoxysilane is joined in silicon dioxde solution, makes the volumetric molar concentration of 4-ammobutyltriethoxysilane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) withered for dithiobenzoic acid ester is added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's or the withered ester solution of dithiobenzoic acid; Dropwise add described first solution of step (1) wherein, the volume ratio added is: the withered ester of dithiobenzoic acid: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of the withered ester of surface grafting dithiobenzoic acid, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and the peroxidation trimethylacetic acid tert-butyl ester by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: the peroxidation trimethylacetic acid tert-butyl ester=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 20

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 4-ammobutyltriethoxysilane is joined in silicon dioxde solution, makes the volumetric molar concentration of 4-ammobutyltriethoxysilane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) withered for dithiobenzoic acid ester is added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's or the withered ester solution of dithiobenzoic acid; Dropwise add described first solution of step (1) wherein, the volume ratio added is: the withered ester of dithiobenzoic acid: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of the withered ester of surface grafting dithiobenzoic acid, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and isopropyl benzene hydroperoxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: isopropyl benzene hydroperoxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 21

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 4-ammobutyltriethoxysilane is joined in silicon dioxde solution, makes the volumetric molar concentration of 4-ammobutyltriethoxysilane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) withered for dithiobenzoic acid ester is added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's or the withered ester solution of dithiobenzoic acid; Dropwise add described first solution of step (1) wherein, the volume ratio added is: the withered ester of dithiobenzoic acid: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of the withered ester of surface grafting dithiobenzoic acid, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Mixed with stearyl methacrylate and tertbutyl peroxide by second solution, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, the second solution: tertbutyl peroxide=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Embodiment 22

(1) first silicon-dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%; 4-ammobutyltriethoxysilane is joined in silicon dioxde solution, makes the volumetric molar concentration of 4-ammobutyltriethoxysilane in silicon dioxde solution be 3mol/L, and at nitrogen atmosphere, reflux 12 hours at 60 DEG C, obtain the first mixed solution; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=10:1, after waiting for that solid precipitates completely, carries out centrifugation to this mixture, and isolated solid is dissolved in above-mentioned toluene, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) withered for dithiobenzoic acid ester is added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's or the withered ester solution of dithiobenzoic acid; Dropwise add described first solution of step (1) wherein, the volume ratio added is: the withered ester of dithiobenzoic acid: the first solution=1:1, at room temperature stirs 8 hours, obtains the second mixed solution; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=4:1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=10:1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the toluene of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of the withered ester of surface grafting dithiobenzoic acid, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the toluene of step (1), obtain the solution that mass body volume concentrations is 3g/mL, be designated as the second solution; Second solution is mixed with stearyl methacrylate and peroxy dicarbonate diisobutyl ester, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:1, second solution: peroxy dicarbonate diisobutyl ester=1:0.001, obtains the 3rd mixed solution; Above-mentioned 3rd mixed solution is heated to 60 DEG C, and the reaction times is 12 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: four mixed solution=10:1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the toluene centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in toluene of surface grafting Polystearylmethacrylate, solution sealing is preserved.

Claims (1)

1. a preparation method for surface grafting Polystearylmethacrylate nano silicon, is characterized in that this preparation method comprises the following steps:

(1) be first scattered in intensive polar solvent by silicon-dioxide, obtain the silicon dioxde solution that mass percent concentration is 10% ~ 40%, described intensive polar solvent is: methyl alcohol, ethanol, methylethylketone, trichloromethane, tetrahydrofuran (THF) or toluene; Aminosilane is joined in silicon dioxde solution, the volumetric molar concentration of aminosilane in silicon dioxde solution is made to be 1 ~ 10mol/L, and at nitrogen atmosphere, reflux 5 ~ 24 hours at 50 ~ 120 DEG C, obtain the first mixed solution, described aminosilane is APTES, 3-TSL 8330,3-dimethyl methoxy silane or 4-ammobutyltriethoxysilane; At normal temperatures normal hexane is added the first mixed solution, adding volume ratio is: normal hexane: the first mixed solution=(5 ~ 15): 1, after waiting for that solid precipitates completely, centrifugation is carried out to this mixture, and isolated solid is dissolved in above-mentioned intensive polar solvent, obtain the solution that mass body volume concentrations is 0.01 ~ 0.4g/mL; Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain the nanosilica solution of surface grafting aminosilane, be designated as the first solution;

(2) chain-transfer agent is added step (1) described intensive polar solvent, obtain the chain-transfer agent solution that mass body volume concentrations is 1 ~ 5g/mL; Dropwise add described first solution of step (1) wherein, the volume ratio added is: chain-transfer agent: the first solution=1:(0.5 ~ 2), at room temperature stir 6 ~ 12 hours, obtain the second mixed solution, described chain-transfer agent is dithiobenzoic acid isopropyl phenyl ester, trithiocarbonate, 4-cyano group-4-(thiobenzoyl) valeric acid, dithio benzoyl or the withered ester of dithiobenzoic acid; Mixed mutually with ethyl acetate by hexanaphthene, obtain mixed solvent, the volume ratio of mixing is: hexanaphthene: ethyl acetate=(2 ~ 6): 1; Mixed solvent is joined at normal temperatures in above-mentioned second mixed solution, the volume ratio added is: mixed solvent: the second mixed solution=(5 ~ 15): 1, by the time precipitate after separating out completely and carry out centrifugation, and the centrifugal product obtained is joined in the intensive polar solvent of step (1) dissolve, obtain the solution that mass body volume concentrations is 0.01 ~ 0.4g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after precipitation, by the at room temperature vacuum-drying of centrifugation product, obtains the nano silicon of surface grafting chain-transfer agent, be designated as the first nano particle;

(3) by above-mentioned first nanoparticulate dispersed in the intensive polar solvent of step (1), obtain the solution that mass body volume concentrations is 2 ~ 10g/mL, be designated as the second solution; Second solution is mixed with stearyl methacrylate and initiator, the volume ratio of mixing is respectively: the second solution: stearyl methacrylate=1:(0.5 ~ 2), second solution: initiator=1:(0.005 ~ 0.05), obtain the 3rd mixed solution, described initiator is any one in benzoyl peroxide, diacetyl peroxide, dioctanoyl peroxide, 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester, isopropyl benzene hydroperoxide, tertbutyl peroxide or peroxy dicarbonate diisobutyl ester; Above-mentioned 3rd mixed solution is heated to 50 ~ 120 DEG C, and the reaction times is 8 ~ 24 hours, obtains the 4th mixed solution; At normal temperatures normal hexane is joined in above-mentioned 4th mixed solution, the volume ratio added is: normal hexane: the 4th mixed solution=(5 ~ 15): 1, after precipitation completely to be precipitated, centrifugation is carried out to this mixture, the intensive polar solvent centrifugal product obtained being joined step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.01 ~ 0.3g/mL; Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain the solution of nano silicon in intensive polar solvent of surface grafting Polystearylmethacrylate.