A kind of nano silicon-acrylic acid composite fluorescence resin and preparation method thereofTechnical field
The invention belongs to fluorescence composite material field, more particularly to a kind of nano silicon-acrylic acid composite fluorescence treeFat and preparation method thereof.
Background technology
Fluorescent paint, is a kind of gorgeous quick-dry enamel of color specially fresh, is coloured with pigment with day-light fluorescence, belongs to acrylic resin paint.FaceColor is especially bright-coloured, excitation is high.So-called fluorescence, refers to a kind of chemiluminescence phenomenon of luminescence generated by light.When certain normal temperature material is through certainIncident light (the typically ultraviolet or X-ray) irradiation of wavelength is planted, excitation state is entered after absorbing luminous energy, and de excitation is sent out simultaneously immediatelySend the emergent light more long than the wavelength of incident light (usual wavelength is in visible light wave range)；And once stop incident light, lightPhenomenon also disappears immediately therewith.With scientific and technological level progress and social life the need for, fluorescent paint increasingly incorporatesIn the life of people.It can be applied to the aspect such as decoration, false proof, Special display.
General fluorescent paint, is carried out by way of mixing fluorescent powder in resin.The fluorescent material of traditional incorporationEnd, including inorganic fluorescent powder and organic fluorescence powder.It is inorganic fluorescent compound light-emitting efficiency high, thermally-stabilised good, but it originatesLimited and dispersed poor in organic polymer, mechanical stability is poor, it is more difficult to process plastotype, and fluorescent powder easily takes offFall.And organic fluorescence powder, though having stronger fluorescent characteristic under solution state, fluorescent characteristic is drastically under solid statesDecline and even disappear, i.e., so-called aggregation inducing Quenching has limited to the preparation and its application of fluorescent paint.
It is the defect for overcoming with solve conventional fluorescent material, can be organic small using the fluorescence with aggregation-induced emission mechanismMolecule, by the connection of chemical bond, the intramolecular phenyl ring motion of fluorescence molecule is fettered, and makes its UV energy for being absorbedMainly discharged by way of fluorescence radiation.So as to realize the solid luminescent of fluorescent material, be conducive to its practical application.
The content of the invention
The purpose of the present invention is directed to the defect existing for existing fluorescent material, there is provided a kind of nano silicon-propyleneSour composite fluorescence resin and preparation method thereof.First by way of surface chemical modification, fluorescence nano silica is prepared, passed throughCross after drying grinds and sieve, will be dispersed in its organic solvent, acrylic monomers is in the organic molten of fluorescence nano silicaPolymerisation is carried out in agent system, the nano silicon for being designed-acrylic acid composite fluorescence resin.
In order to reach above-mentioned technique effect, the present invention is achieved through the following technical solutions：
A kind of nano silicon-acrylic acid composite fluorescence resin, including：
Fluorescence nano silica, 0.1~3wt%；
Acrylate monomer blend, 35~65wt%；
Mixed organic solvents, 30~60wt%；
Initiator, 0.5~5wt%；
Chain-transferring agent, 1~3wt%,
Wherein, the fluorescence nano silica is modified through the chemical modification of tetraphenylethylene derivative institute.
Preferably, the acrylate monomer blend includes：
Methyl methacrylate, 30~55wt%；
Styrene, 5~15wt%；
Isooctyl acrylate monomer, 10~30wt%；
Butyl acrylate, 20~30wt%；
Hydroxy-ethyl acrylate, 5~10wt%；
Methacrylic acid, 1~5wt%.
Preferably, the mixed organic solvents include：
Dimethylbenzene, 35~55vol%；
Butyl acetate, 30~50vol%；
Solvent naphtha S100#, 10~20vol%.
Preferably, the initiator is benzoyl peroxide or azodiisobutyronitrile.
Preferably, the chain-transferring agent is 2,4- diphenyl -4-methyl-1-pentene or lauryl mercaptan.
Further, this case also provides a kind of method for preparing above-mentioned nano silicon-acrylic acid composite fluorescence resin,It passes through following steps and is obtained：
The first step：According to designing quality ratio, fluorescence nano silica is scattered in organic solvent, uses power bracketIt is the Ultrasound Instrument of 100W~500W, ultrasonic disperse 10~30 minutes at room temperature, until fluorescence nano silica is organic moltenIt is uniformly dispersed in agent phase system；
Second step：The fluorescence nano silica dispersions that the first step is obtained are warming up to 60~80 DEG C, acrylate listAfter body mixture, initiator, chain-transferring agent are mixed in proportion, progressively it is added dropwise in system, now the mixing speed of systemAt 400 revs/min~800 revs/min, time for adding was controlled at 2~6 hours for control；
3rd step：Completion of dropwise addition, system is warming up to 90~110 DEG C, reacts 2~8 hours, and cooling obtains nanometer titanium dioxideSilicon-acrylic acid composite fluorescence resin.
Further, this case also provides a kind of method for preparing above-mentioned fluorescence nano silica, and it is by following stepIt is rapid to be obtained：
The first step：The selection alkaline silicon that range of solid content is 10~30wt%, particle size scope is 25~100nm is moltenGlue, adds the silane coupler γ-glycidyl ether oxygen propyl trimethoxy silicon relative to 1~10wt% of alkaline silica sol qualityAlkane, is warming up to 50~70 DEG C, reacts 4~12 hours；
Second step：Add the single benzamido group tetraphenyl with γ-glycidyl ether oxygen propyl trimethoxy silicane equimolar amountsEthene, at 60~80 DEG C, reacts 2~12 hours.After reaction terminates, water removal is gone in vacuum distillation, then in 90~120 DEG C of temperatureLower vacuum drying 12~24 hours, by the sieve of 300 mesh~500 mesh, obtains fluorescence nano silica,
Wherein, the structural formula of single benzamido group tetraphenylethylene is：
The beneficial effects of the invention are as follows：
1st, using the nano-silica surface that is connected and fixed on of chemical bond, realize to aggregation-induced emission effectThe constraint of fluorescence organic molecule is fixed, so as to the stronger fluorescence radiation behavior for making it have.The organo-mineral complexing of preparationWater based emulsion with strong fluorescence property, overcome the aggregation inducing quenching effect that conventional fluorescent luminescent material easily occurs.ExpandThe species of big fluorescent material and application.
2nd, nano silicon-acrylic acid composite fluorescence resin, acrylic resin is depositing in fluorescence nano silicaIn lower in-situ polymerization, both dispersions in Nano grade are realized, coating has uniform after being conducive to final compound resin to solidifyMechanics and fluorescence radiation performance.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present inventionRather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the artMember can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limitedScope.
Embodiment one
A kind of nano silicon-acrylic acid composite fluorescence resin, including：
Fluorescence nano silica, 3wt%；
Acrylate monomer blend, 35wt%；
Mixed organic solvents, 60wt%；
Initiator azodiisobutyronitrile, 1wt%；
Chain-transferring agent lauryl mercaptan, 1wt%,
Wherein, the fluorescence nano silica is modified through the chemical modification of tetraphenylethylene derivative institute.
The acrylate monomer blend includes：
Methyl methacrylate, 55wt%；
Styrene, 5wt%；
Isooctyl acrylate monomer, 10wt%；
Butyl acrylate, 20wt%；
Hydroxy-ethyl acrylate, 8wt%；
Methacrylic acid, 2wt%.
The mixed organic solvents include：
Dimethylbenzene, 35vol%；
Butyl acetate, 50vol%；
Solvent naphtha S100#, 15vol%.
Nano silicon-acrylic acid composite fluorescence resin is obtained by following steps：
The first step：According to designing quality ratio, fluorescence nano silica is scattered in organic solvent, uses power bracketIt is the Ultrasound Instrument of 500W, ultrasonic disperse 30 minutes at room temperature, until fluorescence nano silica is in organic solvent phase systemIt is uniformly dispersed；
Second step：The fluorescence nano silica dispersions that the first step is obtained are warming up to 60 DEG C, and acrylate monomer is mixedAfter compound, initiator, chain-transferring agent are mixed in proportion, progressively it is added dropwise in system, now the mixing speed control of systemAt 800 revs/min, time for adding was controlled at 6 hours；
3rd step：Completion of dropwise addition, system is warming up to 90 DEG C, reacts 8 hours, and cooling obtains nano silicon-acrylic acidComposite fluorescence resin.
Fluorescence nano silica is obtained by following steps：
The first step：The alkaline silica sol that selection range of solid content is 10wt%, particle size scope is 100nm, adds phaseSilane coupler γ-glycidyl ether oxygen propyl trimethoxy silicane for alkaline silica sol quality 1wt%, is warming up to 70DEG C, react 4 hours；
Second step：Add the single benzamido group tetraphenyl with γ-glycidyl ether oxygen propyl trimethoxy silicane equimolar amountsEthene, at 60 DEG C, reacts 2 hours.After reaction terminates, vacuum distillation goes water removal, then be vacuum dried 12 at a temperature of 120 DEG CHour, by the sieve of 300 mesh, fluorescence nano silica is obtained,
The structural formula of wherein described single benzamido group tetraphenylethylene is：
Embodiment two
A kind of nano silicon-acrylic acid composite fluorescence resin, including：
Fluorescence nano silica, 1wt%；
Acrylate monomer blend, 50wt%；
Mixed organic solvents, 47wt%；
Initiator azodiisobutyronitrile, 0.5wt%；
Chain-transferring agent lauryl mercaptan, 1.5wt%,
Wherein, the fluorescence nano silica is modified through the chemical modification of tetraphenylethylene derivative institute.
The acrylate monomer blend includes：
Methyl methacrylate, 40wt%；
Styrene, 10wt%；
Isooctyl acrylate monomer, 15wt%；
Butyl acrylate, 25wt%；
Hydroxy-ethyl acrylate, 5wt%；
Methacrylic acid, 5wt%.
The mixed organic solvents include：
Dimethylbenzene, 55vol%；
Butyl acetate, 35vol%；
Solvent naphtha S100#, 10vol%.
Nano silicon-acrylic acid composite fluorescence resin is obtained by following steps：
The first step：According to designing quality ratio, fluorescence nano silica is scattered in organic solvent, uses power bracketIt is the Ultrasound Instrument of 200W, ultrasonic disperse 15 minutes at room temperature, until fluorescence nano silica is in organic solvent phase systemIt is uniformly dispersed；
Second step：The fluorescence nano silica dispersions that the first step is obtained are warming up to 65 DEG C, and acrylate monomer is mixedAfter compound, initiator, chain-transferring agent are mixed in proportion, progressively it is added dropwise in system, now the mixing speed control of systemAt 500 revs/min, time for adding was controlled at 5 hours；
3rd step：Completion of dropwise addition, system is warming up to 95 DEG C, reacts 6 hours, and cooling obtains nano silicon-acrylic acidComposite fluorescence resin.
Fluorescence nano silica is obtained by following steps：
The first step：The alkaline silica sol that selection range of solid content is 15wt%, particle size scope is 50nm, adds relativeIn the silane coupler γ-glycidyl ether oxygen propyl trimethoxy silicane of alkaline silica sol quality 5wt%, 60 DEG C are warming up to,Reaction 6 hours；
Second step：Add the single benzamido group tetraphenyl with γ-glycidyl ether oxygen propyl trimethoxy silicane equimolar amountsEthene, at 65 DEG C, reacts 4 hours.After reaction terminates, vacuum distillation goes water removal, then be vacuum dried 18 at a temperature of 110 DEG CHour, by the sieve of 400 mesh, fluorescence nano silica is obtained,
The structural formula of wherein described single benzamido group tetraphenylethylene is：
Embodiment three
A kind of nano silicon-acrylic acid composite fluorescence resin, including：
Fluorescence nano silica, 2wt%；
Acrylate monomer blend, 40wt%；
Mixed organic solvents, 51wt%；
Initiator azodiisobutyronitrile, 5wt%；
Chain-transferring agent lauryl mercaptan, 2wt%,
Wherein, the fluorescence nano silica is modified through the chemical modification of tetraphenylethylene derivative institute.
The acrylate monomer blend includes：
Methyl methacrylate, 30wt%；
Styrene, 7wt%；
Isooctyl acrylate monomer, 30wt%；
Butyl acrylate, 22wt%；
Hydroxy-ethyl acrylate, 10wt%；
Methacrylic acid, 1wt%.
The mixed organic solvents include：
Dimethylbenzene, 50vol%；
Butyl acetate, 30vol%；
Solvent naphtha S100#, 20vol%.
Nano silicon-acrylic acid composite fluorescence resin is obtained by following steps：
The first step：According to designing quality ratio, fluorescence nano silica is scattered in organic solvent, uses power bracketIt is the Ultrasound Instrument of 400W, ultrasonic disperse 20 minutes at room temperature, until fluorescence nano silica is in organic solvent phase systemIt is uniformly dispersed；
Second step：The fluorescence nano silica dispersions that the first step is obtained are warming up to 75 DEG C, and acrylate monomer is mixedAfter compound, initiator, chain-transferring agent are mixed in proportion, progressively it is added dropwise in system, now the mixing speed control of systemAt 600 revs/min, time for adding was controlled at 4 hours；
3rd step：Completion of dropwise addition, system is warming up to 100 DEG C, reacts 4 hours, and cooling obtains nano silicon-propyleneSour composite fluorescence resin.
Fluorescence nano silica is obtained by following steps：
The first step：The alkaline silica sol that selection range of solid content is 20wt%, particle size scope is 50nm, adds relativeIn the silane coupler γ-glycidyl ether oxygen propyl trimethoxy silicane of alkaline silica sol quality 8wt%, 55 DEG C are warming up to,Reaction 8 hours；
Second step：Add the single benzamido group tetraphenyl with γ-glycidyl ether oxygen propyl trimethoxy silicane equimolar amountsEthene, at 70 DEG C, reacts 8 hours.After reaction terminates, vacuum distillation goes water removal, then be vacuum dried 20 at a temperature of 100 DEG CHour, by the sieve of 400 mesh, fluorescence nano silica is obtained,
The structural formula of wherein described single benzamido group tetraphenylethylene is：
Example IV
A kind of nano silicon-acrylic acid composite fluorescence resin, including：
Fluorescence nano silica, 0.1wt%；
Acrylate monomer blend, 65wt%；
Mixed organic solvents, 30wt%；
Initiator azodiisobutyronitrile, 1.9wt%；
Chain-transferring agent lauryl mercaptan, 3wt%,
Wherein, the fluorescence nano silica is modified through the chemical modification of tetraphenylethylene derivative institute.
The acrylate monomer blend includes：
Methyl methacrylate, 34wt%；
Styrene, 15wt%；
Isooctyl acrylate monomer, 12wt%；
Butyl acrylate, 30wt%；
Hydroxy-ethyl acrylate, 6wt%；
Methacrylic acid, 3wt%.
The mixed organic solvents include：
Dimethylbenzene, 45vol%；
Butyl acetate, 38vol%；
Solvent naphtha S100#, 17vol%.
Nano silicon-acrylic acid composite fluorescence resin is obtained by following steps：
The first step：According to designing quality ratio, fluorescence nano silica is scattered in organic solvent, uses power bracketIt is the Ultrasound Instrument of 100W, ultrasonic disperse 10 minutes at room temperature, until fluorescence nano silica is in organic solvent phase systemIt is uniformly dispersed；
Second step：The fluorescence nano silica dispersions that the first step is obtained are warming up to 80 DEG C, and acrylate monomer is mixedAfter compound, initiator, chain-transferring agent are mixed in proportion, progressively it is added dropwise in system, now the mixing speed control of systemAt 800 revs/min, time for adding was controlled at 2 hours；
3rd step：Completion of dropwise addition, system is warming up to 110 DEG C, reacts 2 hours, and cooling obtains nano silicon-propyleneSour composite fluorescence resin.
Fluorescence nano silica is obtained by following steps：
The first step：The alkaline silica sol that selection range of solid content is 30wt%, particle size scope is 25nm, adds relativeIn the silane coupler γ-glycidyl ether oxygen propyl trimethoxy silicane of alkaline silica sol quality 10wt%, 50 DEG C are warming up to,Reaction 12 hours；
Second step：Add the single benzamido group tetraphenyl with γ-glycidyl ether oxygen propyl trimethoxy silicane equimolar amountsEthene, at 80 DEG C, reacts 12 hours.After reaction terminates, vacuum distillation goes water removal, then be vacuum dried 24 at a temperature of 90 DEG CHour, by the sieve of 500 mesh, fluorescence nano silica is obtained,
The structural formula of wherein described single benzamido group tetraphenylethylene is：
Although embodiment of the present invention is disclosed as above, it is not limited in listed fortune in specification and implementation methodWith, it can be applied to various suitable the field of the invention completely, for those skilled in the art, can be easily realNow other modification, therefore under the universal limited without departing substantially from claim and equivalency range, the present invention is not limited toSpecific details and shown here as the embodiment with description.