CN104530769A - Method for preparing high-dispersity nanosilicon dioxide particle - Google Patents
Method for preparing high-dispersity nanosilicon dioxide particle Download PDFInfo
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Abstract
The invention relates to a method for preparing high-dispersity nanosilicon dioxide particles. The method comprises the following steps: firstly, modifying nanosilicon dioxide particles to graft an azide group on the surfaces of the nanosilicon dioxide particles, preparing a polymer with a plurality of alkynyl groups on a non-terminal group of the molecular chain in a free radial polymerization mode, and finally the surfaces of the particles with the polymer through click chemistry reaction. The modified nanosilicon dioxide particles prepared by using the method are good in dispersity in organic solvents, overcome the problem of easy conglobation and have great application potential in the fields of coatings, composite materials and the like.
Description
Technical field
The present invention be more particularly directed to a kind of preparation method of high-dispersibility nanometer silicon dioxide particle, belong to polymer chemistry and organic materials technical field.
Background technology
Nano silicon is widely used in fields such as coating, chemical industry, matrix material, environmental protection, food, buildings, but the particle of nano silicon is little, specific surface area is large, interparticle reactive force is strong, very easily reunite, not easily disperse, the defect exposed in application process, cause whole material property to decline, limit it and apply widely.
Dispersed in order to improve it, develop a variety of method, the polyvalent alcohol that utilizes introduced as patent CN 103922352 A improves its dispersiveness in the basic conditions; Patent CN 103097467 A introduces and utilizes Isosorbide-5-Nitrae-butyleneglycol and monoethylene glycol etc. to strengthen its dispersiveness as chain extension agent; In patent CN 102816458 A, nano silicon or its modifier are scattered in organosilane and form dispersion; Also has a large amount of bibliographical information by chemical reaction at its surface grafting polymer compatible with base material, the reactive group of grafting is all in one end of molecular chain or compound, the space steric effect that the molecular chain that will cause due to grafting like this produces, affect the densification of other molecular chain to silica sphere coated, cause silicon dioxide granule well not disperse, or just must can play the effect of dispersion by a large amount of polymkeric substance of grafting.Utilize the structure containing multiple reflecting point on a molecular chain can improve this defect, make molecular chain stretch grafting at particle surface, form multiple rivet arrangement particle is coated, only need a small amount of polymkeric substance just can play good dispersion effect.
The present invention is first by surface modification of silica, multiple azido group that can carry out click chemistry reaction is introduced on its surface, then the multipolymer containing multiple alkynyl on the non-end group of molecular chain is prepared, utilize click chemistry to react multiple azido-s of multiple alkynyl and silica sphere are reacted, molecular chain is crouched down on its surface, reaches good dispersion effect.
Summary of the invention
The object of this invention is to provide a kind of high-dispersibility nanometer silicon dioxide particle and preparation method thereof, to achieve these goals, the technical solution adopted in the present invention is:
(1) silane coupling agent KH560, nano-silicon dioxide particle are in toluene, under 80 ~ 120 DEG C of conditions, after surface modification reaction 12h, then carry out filtering, washing with acetone and drying treatment, obtain surface modified nano silicon; In DMF solvent, under 30 ~ 80 DEG C of conditions, after surface modified nano silicon and sodium azide react 24h, after filtration, water washing and drying treatment, the modified manometer silicon dioxide particle of grafting azido-is obtained.
(2) under initiator existent condition, maleic anhydride and monomer are 1:5 ~ 20 in molar ratio, in toluene solvant, after nitrogen bubble 30min, under 60 ~ 90 DEG C of conditions react 3 ~ 7 h, more after filtration, vacuum drying treatment, obtain multipolymer; Multipolymer and propiolic alcohol are after 2:1 ~ 10:1 mixes in mass ratio, and reflux 15 ~ 25h in tetrahydrofuran (THF), through concentrated postprecipitation in water, more after filtration, vacuum-drying, obtain the multipolymer with alkynyl on the non-end group of molecular chain.
(3) under nitrogen protection; through the copper sulfate of equimolar ratio and the catalysis of sodium ascorbate; on the azido-nano-silicon dioxide particle of graft modification and molecular chain with the multipolymer of alkynyl in DMF solvent; after 70 DEG C of reaction 8 ~ 12h; through centrifugation, obtain high-dispersibility nanometer silicon dioxide particle.
Described initiator can be benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methylethyl ketone peroxide, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
Described monomer can be vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, butyl methacrylate, tert-butyl acrylate, Tert-butyl Methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or Rocryl 410.
the advantage of phase of the present invention:
The present invention, by nano-silicon dioxide particle surface graft modification, obtains the polymkeric substance containing multiple alkynyl on the non-end group of molecular chain, finally utilizes click chemistry to react polymer overmold to particle surface.Adopt the nano-silicon dioxide particle grafting efficiency of the method modification high, scattered, its easy agglomeration traits can be overcome, there is larger application advantage.
Embodiment
Illustrate the present invention is detailed further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
embodiment 1
Get silane coupling agent KH560 0.1g, nano silicon 3g, be scattered in toluene, stirring reaction 12h under 80 DEG C of conditions, filter, with dry after washing with acetone; By the silica modified particle redispersion of drying nano that obtains in 30mL DMF, add 0.5g sodium azide, 30 DEG C of condition stirring reaction 24h, suction filtration, washes rear drying with water, obtains the particle of surface grafting azido-; Get methyl methacrylate 10g, maleic anhydride 2g, BPO 0.015g is dissolved in 50mL toluene, after nitrogen bubble 30min, is placed in 80 DEG C of environment and reacts 5h, filtration, vacuum-drying; Getting the polymkeric substance that 5g obtains is positioned in reaction flask, and add 2.5g propiolic alcohol and 25ml tetrahydrofuran (THF), reflux, after 20 hours, adds a large amount of water, filters final vacuum dry, obtains the polymkeric substance with multiple alkynyl on molecular chain; Get the nano-silicon dioxide particle of 1g grafting azido-and the 0.4g polymer dispersed with multiple alkynyl in 10mL DMF, add each 0.2mL of the aqueous solution having dissolved 5mg copper sulfate and 4mg sodium ascorbate wherein respectively, react 10h under 70 DEG C of nitrogen atmosphere, after high speed centrifugation, obtain high-dispersibility nanometer silicon dioxide particle.
embodiment 2
Other reaction is identical with embodiment 1, just the reaction preparing polymkeric substance is changed into: get methyl methacrylate 40g, maleic anhydride 2g, AIBN 0.04g is dissolved in 100mL toluene, after nitrogen bubble 30min, be placed in 80 DEG C of environment and react 5h, concentrate, be deposited in ether, filtration, vacuum-drying.
embodiment 3
Other reaction is identical with embodiment 1, just methyl methacrylate is replaced by hydroxyethyl methylacrylate.
embodiment 4
Other reaction is identical with embodiment 1, just the process of alkynyl is changed into: get the polymkeric substance that 5g obtains and be positioned in reaction flask, add 0.5g propiolic alcohol and 25ml tetrahydrofuran (THF), reflux is after 20 hours, add a large amount of water, filtration final vacuum is dry, obtains the polymkeric substance with multiple alkynyl on molecular chain.
embodiment 5
Other reaction is identical with embodiment 1, just the process of silica sphere azide is changed into: get silane coupling agent KH560 0.1g, nano silicon 3g, be scattered in toluene, stirring reaction 12h under 120 DEG C of conditions, filters, with dry after washing with acetone; By the silica modified particle redispersion of drying nano that obtains in 30mL DMF, add 0.5g sodium azide, 80 DEG C of condition stirring reaction 24h, suction filtration, washes rear drying with water, obtains the particle of surface grafting azido-.
embodiment 1-embodiment 5 performance test
Claims (3)
1. a preparation method for high-dispersibility nanometer silicon dioxide particle, is characterized in that, described preparation method:
(1) silane coupling agent KH560, nano-silicon dioxide particle are in toluene, under 80 ~ 120 DEG C of conditions, after surface modification reaction 12h, then carry out filtering, washing with acetone and drying treatment, obtain surface modified nano silicon; In DMF solvent, under 30 ~ 80 DEG C of conditions, after surface modified nano silicon and sodium azide react 24h, after filtration, water washing and drying treatment, the modified manometer silicon dioxide particle of grafting azido-is obtained;
(2) under initiator existent condition, maleic anhydride and monomer are 1:5 ~ 20 in molar ratio, in toluene solvant, after nitrogen bubble 30min, under 60 ~ 90 DEG C of conditions react 3 ~ 7 h, more after filtration, vacuum drying treatment, obtain multipolymer; Multipolymer and propiolic alcohol are after 2:1 ~ 10:1 mixes in mass ratio, and reflux 15 ~ 25h in tetrahydrofuran (THF), through concentrated postprecipitation in water, more after filtration, vacuum-drying, obtain the multipolymer with alkynyl on the non-end group of molecular chain;
(3) under nitrogen protection; through the copper sulfate of equimolar ratio and the catalysis of sodium ascorbate; on the azido-nano-silicon dioxide particle of graft modification and molecular chain with the multipolymer of alkynyl in DMF solvent; after 70 DEG C of reaction 8 ~ 12h; through centrifugation, obtain high-dispersibility nanometer silicon dioxide particle.
2. the preparation method of a kind of high-dispersibility nanometer silicon dioxide particle according to claim 1, it is characterized in that, described initiator can be benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methylethyl ketone peroxide, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
3. the preparation method of a kind of high-dispersibility nanometer silicon dioxide particle according to claim 1, it is characterized in that, described monomer can be vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, butyl methacrylate, tert-butyl acrylate, Tert-butyl Methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or Rocryl 410.
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