CN106832089B - A kind of nano silica-acrylic acid composite fluorescence resin and preparation method thereof - Google Patents
A kind of nano silica-acrylic acid composite fluorescence resin and preparation method thereof Download PDFInfo
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- C08F220/10—Esters
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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Abstract
The invention discloses a kind of nano silica-acrylic acid composite fluorescence resin and preparation method thereof, nano silica-acrylic acid composite fluorescence resin includes: 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 tetraphenylethylene derivative institute's chemical modification.Nano silica obtained-acrylic acid composite fluorescence resin has strong fluorescence property according to the present invention, the aggregation inducing quenching effect that conventional fluorescent luminescent material easily occurs is overcome, coating has uniform mechanics and fluorescence radiation performance after being conducive to final compound resin solidification.
Description
Technical field
The invention belongs to fluorescence composite material field, in particular to a kind of nano silica-acrylic acid composite fluorescence tree
Rouge and preparation method thereof.
Background technique
Fluorescent paint is a kind of gorgeous quick-dry enamel of color specially fresh, is coloured with pigment with day-light fluorescence, and acrylic resin paint is belonged to.Face
Color is especially bright-coloured, excitation purity is high.So-called fluorescence refers to a kind of chemiluminescence phenomenon of luminescence generated by light.When certain room temperature substance is through certain
Incident light (the usually ultraviolet light or X-ray) irradiation of kind wavelength, enters excitation state after absorbing luminous energy, and de excitation is sent out simultaneously immediately
Issue the emergent light longer than the wavelength of incident light (usual wavelength is in visible light wave range)；And once stop incident light, it shines
Phenomenon also disappears immediately therewith.With the needs of progress and the social life of scientific and technological level, fluorescent paint increasingly incorporates
In people's lives.It can be applied to decoration, anti-fake, Special display etc..
General fluorescent paint is carried out by way of mixing fluorescent powder in resin.The fluorescent powder of traditional incorporation
End, including inorganic fluorescent powder and organic fluorescence powder.Inorganic fluorescent compound light-emitting is high-efficient, thermostabilization is good, but its source
Limited and in organic polymer dispersibility is poor, and mechanical stability is poor, it is more difficult to process plastotype, and fluorescent powder is easily de-
It falls.And organic fluorescence powder, though having stronger fluorescent characteristic under solution state, fluorescent characteristic is sharply under solid states
Decline even disappears, i.e., so-called aggregation inducing Quenching has limited to the preparation and its application of fluorescent paint.
For the defect for overcoming and solving conventional fluorescent material, it is organic small that the fluorescence with aggregation-induced emission mechanism can be used
Molecule, by the connection of chemical bond, the intramolecular phenyl ring movement of fluorescent molecule is fettered, the UV energy for absorbing it
Mainly discharged by way of fluorescence radiation.To realize the solid luminescent of fluorescent material, be conducive to its practical application.
Summary of the invention
The purpose of the present invention is provide a kind of nano silica-propylene for defect present in existing fluorescent material
Sour composite fluorescence resin and preparation method thereof.First by way of surface chemical modification, fluorescence nano silica is prepared, is passed through
Cross drying grind and be sieved after, will be dispersed in its organic solvent, acrylic monomers is in the organic molten of fluorescence nano silica
Polymerization reaction is carried out in agent system, the nano silica designed-acrylic acid composite fluorescence resin.
In order to reach above-mentioned technical effect, the invention is realized by the following technical scheme:
A kind of nano silica-acrylic acid composite fluorescence resin, comprising:
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 tetraphenylethylene derivative institute's chemical modification.
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 provide it is a kind of prepare above-mentioned nano silica-acrylic acid composite fluorescence resin method,
It is made by following steps:
Step 1: dispersing fluorescence nano silica in organic solvent according to designing quality ratio, using power bracket
For the Ultrasound Instrument of 100W~500W, ultrasonic disperse 10~30 minutes at room temperature, until fluorescence nano silica is organic molten
It is uniformly dispersed in agent phase system；
Step 2: the fluorescence nano silica dispersions that the first step obtains are warming up to 60~80 DEG C, acrylate list
It after body mixture, initiator, chain-transferring agent mix in proportion, is gradually added dropwise in system, at this time the mixing speed of system
At 400 revs/min~800 revs/min, time for adding was controlled at 2~6 hours for control；
Step 3: completion of dropwise addition, system is warming up to 90~110 DEG C, reacts 2~8 hours, and cooling obtains nanometer titanium dioxide
Silicon-acrylic acid composite fluorescence resin.
Further, this case also provides a kind of method for preparing above-mentioned fluorescence nano silica, passes through following step
It is rapid to be made:
Step 1: the alkaline silicon for selecting range of solid content to be 25~100nm for 10~30wt%, particle size range is molten
Silane coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicon relative to 1~10wt% of alkaline silica sol quality is added in glue
Alkane is warming up to 50~70 DEG C, reacts 4~12 hours；
Step 2: being added and the single benzamido group tetraphenyl of γ-glycidyl ether oxygen propyl trimethoxy silicane equimolar amounts
Ethylene reacts 2~12 hours at 60~80 DEG C.After reaction, it is evaporated under reduced pressure, goes to remove water, then in 90~120 DEG C of temperature
Lower vacuum drying 12~24 hours, by 300 mesh~500 mesh sieve, obtains fluorescence nano silica,
Wherein, the structural formula of single benzamido group tetraphenylethylene are as follows:
The beneficial effects of the present invention are:
1, it using the nano-silica surface that is connected and fixed on of chemical bond, realizes to aggregation-induced emission effect
The constraint of fluorescence small organic molecule is fixed, thus the stronger fluorescence radiation behavior made it have.The organo-mineral complexing of preparation
Water based emulsion has strong fluorescence property, overcomes the aggregation inducing quenching effect that conventional fluorescent luminescent material easily occurs.Expand
The big type and application of fluorescent material.
2, nano silica-acrylic acid composite fluorescence resin, acrylic resin are depositing in fluorescence nano silica
In lower in-situ polymerization, the two is realized in the dispersion of Nano grade, coating has uniformly after being conducive to final compound resin solidification
Mechanics and fluorescence radiation performance.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment one
A kind of nano silica-acrylic acid composite fluorescence resin, comprising:
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 tetraphenylethylene derivative institute's chemical modification.
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 silica-acrylic acid composite fluorescence resin is made by following steps:
Step 1: dispersing fluorescence nano silica in organic solvent according to designing quality ratio, using power bracket
For the Ultrasound Instrument of 500W, ultrasonic disperse 30 minutes at room temperature, until fluorescence nano silica is in organic solvent phase system
It is uniformly dispersed；
Step 2: the fluorescence nano silica dispersions that the first step obtains are warming up to 60 DEG C, acrylate monomer is mixed
It after conjunction object, initiator, chain-transferring agent mix in proportion, is gradually added dropwise in system, at this time the mixing speed control of system
At 800 revs/min, time for adding was controlled at 6 hours；
Step 3: completion of dropwise addition, system is warming up to 90 DEG C, reacts 8 hours, and cooling obtains nano silica-acrylic acid
Composite fluorescence resin.
Fluorescence nano silica is made by following steps:
Step 1: selecting the alkaline silica sol that range of solid content is 100nm for 10wt%, particle size range, phase is added
For silane coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane of alkaline silica sol quality 1wt%, it is warming up to 70
DEG C, it reacts 4 hours；
Step 2: being added and the single benzamido group tetraphenyl of γ-glycidyl ether oxygen propyl trimethoxy silicane equimolar amounts
Ethylene reacts 2 hours at 60 DEG C.After reaction, it is evaporated under reduced pressure, goes to remove water, then be dried in vacuo 12 at a temperature of 120 DEG C
Hour, by the sieve of 300 mesh, fluorescence nano silica is obtained,
The wherein structural formula of single benzamido group tetraphenylethylene are as follows:
Embodiment two
A kind of nano silica-acrylic acid composite fluorescence resin, comprising:
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 tetraphenylethylene derivative institute's chemical modification.
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 silica-acrylic acid composite fluorescence resin is made by following steps:
Step 1: dispersing fluorescence nano silica in organic solvent according to designing quality ratio, using power bracket
For the Ultrasound Instrument of 200W, ultrasonic disperse 15 minutes at room temperature, until fluorescence nano silica is in organic solvent phase system
It is uniformly dispersed；
Step 2: the fluorescence nano silica dispersions that the first step obtains are warming up to 65 DEG C, acrylate monomer is mixed
It after conjunction object, initiator, chain-transferring agent mix in proportion, is gradually added dropwise in system, at this time the mixing speed control of system
At 500 revs/min, time for adding was controlled at 5 hours；
Step 3: completion of dropwise addition, system is warming up to 95 DEG C, reacts 6 hours, and cooling obtains nano silica-acrylic acid
Composite fluorescence resin.
Fluorescence nano silica is made by following steps:
Step 1: selecting the alkaline silica sol that range of solid content is 50nm for 15wt%, particle size range, it is added opposite
In silane coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane of alkaline silica sol quality 5wt%, 60 DEG C are warming up to,
Reaction 6 hours；
Step 2: being added and the single benzamido group tetraphenyl of γ-glycidyl ether oxygen propyl trimethoxy silicane equimolar amounts
Ethylene reacts 4 hours at 65 DEG C.After reaction, it is evaporated under reduced pressure, goes to remove water, then be dried in vacuo 18 at a temperature of 110 DEG C
Hour, by the sieve of 400 mesh, fluorescence nano silica is obtained,
The wherein structural formula of single benzamido group tetraphenylethylene are as follows:
Embodiment three
A kind of nano silica-acrylic acid composite fluorescence resin, comprising:
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 tetraphenylethylene derivative institute's chemical modification.
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 silica-acrylic acid composite fluorescence resin is made by following steps:
Step 1: dispersing fluorescence nano silica in organic solvent according to designing quality ratio, using power bracket
For the Ultrasound Instrument of 400W, ultrasonic disperse 20 minutes at room temperature, until fluorescence nano silica is in organic solvent phase system
It is uniformly dispersed；
Step 2: the fluorescence nano silica dispersions that the first step obtains are warming up to 75 DEG C, acrylate monomer is mixed
It after conjunction object, initiator, chain-transferring agent mix in proportion, is gradually added dropwise in system, at this time the mixing speed control of system
At 600 revs/min, time for adding was controlled at 4 hours；
Step 3: completion of dropwise addition, system is warming up to 100 DEG C, reacts 4 hours, and cooling obtains nano silica-propylene
Sour composite fluorescence resin.
Fluorescence nano silica is made by following steps:
Step 1: selecting the alkaline silica sol that range of solid content is 50nm for 20wt%, particle size range, it is added opposite
In silane coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane of alkaline silica sol quality 8wt%, 55 DEG C are warming up to,
Reaction 8 hours；
Step 2: being added and the single benzamido group tetraphenyl of γ-glycidyl ether oxygen propyl trimethoxy silicane equimolar amounts
Ethylene reacts 8 hours at 70 DEG C.After reaction, it is evaporated under reduced pressure, goes to remove water, then be dried in vacuo 20 at a temperature of 100 DEG C
Hour, by the sieve of 400 mesh, fluorescence nano silica is obtained,
The wherein structural formula of single benzamido group tetraphenylethylene are as follows:
Example IV
A kind of nano silica-acrylic acid composite fluorescence resin, comprising:
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 tetraphenylethylene derivative institute's chemical modification.
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 silica-acrylic acid composite fluorescence resin is made by following steps:
Step 1: dispersing fluorescence nano silica in organic solvent according to designing quality ratio, using power bracket
For the Ultrasound Instrument of 100W, ultrasonic disperse 10 minutes at room temperature, until fluorescence nano silica is in organic solvent phase system
It is uniformly dispersed；
Step 2: the fluorescence nano silica dispersions that the first step obtains are warming up to 80 DEG C, acrylate monomer is mixed
It after conjunction object, initiator, chain-transferring agent mix in proportion, is gradually added dropwise in system, at this time the mixing speed control of system
At 800 revs/min, time for adding was controlled at 2 hours；
Step 3: completion of dropwise addition, system is warming up to 110 DEG C, reacts 2 hours, and cooling obtains nano silica-propylene
Sour composite fluorescence resin.
Fluorescence nano silica is made by following steps:
Step 1: selecting the alkaline silica sol that range of solid content is 25nm for 30wt%, particle size range, it is added opposite
In silane coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane of alkaline silica sol quality 10wt%, 50 DEG C are warming up to,
Reaction 12 hours；
Step 2: being added and the single benzamido group tetraphenyl of γ-glycidyl ether oxygen propyl trimethoxy silicane equimolar amounts
Ethylene reacts 12 hours at 80 DEG C.After reaction, it is evaporated under reduced pressure, goes to remove water, then be dried in vacuo 24 at a temperature of 90 DEG C
Hour, by the sieve of 500 mesh, fluorescence nano silica is obtained,
The wherein structural formula of single benzamido group tetraphenylethylene are as follows:
Although the embodiments of the present invention have been disclosed as above, but it is not limited in listed fortune in specification and embodiments
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily real
Now other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is not limited to
Specific details and embodiment shown and described herein.
Claims (6)
1. a kind of nano silica-acrylic acid composite fluorescence resin characterized by comprising
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 tetraphenylethylene derivative institute's chemical modification, the fluorescence nano two
Silica can be made by following steps:
Step 1: the alkaline silica sol for selecting range of solid content to be 25~100nm for 10~30wt%, particle size range, adds
Enter silane coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane relative to 1~10wt% of alkaline silica sol quality, rises
Temperature is reacted 4~12 hours to 50~70 DEG C；
Step 2: addition and the single benzamido group tetraphenylethylene of γ-glycidyl ether oxygen propyl trimethoxy silicane equimolar amounts,
At 60~80 DEG C, react 2~12 hours, after reaction, vacuum distillation goes to remove water, then vacuum at a temperature of 90~120 DEG C
It is 12~24 hours dry, by 300 mesh~500 mesh sieve, obtain fluorescence nano silica, the list benzamido group four
The structural formula of phenylethylene are as follows:
2. nano silica as described in claim 1-acrylic acid composite fluorescence resin, which is characterized in that the acrylic acid
Ester monomer mixture 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%.
3. nano silica as described in claim 1-acrylic acid composite fluorescence resin, which is characterized in that described to be mixed with
Solvent includes:
Dimethylbenzene, 35~55vol%；
Butyl acetate, 30~50vol%；
Solvent naphtha S100#, 10~20vol%.
4. nano silica-acrylic acid composite fluorescence resin as described in claim 1, which is characterized in that the initiator
For benzoyl peroxide or azodiisobutyronitrile.
5. nano silica as described in claim 1-acrylic acid composite fluorescence resin, which is characterized in that the chain tra nsfer
Agent is 2,4- diphenyl -4-methyl-1-pentene or lauryl mercaptan.
6. a kind of such as nano silica according to any one of claims 1 to 5-acrylic acid composite fluorescence resin preparation side
Method, which is characterized in that be made by following steps:
Step 1: dispersing fluorescence nano silica in organic solvent according to designing quality ratio, it is using power bracket
The Ultrasound Instrument of 100W~500W, ultrasonic disperse 10~30 minutes at room temperature, until fluorescence nano silica is in organic solvent
It is uniformly dispersed in phase system；
Step 2: the fluorescence nano silica dispersions that the first step obtains are warming up to 60~80 DEG C, acrylate monomer is mixed
It after conjunction object, initiator, chain-transferring agent mix in proportion, is gradually added dropwise in system, at this time the mixing speed control of system
At 400 revs/min~800 revs/min, time for adding was controlled at 2~6 hours；
Step 3: completion of dropwise addition, system is warming up to 90~110 DEG C, reacts 2~8 hours, and cooling obtains nano silica-the third
Olefin(e) acid composite fluorescence resin.
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| CN109233738A (en) * | 2018-08-31 | 2019-01-18 | 江苏科技大学 | Fluorescence adhesive and the preparation method and application thereof based on aggregation-induced emission mechanism |
| CN112482040B (en) * | 2020-11-19 | 2022-03-29 | 江苏科技大学 | Super-hydrophobic fiber cloth with fluorescent property and preparation method thereof |
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| CN102911530A (en) * | 2012-11-07 | 2013-02-06 | 北京化工大学 | Preparation method capable of realizing chemical blending of modified nano silicon dioxide particles in acrylate monomer |
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| CN105883827A (en) * | 2016-04-20 | 2016-08-24 | 苏州吉人高新材料股份有限公司 | Silica sol having fluorescence properties and preparation method thereof |
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| CN102911530A (en) * | 2012-11-07 | 2013-02-06 | 北京化工大学 | Preparation method capable of realizing chemical blending of modified nano silicon dioxide particles in acrylate monomer |
| CN105273556A (en) * | 2015-11-30 | 2016-01-27 | 桂林市和鑫防水装饰材料有限公司 | Preparation method of polyacrylate/nano silicon dioxide composite emulsion coating material |
| CN105883827A (en) * | 2016-04-20 | 2016-08-24 | 苏州吉人高新材料股份有限公司 | Silica sol having fluorescence properties and preparation method thereof |
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