CN104497641B - The preparation method of surface grafting Polystearylmethacrylate nano silicon - Google Patents
The preparation method of surface grafting Polystearylmethacrylate nano silicon Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of surface grafting Polystearylmethacrylate nano silicon, belong to nano grain surface graft modification field.The present invention uses reversible addition to temper the polymerization of transfer, first in intensive polar solvent, amino silane is grafted to nano-silica surface；Then by the combination of the thioesters functional group on chain-transferring agent with amido functional group, chain-transferring agent is grafted to nano grain surface through these amino silanes；Finally being provided free radical by initiator, the monomer of octadecyl methacrylate is at chain-transferring agent end polymeric.Polystearylmethacrylate grafted silica nano-particle prepared by this method, improves the dispersibility in nano silicon dispersibility in low-density in polyethylene and crosslinked polyethylene matrix.The inventive method is to improve the performances such as the mechanics of polyvinyl nano composite material, electricity further to have established solid foundation.
Description
Technical field
The present invention relates to the preparation method of a kind of surface grafting Polystearylmethacrylate nano silicon, belong to nanometer
Grain surface graft modification field.
Background technology
Since entering 21 century, the application of nanotechnology gets more and more, and the impetus of material industry is not allowed gently by especially
Depending on.Each industrialized country all puts into substantial contribution research nano-macromolecule material, to adapt to growing industrial requirement,
And gradually form an international competition.
Nano-particle adds the performance boost of macromolecular material, and to be nanotechnology important to one of material Industrial driving effect
Embodying, suitable nano-particle adds sides such as can improving the mechanics of macromolecular material, optics, electricity, biology well
The performance in face.But, nano-particle has the advantages that volume is little and surface energy is big, generally with high molecular polymerization matrix not phase
Hold, and due to mutual captivation, cause nano-particle easily to be reunited, thus reunite with micron-scale in complex media
Coexist with the form of nano-particle and be distributed.From the point of view of nano-dispersibility angle, above-mentioned complex media can not be referred to as really
Nano-filled composite in meaning, existing research also indicate that nano-dispersibility be the key affecting nano-filled composite performance because of
Element.Therefore, before nano-particle adds high molecular polymer matrix to, generally require and it is modified, i.e. use certain
Nano grain surface modified by material, changes mi-crochemistry and the physical property at interface between nano-particle and polymeric matrix, thus
Improve nano-particle dispersibility in polymeric matrix, give full play of the characteristic that nano-particle is excellent.
Nano grain surface graft modification generally has two class methods, i.e. physical modification and chemical modification.The former refer to by absorption,
Particle surface is modified by the physical means such as coating, cladding；The latter refers to by dressing agent molecule and nano grain surface atom
Or special functional group occurs chemical reaction, thus it is fixing to realize grafting.Wherein, the nano-particle after chemical modification processes divides
Dissipate property more preferable, obtained in actual applications promoting in large quantities.
Chemical modification includes surfactant method and surface grafting polymerization method: the surfactant that (1) is commonly used has: silanes is even
Connection agent, stearic acid and organosilicon etc., the method is simple to operate, is the most frequently used chemical modification method, but owing to living in surface
Property agent is not the most macromolecular material, the biggest with the molecular structure of polymeric matrix and molecular weight difference, it is impossible to polymer chain phase
Infiltration mutually, thus unsatisfactory to the improvement effect of nano-particle dispersibility；(2) surface grafting polymerization method has become as nanometer
Granule modified important means, glycerol polymerization species is many, and controllability is good.And controllable free-radical polymerisation method is surface at present
A topmost class method in graft polymerization method.
Controllable free-radical polymerisation method utilizes the balance between Propagating Radical and all kinds of dormancy kind, control polymer molecular weight,
Molecular weight distribution and the Raolical polymerizable of terminated functional, including oxygen nitrogen stable free radical polymerization method, atom transfer freely
Base polymerization and reversible addition～chain rupture transfer polymerization method.Polymer brush surface graft modification nano-particle relative to other
Method, the suitable monomers kind of reversible addition～chain rupture transfer polymerization method is more, and reaction condition requires relatively low, graft polymers
Molecular weight distribution narrower, post processing is simple, it is adaptable to the multiple system such as solution, suspension polymerisation.Due to these advantages, can
Inverse addition～chain rupture transfer polymerization method become the important method of nano grain surface graft modification, in the preparation of nano-filled composite
In be widely used.
In Polymer Material Industry, polyethylene is good with its chemical stability, cheap, mature preparation process, insulating properties
Advantage can be waited well, occupy first of the yield of general synthetic resin, be widely used in agricultural, packaging, electric, mechanical,
The aspect such as automobile, daily use Sundry goods.Polyethylene includes Low Density Polyethylene, high density polyethylene (HDPE), crosslinked polyethylene etc., along with
Emerging in large numbers of new technique, the performance of polyethylene is in constantly improvement, and cost is persistently reducing, high-performance polyethylene technical field simultaneously
Competition be also growing more intense.Add nano-particle and be undoubtedly a focus of high-performance polyethylene based composite dielectric research direction.
Summary of the invention
The purpose of the present invention is to propose to the preparation method of a kind of surface grafting Polystearylmethacrylate nano silicon, with
Improve nano silicon dispersibility in polyethylene, thus provide for preparing high-performance polyethylene base nano-filled composite
Maximum likelihood.
The preparation method of the surface grafting Polystearylmethacrylate nano silicon that the present invention proposes, including following step
Rapid:
(1) first silicon dioxide is scattered in intensive polar solvent, obtains the dioxy that mass percent concentration is 10%～40%
SiClx solution, described intensive polar solvent is: methanol, ethanol, butanone, chloroform, oxolane or toluene；Will
Amino silane joins in silicon dioxde solution, and making amino silane molar concentration in silicon dioxde solution is 1～10
Mol/L, and at nitrogen atmosphere, reflux 5～24 hours at 50～120 DEG C, obtain the first mixed liquor, described amino silane
For APTES, 3-TSL 8330,3-dimethyl methoxy silane or 4-
Ammobutyltriethoxysilane；Normal hexane adds the first mixed liquor at normal temperatures, and adding volume ratio is: normal hexane: the
One mixed liquor=(5～15): 1, after waiting that solid precipitates completely, are centrifuged this mixture separating, and by isolated
Solid is dissolved in above-mentioned intensive polar solvent, obtains the solution that mass body volume concentrations is 0.01～0.4g/mL；Repeat above-mentioned precipitation-
Centrifugal-dissolving step, finally obtains the nanosilica solution of surface grafting amino silane, is designated as the first solution；
(2) chain-transferring agent adding step (1) described intensive polar solvent, obtaining mass body volume concentrations is 1～5g/mL
Chain-transferring agent solution；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is: chain-transferring agent: the
One solution=1:(0.5～2), it is stirred at room temperature 6～12 hours, obtains the second mixed liquor, described chain-transferring agent is two
Thiobenzoate isopropyl phenyl ester, trithiocarbonate, 4-cyano group-4-(thiobenzoyl) valeric acid, dithio benzoyl or two
The withered ester of thiobenzoate；Being mixed mutually with ethyl acetate by hexamethylene, obtain mixed solvent, the volume ratio of mixing is: hexamethylene:
Ethyl acetate=(2～6): 1；Being joined by mixed solvent in above-mentioned second mixed liquor at normal temperatures, the volume ratio of addition is:
Mixed solvent: the second mixed liquor=(5～15): 1, waits until that precipitation carries out centrifugation after separating out completely, and by obtain from
Heart product joins in the intensive polar solvent of step (1) and dissolves, and obtains 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 Chen Dian, by centrifugation product in room temperature
Lower vacuum drying, obtains the nano silicon of surface grafting chain-transferring agent, is designated as the first nano-particle；
(3) above-mentioned first nano-particle is scattered in the intensive polar solvent of step (1), obtain mass body volume concentrations be 2～
The solution of 10g/mL, is designated as the second solution；Second solution is mixed with octadecyl methacrylate and initiator, mixing
Volume ratio is respectively as follows: the second solution: octadecyl methacrylate=1:(0.5～2), the second solution: initiator=1:(0.005～
0.05), obtain the 3rd mixed liquor, described initiator be benzoyl peroxide, diacetyl peroxide, dioctanoyl peroxide,
2,2'-Azobis(2,4-dimethylvaleronitrile), azodiisobutyronitrile, peroxidized t-butyl perbenzoate, the peroxidating pivalic acid tert-butyl ester, isopropylbenzene peroxide
Change any one of hydrogen, tert-butyl hydroperoxide or peroxy dicarbonate diisobutyl ester；Above-mentioned 3rd mixed liquor is heated to
50～120 DEG C, the response time is 8～24 hours, obtains the 4th mixed liquor；At normal temperatures normal hexane is joined above-mentioned
In four mixed liquors, the volume ratio of addition is: normal hexane: the 4th mixed liquor=(5～15): 1, after precipitation completely to be precipitated,
Being centrifuged this mixture separating, the intensive polar solvent that the centrifugal product obtained joins step (1) dissolves, and obtains
Mass body volume concentrations is the solution of 0.01～0.3g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain surface
The nano silicon of grafting Polystearylmethacrylate solution in intensive polar solvent.
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 by reversible addition～disconnected
Split chain transfer polymerization method to be incorporated in polyethylene based composition system, due to Polystearylmethacrylate and polyethylene backbone
The common exercising result of the Van der Waals force being mutually wound around and attract each other between screen nano granule, improves nano silicon
The dispersibility in polyethylene in low-density, then after low density polyethylene cross-linked, also significantly improves nanometer titanium dioxide
Silicon dispersibility in crosslinked polyethylene matrix.The nano grain surface grafting method that the present invention proposes is to improve poly-second further
The performances such as the mechanics of thiazolinyl nano composite material, electricity have established solid foundation.In terms of mechanics, polyethylene can be improved
The storage modulus of based nano composite material, elastic modelling quantity and hardness modulus；In terms of calorifics, its glassy transition can be improved
Temperature；In terms of optics, the absorbance of light can be improved, and improve material to ultraviolet and ultrared shield effectiveness；?
Electricity aspect, can improve its breakdown voltage, and suppress space charge.
The nano-silica surface grafting method used in the present invention has universality, is particularly well-suited to surface and has hydroxyl base
The nano-particle of group.
Accompanying drawing explanation
Fig. 1 is non-grafted in embodiment 1 and the thermogravimetic analysis (TGA) knot of the nano silicon of grafting Polystearylmethacrylate
Really；
Fig. 2 is non-grafted in embodiment 1 and the infrared spectrum of the nano silicon of grafting Polystearylmethacrylate；
Fig. 3 is the scanning electron microscope (SEM) photograph of non-grafted nano silicon compound crosslinked polyethylene in embodiment 1；
Fig. 4 is the scanning electricity of the nano silicon compound crosslinked polyethylene being grafted Polystearylmethacrylate in embodiment 1
Mirror figure.
Detailed description of the invention
The preparation method of the surface grafting Polystearylmethacrylate nano silicon that the present invention proposes, including following step
Rapid:
(1) first silicon dioxide is scattered in intensive polar solvent, obtains the dioxy that mass percent concentration is 10%～40%
SiClx solution, described intensive polar solvent is: methanol, ethanol, butanone, chloroform, oxolane or toluene；Will
Amino silane joins in silicon dioxde solution, and making amino silane molar concentration in silicon dioxde solution is 1～10
Mol/L, and at nitrogen atmosphere, reflux 5～24 hours at 50～120 DEG C, obtain the first mixed liquor, described amino silane
For APTES, 3-TSL 8330,3-dimethyl methoxy silane or 4-
Ammobutyltriethoxysilane；Normal hexane adds the first mixed liquor at normal temperatures, and adding volume ratio is: normal hexane: the
One mixed liquor=(5～15): 1, after waiting that solid precipitates completely, are centrifuged this mixture separating, and by isolated
Solid is dissolved in above-mentioned intensive polar solvent, obtains the solution that mass body volume concentrations is 0.01～0.4g/mL；Repeat above-mentioned precipitation-
Centrifugal-dissolving step, finally obtains the nanosilica solution of surface grafting amino silane, is designated as the first solution；
(2) chain-transferring agent adding step (1) described intensive polar solvent, obtaining mass body volume concentrations is 1～5g/mL
Chain-transferring agent solution；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is: chain-transferring agent: the
One solution=1:(0.5～2), it is stirred at room temperature 6～12 hours, obtains the second mixed liquor, described chain-transferring agent is two
Thiobenzoate isopropyl phenyl ester, trithiocarbonate, 4-cyano group-4-(thiobenzoyl) valeric acid, dithio benzoyl or two
The withered ester of thiobenzoate；Being mixed mutually with ethyl acetate by hexamethylene, obtain mixed solvent, the volume ratio of mixing is: hexamethylene:
Ethyl acetate=(2～6): 1；Being joined by mixed solvent in above-mentioned second mixed liquor at normal temperatures, the volume ratio of addition is:
Mixed solvent: the second mixed liquor=(5～15): 1, waits until that precipitation carries out centrifugation after separating out completely, and by obtain from
Heart product joins in the intensive polar solvent of step (1) and dissolves, and obtains 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 Chen Dian, by centrifugation product in room temperature
Lower vacuum drying, obtains the nano silicon of surface grafting chain-transferring agent, is designated as the first nano-particle；
(3) above-mentioned first nano-particle is scattered in the intensive polar solvent of step (1), obtain mass body volume concentrations be 2～
The solution of 10g/mL, is designated as the second solution；Second solution is mixed with octadecyl methacrylate and initiator, mixing
Volume ratio is respectively as follows: the second solution: octadecyl methacrylate=1:(0.5～2), the second solution: initiator=1:(0.005～
0.05), obtain the 3rd mixed liquor, described initiator be benzoyl peroxide, diacetyl peroxide, dioctanoyl peroxide,
2,2'-Azobis(2,4-dimethylvaleronitrile), azodiisobutyronitrile, peroxidized t-butyl perbenzoate, the peroxidating pivalic acid tert-butyl ester, isopropylbenzene peroxide
Change any one of hydrogen, tert-butyl hydroperoxide or peroxy dicarbonate diisobutyl ester；Above-mentioned 3rd mixed liquor is heated to
50～120 DEG C, the response time is 8～24 hours, obtains the 4th mixed liquor；At normal temperatures normal hexane is joined above-mentioned
In four mixed liquors, the volume ratio of addition is: normal hexane: the 4th mixed liquor=(5～15): 1, after precipitation completely to be precipitated,
Being centrifuged this mixture separating, the intensive polar solvent that the centrifugal product obtained joins step (1) dissolves, and obtains
Mass body volume concentrations is the solution of 0.01～0.3g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain surface
The nano silicon of grafting Polystearylmethacrylate solution in intensive polar solvent.
The embodiment of the inventive method introduced below:
Embodiment 1
(1) first silicon dioxide is scattered in methanol, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
APTES joins in silicon dioxde solution, makes APTES at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned methanol, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) dithiobenzoic acid isopropyl phenyl ester being added step (1) described methanol, obtaining mass body volume concentrations is 3g/mL
Dithiobenzoic acid isopropylbenzene ester solution；It is added dropwise over described first solution of step (1), the volume ratio of addition wherein
For: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, it is stirred at room temperature 8 hours, obtains the second mixed liquor；Will
Hexamethylene mixes mutually with ethyl acetate, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；Will
Mixed solvent joins in above-mentioned second mixed liquor at normal temperatures, and the volume ratio of addition is: mixed solvent: the second mixed liquor
=10:1, waits until that precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins the methanol of step (1)
Middle dissolving, obtains the solution that mass body volume concentrations is 0.3g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Until supernatant liquid is colourless after Chen Dian, centrifugation product is at room temperature vacuum dried, obtains surface grafting dithio benzene first
The nano silicon of acid isopropyl phenyl ester, is designated as the first nano-particle；
(3) being scattered in the methanol of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and benzoyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Alcohol dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in methanol, solution is sealed and preserves.
Thermogravimetic analysis (TGA): Fig. 1 is the thermogravimetic analysis (TGA) test result of nano-particle, and vertical coordinate represents percentage shared by residual mass
Ratio, abscissa represents temperature.Seeing from figure, non-grafted nano-particle residual mass percentage ratio when 800 DEG C is 97.4%,
The quality of loss includes oh group and the surfactant of nano grain surface.Polystearylmethacrylate engrafted nanometer two
Silicon oxide quality when 800 DEG C also remains 50.4%, and Polystearylmethacrylate almost accounts for nano-particle gross mass half.
FTIR spectrum: Fig. 2 is the Fourier infrared spectrum of nano-particle, and abscissa represents wave number, and vertical coordinate represents
Absorbance.The nano-particle of Polystearylmethacrylate grafting occurs in that the strongest suction at 2855 and 2924cm～1
Receive peak, corresponding to hydrocarbyl functional group (as shown in Figure 1) corresponding on Polystearylmethacrylate molecule, wherein 2957cm～
Absworption peak at 1 is likely to be flooded by adjacent strong absworption peak.
Thermogravimetic analysis (TGA) and Fourier infrared spectrum analysis all indicate Polystearylmethacrylate and have been grafted on nanometer
On grain.
Respectively by the non-grafted and nano-particle of grafted polymer brushes and polyethylene melt blending on close formula mixing roll, preparation is multiple
Close Low Density Polyethylene, and make the sample being available for scanning electron microscopic observation.Use the micro-of scanning electron microscope observation bi-material section
See pattern, find that nano-particle dispersion effect in Low Density Polyethylene of graft polymers is preferable.
After two kinds of nano combined Low Density Polyethylenes are used cross-linking agent hot pressing crosslinking, make the poly-second of nano combined crosslinking
Alkene, same Fig. 3 and Fig. 4 using scanning electron microscope to obtain, observes its microscopic appearance, finds surface grafting polymethylacrylic acid
The nano-particle of octadecyl ester dispersion effect in crosslinked polyethylene is good, and 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%；Will
APTES joins in silicon dioxde solution, makes APTES at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned ethanol, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) dithiobenzoic acid isopropyl phenyl ester being added step (1) described ethanol, obtaining mass body volume concentrations is 3g/mL
Dithiobenzoic acid isopropylbenzene ester solution；It is added dropwise over described first solution of step (1), the volume ratio of addition wherein
For: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, it is stirred at room temperature 8 hours, obtains the second mixed liquor；Will
Hexamethylene mixes mutually with ethyl acetate, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；Will
Mixed solvent joins in above-mentioned second mixed liquor at normal temperatures, and the volume ratio of addition is: mixed solvent: the second mixed liquor
=10:1, waits until that precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins the ethanol of step (1)
Middle dissolving, obtains the solution that mass body volume concentrations is 0.3g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Until supernatant liquid is colourless after Chen Dian, centrifugation product is at room temperature vacuum dried, obtains surface grafting dithio benzene first
The nano silicon of acid isopropyl phenyl ester, is designated as the first nano-particle；
(3) being scattered in the ethanol of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and benzoyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the second of step (1)
Alcohol dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of surface grafting Polystearylmethacrylate solution in ethanol, solution is sealed and preserves.
Embodiment 3
(1) first silicon dioxide is scattered in butanone, obtains the silicon dioxde solution that mass percent concentration is 30%；
APTES is joined in silicon dioxde solution, make APTES at dioxy
Molar concentration in SiClx solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；
Normal hexane adds the first mixed liquor at normal temperatures, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits solid
Completely after precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned butanone, obtain quality
Volumetric concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silicone
The nanosilica solution of alkane, is designated as the first solution；
(2) dithiobenzoic acid isopropyl phenyl ester being added step (1) described butanone, obtaining mass body volume concentrations is 3g/mL
Dithiobenzoic acid isopropylbenzene ester solution；It is added dropwise over described first solution of step (1), the volume ratio of addition wherein
For: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, it is stirred at room temperature 8 hours, obtains the second mixed liquor；Will
Hexamethylene mixes mutually with ethyl acetate, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；Will
Mixed solvent joins in above-mentioned second mixed liquor at normal temperatures, and the volume ratio of addition is: mixed solvent: the second mixed liquor
=10:1, waits until that precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins the first and second of step (1)
Ketone dissolves, obtains the solution that mass body volume concentrations is 0.3g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Until supernatant liquid is colourless after Chen Dian, centrifugation product is at room temperature vacuum dried, obtains surface grafting dithio benzene first
The nano silicon of acid isopropyl phenyl ester, is designated as the first nano-particle；
(3) being scattered in the butanone of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and benzoyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Ethyl ketone dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in butanone, solution is sealed and preserves.
Embodiment 4
(1) first silicon dioxide is scattered in chloroform, obtains the silicon dioxde solution that mass percent concentration is 30%；
APTES is joined in silicon dioxde solution, make APTES at dioxy
Molar concentration in SiClx solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 55 DEG C；
Normal hexane adds the first mixed liquor at normal temperatures, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits solid
Completely after precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned chloroform, obtain matter
Amount volumetric concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino
The nanosilica solution of silane, is designated as the first solution；
(2) dithiobenzoic acid isopropyl phenyl ester being added step (1) described chloroform, obtaining mass body volume concentrations is 3g/mL
Dithiobenzoic acid isopropylbenzene ester solution；It is added dropwise over described first solution of step (1), the volume ratio of addition wherein
For: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, it is stirred at room temperature 8 hours, obtains the second mixed liquor；Will
Hexamethylene mixes mutually with ethyl acetate, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；Will
Mixed solvent joins in above-mentioned second mixed liquor at normal temperatures, and the volume ratio of addition is: mixed solvent: the second mixed liquor
=10:1, waits until that precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins the trichlorine of step (1)
Methane dissolves, obtains the solution that mass body volume concentrations is 0.3g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step
Suddenly, until supernatant liquid is colourless after Chen Dian, centrifugation product is at room temperature vacuum dried, obtains surface grafting dithio
The nano silicon of benzoic acid isopropyl phenyl ester, is designated as the first nano-particle；
(3) being scattered in the chloroform of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and benzoyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 55 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the three of step (1)
Chloromethanes dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step
Suddenly, obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in chloroform, solution is sealed
Preserve.
Embodiment 5
(1) first silicon dioxide is scattered in oxolane, obtains the silicon dioxde solution that mass percent concentration is 30%；
APTES is joined in silicon dioxde solution, make APTES at dioxy
Molar concentration in SiClx solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；
Normal hexane adds the first mixed liquor at normal temperatures, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits solid
Completely after precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned oxolane, obtain matter
Amount volumetric concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino
The nanosilica solution of silane, is designated as the first solution；
(2) dithiobenzoic acid isopropyl phenyl ester being added step (1) described oxolane, obtaining mass body volume concentrations is 3g/mL
Dithiobenzoic acid isopropylbenzene ester solution；It is added dropwise over described first solution of step (1), the volume ratio of addition wherein
For: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, it is stirred at room temperature 8 hours, obtains the second mixed liquor；Will
Hexamethylene mixes mutually with ethyl acetate, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；Will
Mixed solvent joins in above-mentioned second mixed liquor at normal temperatures, and the volume ratio of addition is: mixed solvent: the second mixed liquor
=10:1, waits until that precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins the tetrahydrochysene of step (1)
Furan dissolves, obtains the solution that mass body volume concentrations is 0.3g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step
Suddenly, until supernatant liquid is colourless after Chen Dian, centrifugation product is at room temperature vacuum dried, obtains surface grafting dithio
The nano silicon of benzoic acid isopropyl phenyl ester, is designated as the first nano-particle；
(3) being scattered in the oxolane of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and benzoyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the four of step (1)
Hydrogen furan dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step
Suddenly, obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in oxolane, solution is sealed
Preserve.
Embodiment 6
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
APTES joins in silicon dioxde solution, makes APTES at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) dithiobenzoic acid isopropyl phenyl ester being added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL
Dithiobenzoic acid isopropylbenzene ester solution；It is added dropwise over described first solution of step (1), the volume ratio of addition wherein
For: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, it is stirred at room temperature 8 hours, obtains the second mixed liquor；Will
Hexamethylene mixes mutually with ethyl acetate, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；Will
Mixed solvent joins in above-mentioned second mixed liquor at normal temperatures, and the volume ratio of addition is: mixed solvent: the second mixed liquor
=10:1, waits until that precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins the toluene of step (1)
Middle dissolving, obtains the solution that mass body volume concentrations is 0.3g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Until supernatant liquid is colourless after Chen Dian, centrifugation product is at room temperature vacuum dried, obtains surface grafting dithio benzene first
The nano silicon of acid isopropyl phenyl ester, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and benzoyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Benzene dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, solution is sealed and preserves.
Embodiment 7
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
3-TSL 8330 joins in silicon dioxde solution, makes 3-TSL 8330 at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) dithiobenzoic acid isopropyl phenyl ester being added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL
Dithiobenzoic acid isopropylbenzene ester solution；It is added dropwise over described first solution of step (1), the volume ratio of addition wherein
For: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, it is stirred at room temperature 8 hours, obtains the second mixed liquor；Will
Hexamethylene mixes mutually with ethyl acetate, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；Will
Mixed solvent joins in above-mentioned second mixed liquor at normal temperatures, and the volume ratio of addition is: mixed solvent: the second mixed liquor
=10:1, waits until that precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins the toluene of step (1)
Middle dissolving, obtains the solution that mass body volume concentrations is 0.3g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Until supernatant liquid is colourless after Chen Dian, centrifugation product is at room temperature vacuum dried, obtains surface grafting dithio benzene first
The nano silicon of acid isopropyl phenyl ester, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and benzoyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Benzene dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, solution is sealed and preserves.
Embodiment 8
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
3-dimethyl methoxy silane joins in silicon dioxde solution, makes 3-dimethyl methoxy silane at dioxy
Molar concentration in SiClx solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；
Normal hexane adds the first mixed liquor at normal temperatures, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits solid
Completely after precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain mass body
Volume concentrations is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, be designated as the first solution；
(2) dithiobenzoic acid isopropyl phenyl ester being added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL
Dithiobenzoic acid isopropylbenzene ester solution；It is added dropwise over described first solution of step (1), the volume ratio of addition wherein
For: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, it is stirred at room temperature 8 hours, obtains the second mixed liquor；Will
Hexamethylene mixes mutually with ethyl acetate, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；Will
Mixed solvent joins in above-mentioned second mixed liquor at normal temperatures, and the volume ratio of addition is: mixed solvent: the second mixed liquor
=10:1, waits until that precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins the toluene of step (1)
Middle dissolving, obtains the solution that mass body volume concentrations is 0.3g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Until supernatant liquid is colourless after Chen Dian, centrifugation product is at room temperature vacuum dried, obtains surface grafting dithio benzene first
The nano silicon of acid isopropyl phenyl ester, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and benzoyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Benzene dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, solution is sealed and preserves.
Embodiment 9
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
4-ammobutyltriethoxysilane joins in silicon dioxde solution, makes 4-ammobutyltriethoxysilane at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) dithiobenzoic acid isopropyl phenyl ester being added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL
Dithiobenzoic acid isopropylbenzene ester solution；It is added dropwise over described first solution of step (1), the volume ratio of addition wherein
For: dithiobenzoic acid isopropyl phenyl ester: the first solution=1:1, it is stirred at room temperature 8 hours, obtains the second mixed liquor；Will
Hexamethylene mixes mutually with ethyl acetate, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；Will
Mixed solvent joins in above-mentioned second mixed liquor at normal temperatures, and the volume ratio of addition is: mixed solvent: the second mixed liquor
=10:1, waits until that precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins the toluene of step (1)
Middle dissolving, obtains the solution that mass body volume concentrations is 0.3g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Until supernatant liquid is colourless after Chen Dian, centrifugation product is at room temperature vacuum dried, obtains surface grafting dithio benzene first
The nano silicon of acid isopropyl phenyl ester, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and benzoyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Benzene dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, solution is sealed and preserves.
Embodiment 10
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
4-ammobutyltriethoxysilane joins in silicon dioxde solution, makes 4-ammobutyltriethoxysilane at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) trithiocarbonate is added step (1) described toluene, obtain the trithio that mass body volume concentrations is 3g/mL
For carbonate solution；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is: dihydrogen thiocarbonate.
Ester: the first solution=1:1, is stirred at room temperature 8 hours, obtains the second mixed liquor；Hexamethylene is mixed mutually with ethyl acetate,
Obtaining mixed solvent, the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；On mixed solvent is joined at normal temperatures
Stating in the second mixed liquor, the volume ratio of addition is: mixed solvent: the second mixed liquor=10:1, waits until that precipitation separates out completely laggard
Row centrifugation, and the centrifugal product obtained is joined dissolving in the toluene of step (1), obtaining mass body volume concentrations is
The solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after Chen Dian, will be from
Heart separation product is at room temperature vacuum dried, and obtains the nano silicon of surface grafting trithiocarbonate, is designated as first and receives
Rice grain；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and benzoyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Benzene dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, solution is sealed and preserves.
Embodiment 11
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
4-ammobutyltriethoxysilane joins in silicon dioxde solution, makes 4-ammobutyltriethoxysilane at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) 4-cyano group-4-(thiobenzoyl) valeric acid is added step (1) described toluene, obtain mass body volume concentrations
4-cyano group-4-(thiobenzoyl) valeric acid solution for 3g/mL；It is added dropwise over step (1) wherein described first molten
Liquid, the volume ratio of addition is: 4-cyano group-4-(thiobenzoyl) valeric acid: the first solution=1:1, is stirred at room temperature 8 little
Time, obtain the second mixed liquor；Being mixed mutually with ethyl acetate by hexamethylene, obtain mixed solvent, the volume ratio of mixing is: ring
Hexane: ethyl acetate=4:1；Being joined by mixed solvent in above-mentioned second mixed liquor at normal temperatures, the volume ratio of addition is:
Mixed solvent: the second mixed liquor=10:1, waits until that precipitation carries out centrifugation after separating out completely, and is added by the centrifugal product obtained
Enter in the toluene of step (1) dissolving, obtain the solution that mass body volume concentrations is 0.3g/mL；Repeat above-mentioned precipitation-from
Heart separation-dissolving step, until supernatant liquid is colourless after Chen Dian, is at room temperature vacuum dried centrifugation product, obtains
The nano silicon of surface grafting 4-cyano group-4-(thiobenzoyl) valeric acid, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and benzoyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Benzene dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, solution is sealed and preserves.
Embodiment 12
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
4-ammobutyltriethoxysilane joins in silicon dioxde solution, makes 4-ammobutyltriethoxysilane at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) dithio benzoyl is added step (1) described toluene, obtain two sulfur that mass body volume concentrations is 3g/mL
For benzoyl solution；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is: dithio benzene first
Acyl: the first solution=1:1, is stirred at room temperature 8 hours, obtains the second mixed liquor；Hexamethylene is mixed mutually with ethyl acetate,
Obtaining mixed solvent, the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；On mixed solvent is joined at normal temperatures
Stating in the second mixed liquor, the volume ratio of addition is: mixed solvent: the second mixed liquor=10:1, waits until that precipitation separates out completely laggard
Row centrifugation, and the centrifugal product obtained is joined dissolving in the toluene of step (1), obtaining mass body volume concentrations is
The solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step, until supernatant liquid is colourless after Chen Dian, will be from
Heart separation product is at room temperature vacuum dried, and obtains the nano silicon of surface grafting dithio benzoyl, is designated as first and receives
Rice grain；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and benzoyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Benzene dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, solution is sealed and preserves.
Embodiment 13
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
4-ammobutyltriethoxysilane joins in silicon dioxde solution, makes 4-ammobutyltriethoxysilane at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) withered for dithiobenzoic acid ester being added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's
Or the withered ester solution of dithiobenzoic acid；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is:
The withered ester of dithiobenzoic acid: the first solution=1:1, is stirred at room temperature 8 hours, obtains the second mixed liquor；By hexamethylene and
Ethyl acetate mixes mutually, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；By mixed solvent
Joining in above-mentioned second mixed liquor at normal temperatures, the volume ratio of addition is: mixed solvent: the second mixed liquor=10:1, waits until
Precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins dissolving in the toluene of step (1),
It is the solution of 0.3g/mL to mass body volume concentrations；Repeat above-mentioned precipitation-centrifugation-dissolving step, until after Chen Dian
Supernatant liquid is colourless, is at room temperature vacuum dried by centrifugation product, obtains receiving of the withered ester of surface grafting dithiobenzoic acid
Rice silicon dioxide, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and benzoyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: benzoyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Benzene dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, solution is sealed and preserves.
Embodiment 14
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
4-ammobutyltriethoxysilane joins in silicon dioxde solution, makes 4-ammobutyltriethoxysilane at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) withered for dithiobenzoic acid ester being added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's
Or the withered ester solution of dithiobenzoic acid；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is:
The withered ester of dithiobenzoic acid: the first solution=1:1, is stirred at room temperature 8 hours, obtains the second mixed liquor；By hexamethylene and
Ethyl acetate mixes mutually, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；By mixed solvent
Joining in above-mentioned second mixed liquor at normal temperatures, the volume ratio of addition is: mixed solvent: the second mixed liquor=10:1, waits until
Precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins dissolving in the toluene of step (1),
It is the solution of 0.3g/mL to mass body volume concentrations；Repeat above-mentioned precipitation-centrifugation-dissolving step, until after Chen Dian
Supernatant liquid is colourless, is at room temperature vacuum dried by centrifugation product, obtains receiving of the withered ester of surface grafting dithiobenzoic acid
Rice silicon dioxide, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and diacetyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: diacetyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Benzene dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, solution is sealed and preserves.
Embodiment 15
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
4-ammobutyltriethoxysilane joins in silicon dioxde solution, makes 4-ammobutyltriethoxysilane at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) withered for dithiobenzoic acid ester being added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's
Or the withered ester solution of dithiobenzoic acid；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is:
The withered ester of dithiobenzoic acid: the first solution=1:1, is stirred at room temperature 8 hours, obtains the second mixed liquor；By hexamethylene and
Ethyl acetate mixes mutually, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；By mixed solvent
Joining in above-mentioned second mixed liquor at normal temperatures, the volume ratio of addition is: mixed solvent: the second mixed liquor=10:1, waits until
Precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins dissolving in the toluene of step (1),
It is the solution of 0.3g/mL to mass body volume concentrations；Repeat above-mentioned precipitation-centrifugation-dissolving step, until after Chen Dian
Supernatant liquid is colourless, is at room temperature vacuum dried by centrifugation product, obtains receiving of the withered ester of surface grafting dithiobenzoic acid
Rice silicon dioxide, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and dioctanoyl peroxide, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: dioctanoyl peroxide=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Benzene dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, solution is sealed and preserves.
Embodiment 16
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
4-ammobutyltriethoxysilane joins in silicon dioxde solution, makes 4-ammobutyltriethoxysilane at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) withered for dithiobenzoic acid ester being added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's
Or the withered ester solution of dithiobenzoic acid；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is:
The withered ester of dithiobenzoic acid: the first solution=1:1, is stirred at room temperature 8 hours, obtains the second mixed liquor；By hexamethylene and
Ethyl acetate mixes mutually, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；By mixed solvent
Joining in above-mentioned second mixed liquor at normal temperatures, the volume ratio of addition is: mixed solvent: the second mixed liquor=10:1, waits until
Precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins dissolving in the toluene of step (1),
It is the solution of 0.3g/mL to mass body volume concentrations；Repeat above-mentioned precipitation-centrifugation-dissolving step, until after Chen Dian
Supernatant liquid is colourless, is at room temperature vacuum dried by centrifugation product, obtains receiving of the withered ester of surface grafting dithiobenzoic acid
Rice silicon dioxide, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and 2,2'-Azobis(2,4-dimethylvaleronitrile), the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: 2,2'-Azobis(2,4-dimethylvaleronitrile)=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Benzene dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, solution is sealed and preserves.
Embodiment 17
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
4-ammobutyltriethoxysilane joins in silicon dioxde solution, makes 4-ammobutyltriethoxysilane at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) withered for dithiobenzoic acid ester being added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's
Or the withered ester solution of dithiobenzoic acid；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is:
The withered ester of dithiobenzoic acid: the first solution=1:1, is stirred at room temperature 8 hours, obtains the second mixed liquor；By hexamethylene and
Ethyl acetate mixes mutually, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；By mixed solvent
Joining in above-mentioned second mixed liquor at normal temperatures, the volume ratio of addition is: mixed solvent: the second mixed liquor=10:1, waits until
Precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins dissolving in the toluene of step (1),
It is the solution of 0.3g/mL to mass body volume concentrations；Repeat above-mentioned precipitation-centrifugation-dissolving step, until after Chen Dian
Supernatant liquid is colourless, is at room temperature vacuum dried by centrifugation product, obtains receiving of the withered ester of surface grafting dithiobenzoic acid
Rice silicon dioxide, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and azodiisobutyronitrile, the body of mixing
Long-pending than being respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: azodiisobutyronitrile=1:0.001, obtain
3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；?
Being joined by normal hexane under room temperature in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Benzene dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, solution is sealed and preserves.
Embodiment 18
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
4-ammobutyltriethoxysilane joins in silicon dioxde solution, makes 4-ammobutyltriethoxysilane at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) withered for dithiobenzoic acid ester being added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's
Or the withered ester solution of dithiobenzoic acid；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is:
The withered ester of dithiobenzoic acid: the first solution=1:1, is stirred at room temperature 8 hours, obtains the second mixed liquor；By hexamethylene and
Ethyl acetate mixes mutually, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；By mixed solvent
Joining in above-mentioned second mixed liquor at normal temperatures, the volume ratio of addition is: mixed solvent: the second mixed liquor=10:1, waits until
Precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins dissolving in the toluene of step (1),
It is the solution of 0.3g/mL to mass body volume concentrations；Repeat above-mentioned precipitation-centrifugation-dissolving step, until after Chen Dian
Supernatant liquid is colourless, is at room temperature vacuum dried by centrifugation product, obtains receiving of the withered ester of surface grafting dithiobenzoic acid
Rice silicon dioxide, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and peroxidized t-butyl perbenzoate, mixed
The volume ratio closed is respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: peroxidized t-butyl perbenzoate
=1:0.001, obtains the 3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains
4th mixed liquor；Being joined by normal hexane at normal temperatures in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: the
Four mixed liquors=10:1, after precipitation completely to be precipitated, is centrifuged this mixture separating, and the centrifugal product that will obtain adds
Toluene to step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugal point
From-dissolving step, obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, to molten
Liquid-tight envelope preserves.
Embodiment 19
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
4-ammobutyltriethoxysilane joins in silicon dioxde solution, makes 4-ammobutyltriethoxysilane at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) withered for dithiobenzoic acid ester being added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's
Or the withered ester solution of dithiobenzoic acid；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is:
The withered ester of dithiobenzoic acid: the first solution=1:1, is stirred at room temperature 8 hours, obtains the second mixed liquor；By hexamethylene and
Ethyl acetate mixes mutually, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；By mixed solvent
Joining in above-mentioned second mixed liquor at normal temperatures, the volume ratio of addition is: mixed solvent: the second mixed liquor=10:1, waits until
Precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins dissolving in the toluene of step (1),
It is the solution of 0.3g/mL to mass body volume concentrations；Repeat above-mentioned precipitation-centrifugation-dissolving step, until after Chen Dian
Supernatant liquid is colourless, is at room temperature vacuum dried by centrifugation product, obtains receiving of the withered ester of surface grafting dithiobenzoic acid
Rice silicon dioxide, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and the peroxidating pivalic acid tert-butyl ester, mixed
The volume ratio closed is respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: the peroxidating pivalic acid tert-butyl ester
=1:0.001, obtains the 3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains
4th mixed liquor；Being joined by normal hexane at normal temperatures in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: the
Four mixed liquors=10:1, after precipitation completely to be precipitated, is centrifuged this mixture separating, and the centrifugal product that will obtain adds
Toluene to step (1) dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugal point
From-dissolving step, obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, to molten
Liquid-tight envelope preserves.
Embodiment 20
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
4-ammobutyltriethoxysilane joins in silicon dioxde solution, makes 4-ammobutyltriethoxysilane at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) withered for dithiobenzoic acid ester being added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's
Or the withered ester solution of dithiobenzoic acid；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is:
The withered ester of dithiobenzoic acid: the first solution=1:1, is stirred at room temperature 8 hours, obtains the second mixed liquor；By hexamethylene and
Ethyl acetate mixes mutually, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；By mixed solvent
Joining in above-mentioned second mixed liquor at normal temperatures, the volume ratio of addition is: mixed solvent: the second mixed liquor=10:1, waits until
Precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins dissolving in the toluene of step (1),
It is the solution of 0.3g/mL to mass body volume concentrations；Repeat above-mentioned precipitation-centrifugation-dissolving step, until after Chen Dian
Supernatant liquid is colourless, is at room temperature vacuum dried by centrifugation product, obtains receiving of the withered ester of surface grafting dithiobenzoic acid
Rice silicon dioxide, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and isopropyl benzene hydroperoxide, mixing
Volume ratio is respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: isopropyl benzene hydroperoxide=1:0.001,
Obtain the 3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；
Being joined by normal hexane at normal temperatures in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Benzene dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, solution is sealed and preserves.
Embodiment 21
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
4-ammobutyltriethoxysilane joins in silicon dioxde solution, makes 4-ammobutyltriethoxysilane at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) withered for dithiobenzoic acid ester being added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's
Or the withered ester solution of dithiobenzoic acid；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is:
The withered ester of dithiobenzoic acid: the first solution=1:1, is stirred at room temperature 8 hours, obtains the second mixed liquor；By hexamethylene and
Ethyl acetate mixes mutually, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；By mixed solvent
Joining in above-mentioned second mixed liquor at normal temperatures, the volume ratio of addition is: mixed solvent: the second mixed liquor=10:1, waits until
Precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins dissolving in the toluene of step (1),
It is the solution of 0.3g/mL to mass body volume concentrations；Repeat above-mentioned precipitation-centrifugation-dissolving step, until after Chen Dian
Supernatant liquid is colourless, is at room temperature vacuum dried by centrifugation product, obtains receiving of the withered ester of surface grafting dithiobenzoic acid
Rice silicon dioxide, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and tert-butyl hydroperoxide, mixing
Volume ratio is respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: tert-butyl hydroperoxide=1:0.001,
Obtain the 3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours, obtains the 4th mixed liquor；
Being joined by normal hexane at normal temperatures in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane: four mixed liquors=10:1,
After precipitation completely to be precipitated, it is centrifuged this mixture separating, the centrifugal product obtained is joined the first of step (1)
Benzene dissolves, and obtains the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step,
Obtain the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, solution is sealed and preserves.
Embodiment 22
(1) first silicon dioxide is scattered in toluene, obtains the silicon dioxde solution that mass percent concentration is 30%；Will
4-ammobutyltriethoxysilane joins in silicon dioxde solution, makes 4-ammobutyltriethoxysilane at silicon dioxide
Molar concentration in solution is 3mol/L, and at nitrogen atmosphere, refluxes 12 hours, obtain the first mixed liquor at 60 DEG C；?
Normal hexane adds under room temperature the first mixed liquor, and adding volume ratio is: normal hexane: the first mixed liquor=10:1, waits that solid is complete
After full precipitation, it is centrifuged this mixture separating, and isolated solid is dissolved in above-mentioned toluene, obtain quality volume
Concentration is the solution of 0.3g/mL；Repeat above-mentioned precipitation-centrifugal-dissolving step, finally obtain surface grafting amino silane
Nanosilica solution, is designated as the first solution；
(2) withered for dithiobenzoic acid ester being added step (1) described toluene, obtaining mass body volume concentrations is 3g/mL's
Or the withered ester solution of dithiobenzoic acid；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is:
The withered ester of dithiobenzoic acid: the first solution=1:1, is stirred at room temperature 8 hours, obtains the second mixed liquor；By hexamethylene and
Ethyl acetate mixes mutually, obtains mixed solvent, and the volume ratio of mixing is: hexamethylene: ethyl acetate=4:1；By mixed solvent
Joining in above-mentioned second mixed liquor at normal temperatures, the volume ratio of addition is: mixed solvent: the second mixed liquor=10:1, waits until
Precipitation carries out centrifugation after separating out completely, and the centrifugal product obtained joins dissolving in the toluene of step (1),
It is the solution of 0.3g/mL to mass body volume concentrations；Repeat above-mentioned precipitation-centrifugation-dissolving step, until after Chen Dian
Supernatant liquid is colourless, is at room temperature vacuum dried by centrifugation product, obtains receiving of the withered ester of surface grafting dithiobenzoic acid
Rice silicon dioxide, is designated as the first nano-particle；
(3) being scattered in the toluene of step (1) by above-mentioned first nano-particle, obtaining mass body volume concentrations is 3g/mL
Solution, be designated as the second solution；Second solution is mixed with octadecyl methacrylate and peroxy dicarbonate diisobutyl ester,
The volume ratio of mixing is respectively as follows: the second solution: octadecyl methacrylate=1:1, the second solution: peroxy dicarbonate two isobutyl
Ester=1:0.001, obtains the 3rd mixed liquor；Above-mentioned 3rd mixed liquor is heated to 60 DEG C, and the response time is 12 hours,
To the 4th mixed liquor；Being joined by normal hexane at normal temperatures in above-mentioned 4th mixed liquor, the volume ratio of addition is: normal hexane:
Four mixed liquors=10:1, after precipitation completely to be precipitated, is centrifuged this mixture separating, is added by the centrifugal product obtained
Enter the toluene dissolving to step (1), obtain the solution that mass body volume concentrations is 0.2g/mL；Repeat above-mentioned precipitation-centrifugal
Separation-dissolving step, obtains the nano silicon of the surface grafting Polystearylmethacrylate solution in toluene, right
Solution seals and preserves.
Claims (1)
1. the preparation method of a surface grafting Polystearylmethacrylate nano silicon, it is characterised in that this is prepared
Method comprises the following steps:
(1) first silicon dioxide is scattered in intensive polar solvent, obtains the dioxy that mass percent concentration is 10%～40%
SiClx solution, described intensive polar solvent is: methanol, ethanol, butanone, chloroform, oxolane or toluene；Will
Amino silane joins in silicon dioxde solution, and making amino silane molar concentration in silicon dioxde solution is 1～10
Mol/L, and at nitrogen atmosphere, reflux 5～24 hours at 50～120 DEG C, obtain the first mixed liquor, described amino silane
For APTES, 3-TSL 8330,3-dimethyl methoxy silane or 4-
Ammobutyltriethoxysilane；Normal hexane adds the first mixed liquor at normal temperatures, and adding volume ratio is: normal hexane: the
One mixed liquor=(5～15): 1, after waiting that solid precipitates completely, are centrifuged this mixture separating, and by isolated
Solid is dissolved in above-mentioned intensive polar solvent, obtains the solution that mass body volume concentrations is 0.01～0.4g/mL；Repeat above-mentioned precipitation-
Centrifugal-dissolving step, finally obtains the nanosilica solution of surface grafting amino silane, is designated as the first solution；
(2) chain-transferring agent adding step (1) described intensive polar solvent, obtaining mass body volume concentrations is 1～5g/mL
Chain-transferring agent solution；Being added dropwise over described first solution of step (1) wherein, the volume ratio of addition is: chain-transferring agent: the
One solution=1:(0.5～2), it is stirred at room temperature 6～12 hours, obtains the second mixed liquor, described chain-transferring agent is two
Thiobenzoate isopropyl phenyl ester, trithiocarbonate, 4-cyano group-4-(thiobenzoyl) valeric acid, dithio benzoyl or two
The withered ester of thiobenzoate；Being mixed mutually with ethyl acetate by hexamethylene, obtain mixed solvent, the volume ratio of mixing is: hexamethylene:
Ethyl acetate=(2～6): 1；Being joined by mixed solvent in above-mentioned second mixed liquor at normal temperatures, the volume ratio of addition is:
Mixed solvent: the second mixed liquor=(5～15): 1, waits until that precipitation carries out centrifugation after separating out completely, and by obtain from
Heart product joins in the intensive polar solvent of step (1) and dissolves, and obtains 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 Chen Dian, by centrifugation product in room temperature
Lower vacuum drying, obtains the nano silicon of surface grafting chain-transferring agent, is designated as the first nano-particle；
(3) above-mentioned first nano-particle is scattered in the intensive polar solvent of step (1), obtain mass body volume concentrations be 2～
The solution of 10g/mL, is designated as the second solution；Second solution is mixed with octadecyl methacrylate and initiator, mixing
Volume ratio is respectively as follows: the second solution: octadecyl methacrylate=1:(0.5～2), the second solution: initiator=1:(0.005～
0.05), obtain the 3rd mixed liquor, described initiator be benzoyl peroxide, diacetyl peroxide, dioctanoyl peroxide,
2,2'-Azobis(2,4-dimethylvaleronitrile), azodiisobutyronitrile, peroxidized t-butyl perbenzoate, the peroxidating pivalic acid tert-butyl ester, isopropylbenzene peroxide
Change any one of hydrogen, tert-butyl hydroperoxide or peroxy dicarbonate diisobutyl ester；Above-mentioned 3rd mixed liquor is heated to
50～120 DEG C, the response time is 8～24 hours, obtains the 4th mixed liquor；At normal temperatures normal hexane is joined above-mentioned
In four mixed liquors, the volume ratio of addition is: normal hexane: the 4th mixed liquor=(5～15): 1, after precipitation completely to be precipitated,
Being centrifuged this mixture separating, the intensive polar solvent that the centrifugal product obtained joins step (1) dissolves, and obtains
Mass body volume concentrations is the solution of 0.01～0.3g/mL；Repeat above-mentioned precipitation-centrifugation-dissolving step, obtain surface
The nano silicon of grafting Polystearylmethacrylate solution in intensive polar solvent.
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| CN201410816910.7A CN104497641B (en) | 2014-12-24 | 2014-12-24 | The preparation method of surface grafting Polystearylmethacrylate nano silicon |
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| CN201410816910.7A CN104497641B (en) | 2014-12-24 | 2014-12-24 | The preparation method of surface grafting Polystearylmethacrylate nano silicon |
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