CN104046350B - A kind of fluorescent microsphere and preparation method and application - Google Patents
A kind of fluorescent microsphere and preparation method and application Download PDFInfo
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- CN104046350B CN104046350B CN201310083682.2A CN201310083682A CN104046350B CN 104046350 B CN104046350 B CN 104046350B CN 201310083682 A CN201310083682 A CN 201310083682A CN 104046350 B CN104046350 B CN 104046350B
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Abstract
The present invention relates to a kind of fluorescent brightening microballoons and preparation method thereof.The grain size of the fluorescent microsphere is in 0.1~10 micron range, and not only sphericity is good, and particle diameter distribution is narrow, but also carries fluorescent brightening group.The fluorescent brightening group uniformly or randomly intersperses among in polysiloxanes microballoon or its surface, so that polysiloxanes microballoon has fluorescent brightening effect, fastness to light is high, and has excellent heat resistance and high chemical stability, can absorb ultraviolet light, prevent product aging, it is particularly suitable for the product of script yellowish, assigns product bright white appearance, in colored article, colored article can be made more dazzlingly beautiful, the brightness for product can be increased in black products.Another aspect of the present invention provides the preparation method of above-mentioned fluorescent microsphere and its photodiffusion material of preparation.
Description
Technical field
The present invention relates to the field of polymers, and in particular to it is a kind of it is spherical, particle diameter distribution is very narrow, and with fluorescent brightening effect
Polysiloxanes microballoon of fruit and preparation method thereof.
Background technology
Silicones has good thermal stability and lower optical index, and can be made by different preparation processes
Standby to have provided proper sphere shape, different-grain diameter characteristic distributions polysiloxanes microballoon is widely used in plastics, rubber, cosmetics and ink
Property-modifying additive.In plastic industry, light scattering property, fire-retardant of the light diffusing agent for improving clear plastic articles can be used as
Property, impact resilience and sliding.But in existing processing technology, in order to improve the appearance or anti-ultraviolet property of product, volume is also needed
Outer addition fluorescent whitening agent or ultra-violet absorber.
Fluorescent whitening agent is different from ultra-violet absorber and fluorescent dye, in addition to that can absorb sightless ultraviolet light
Outside, and longer wavelengths of blue or violet visible can be translated into, and because its with yellow light complementary light each other, can be with
The more Bai Gengliang so that product seems.And fluorescent dye can absorb visible light, send out longer wavelengths of visible fluorescence, generate photic hair
The fluorescent effect of light.Currently, being also rarely reported to the research with fluorescent brightening effect polysiloxanes microballoon and preparation method thereof.
On the other hand, the preparation method of polysiloxanes microballoon is mainly existed by three-functionality-degree and the above degree of functionality silane monomer
The effect of acid or basic catalyst issues raw hydrolysis-condensation reaction and obtains microballoon.There is particle diameter distributions for existing preparation method
Not easy to control, spherical not regular enough easy adhesion, silicone hydroxyl group（Si-OH）Remain it is more, be not easy industry amplification, production efficiency and solid
The defects of content is not high.Currently, there are no solutions to the problems described above.
Polysiloxanes microballoon is produced with interface method as described in Japan Patent JP63077940, in interface water occurs for monomer
Solution, the silanol after hydrolysis are dissolved in water, and granular of polyorganosiloxane is generated to which polycondensation reaction occur under the ammonium hydroxide effect in water phase,
But this method hydrolyzes face and is difficult to control, and stirring is more demanding, while stirring is larger to grain diameter influence, thus is easy to cause grain size point
Cloth is uneven.
WO2008/147072A1, which is disclosed, uses two-step method, first hydrolyzes trialkoxy silane in acid condition, waits hydrolyzing
After the completion, basic catalyst is added, stirs to after there is white opacity, is placed in stable state.Alcoxyl is then added wherein
Base trialkyl silica hydride compounds are to remove remaining silicone hydroxyl.
The advantages of WO2008/147072A1, is that having carried out surface water repellent to particle is modified post-processing, improves its hydrophobicity
And thermal stability.Disadvantage is that production efficiency is not high, the dosage if do not greatly improved catalyst and water, will be difficult with this preparation method
To prepare the particle less than 2 microns.Further drawback is that operation control is more difficult, due under stiring, due to being hindered between particle
It is not strong every acting on, it is easy adhesion in reaction, causes particle irregular or even gelation.
Invention content
The purpose of the present invention is to provide a kind of polysiloxanes microballoons, due to containing fluorescent brightening group in its structure,
Therefore there is fluorescent brightening effect, and with the advantages that good sphericity, particle diameter distribution is narrow, and thermal stability is good.
Another object of the present invention is to provide the preparation methods of the polysiloxanes microballoon.
Another object of the present invention is to provide a kind of photodiffusion material including the polysiloxanes microballoon.
The above-mentioned purpose of the present invention is achieved by following technical solution：
A kind of polysiloxanes microballoon is provided, it includes：
0~0.2 molfraction, preferably 0.01~0.2 molfraction, general formula（Ⅰ）The unit of representative：[(R1)2SiO2/2]
（Ⅰ）,
0.01~0.99 molfraction, preferably 0.1~0.7 molfraction, general formula（Ⅱ）The unit of representative：[R1SiO3/2]
（Ⅱ）,
0~0.2 molfraction general formula（Ⅲ）The unit of representative：[SiO4/2] （Ⅲ）,
And 0.01~0.99 molfraction, preferably 0.01~0.2 molfraction, general formula（Ⅳ）The unit of representative：
（Ⅳ）
Wherein：
The R1It is C to be independently selected from substituted or non-substituted carbon chain lengths1~20Linear or branched alkyl group, naphthenic base, alkene
Base, aryl, aralkyl；The substituent group is selected from halogen, amino acryloxy, methacryloxy, epoxy group, epoxy third
Oxygroup or carboxyl；
The X is selected from diphenylethylene, Coumarins, pyrazolines, benzo oxygen nitrogen class or phthalimide class
Fluorescent brightening group；
The R4For hydrogen-based or C1~20Alkyl；
The n is 0,1,2 or 3.
Preferably, the R1Can be selected from substituted or non-substituted methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl,
Octyl, decyl, undecyl, dodecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, 19
Alkyl, eicosyl, vinyl, allyl, phenyl, tolyl, naphthalene, benzyl, phenethyl, cyclopenta, cyclohexyl or cycloheptyl
Base.It is further preferred that the R1For methyl.
Preferably, the substituent group is halogen, amino acryloxy, methacryloxy, epoxy group, the third oxygen of epoxy
Base or carboxyl.
Preferably, the X can be selected from double triazine amino-stilbene classes, dibenzoxazine class, 3- phenyl coumarins class or
Bis-styrylbiphenyl class group.
Such as the fluorescent brightening unit structure formula of double triazine amino-stilbene classes is：
Wherein A, B C1~10Aromatic amine, fatty amine, cyclammonium and C1~6Alkyl and alkoxy；
Dibenzoxazine class fluorescent brightening unit structure formula is：
A is hydrogen-based or C1~6Alkyl；
3- phenyl coumarin class fluorescent brightening unit structure formulas are：
。
A kind of embodiment according to the present invention, the fluorescent brightening group uniformly or randomly intersperse among polysiloxanes
In microballoon.In another embodiment of the invention, the fluorescent brightening group is covered in the external table of polysiloxanes microballoon
On face.In the other embodiment of the present invention, a part of fluorescent brightening group uniformly or randomly intersperses among poly- silicon
In oxygen alkane microballoon, fluorescent brightening group described in another part is covered on the outer surface of polysiloxanes microballoon.
In the present invention, the unit that general formula I and general formula III represent can not also exist, the unit that only general formula II is represented at this time
Constitute the agent structure of polysiloxanes microballoon.It will be appreciated by those skilled in the art that when the unit that general formula I and/or general formula III represent is deposited
When, respective content can be changed as needed, to form the agent structure of polysiloxanes together with the unit that general formula II is represented.
Invention also provides the preparation methods for preparing the polysiloxanes microballoon, including following steps：
S1. by chemical formula（Ⅴ）And chemical formula（Ⅵ）Mixture dissolving in ethanol, heating reaction, then vacuum pumps
Low-boiling-point substance obtains the oxysilane alcoholic solution A with fluorescent brightening group；
S2. by formula（Ⅶ）Compound hydrolyze in the presence of acidic in deionized water, the silanol hydrolyzed
Solution or the silanol solution B of part polycondensation；
S3. above-mentioned solution A and B are mixed, dispersion stabilizer and surfactant is added, alkalinity is added after mixing and urges
Agent, pH are 8~12, stop stirring after being uniformly mixed, and keep static condition, are obtained milky white comprising polysiloxanes microballoon
Dispersion liquid, product obtain the polysiloxanes microballoon with fluorescent brightening effect after being filtered, washed, drying, crush；
The chemical formula（Ⅴ）、（Ⅵ）、（Ⅶ）Respectively：
（Ⅴ）；
X-R5
（Ⅵ）；
R1Si(OR2)3
（Ⅶ）；
Wherein：
The n is 0,1,2 or 3；
The R1It is C to be independently selected from substituted or non-substituted carbon chain lengths1~20Linear or branched alkyl group, naphthenic base, alkene
Base, aryl, aralkyl；Substituent group is selected from halogen, amino acryloxy, methacryloxy, epoxy group, glycidoxy
Or carboxyl；
The R2It is independently selected from C1~6Alkyl, such as methyl, ethyl, propyl, butyl, amyl, hexyl；
The R3Selected from C1~10Aromatic amine or fatty amine, aryl, aralkyl or C1~6Alkyl；
The R4For hydrogen atom or C1~20Alkyl；
The R5For the group that can be reacted with amino, preferably-COOH ,-COCl ,-Cl or-OH groups；
The X is the fluorescence of diphenylethylene, Coumarins, pyrazolines, benzo oxygen nitrogen class or phthalimide class
Brighten group.
Preferably, by formula in step S2（Ⅷ）With formula（Ⅸ）The compound and formula of expression（Ⅶ）The compound of expression adds together
Adiabatic reaction is carried out in the deionized water for entering to be mixed with acidic catalyst,
(R1)2Si(OR2)2
（Ⅷ）
Si(OR2)4
（Ⅸ）.
Preferably, in step S1, in terms of molar part, by molar ratio 1：0.8 ~ 1 chemical formula（V）And chemical formula（VI）Mixing
Afterwards, it is dissolved in 2 ~ 10 moles of ethyl alcohol, is warming up to 30 ~ 80 DEG C, after reacting 2-5 hours, then vacuum pumps low-boiling-point substance, obtains
Oxysilane alcoholic solution A with fluorescent brightening group.
Preferably, in step S2, in terms of molar part, by 1 mole by three-functionality-degree alkylsiloxane, and two officials when needing
The mixture addition of three kinds of monomer compositions of energy degree alkylsiloxane and/or tetra functional alkylsiloxane is mixed with 0.001 ~ 2 mole
In 10 ~ 200 molar part deionized waters of part acidic catalyst, adiabatic reaction is carried out at 5 ~ 80 DEG C, is stirred at least 2 hours, is obtained
To homogeneous and transparent silanol solution or the silanol solution B of part polycondensation；
The molar ratio of the two degrees of functionality alkylsiloxane, three-functionality-degree alkylsiloxane and tetra functional alkylsiloxane
It is 0.01 ~ 0.2：0.01~0.99：0.01~0.2.
Preferably, in step S3, the solution A and B, by siloxanes molar ratio 0.01 ~ 0.99：1 mixing, preferably 0.01 ~
0.2:1。
Preferably, heating temperature described in S1 is 30 ~ 80 DEG C, and the reaction time is 2-5 hours.
Preferably, adiabatic reaction temperature described in S2 is mixing time at least 2 hours at 5 ~ 80 DEG C.
Preferably, the reaction temperature that A described in S3, B solution mix is controlled at 5~50 DEG C, is stirred after basic catalyst is added
It is 0.5~10 minute to mix the time, and time of repose is 0.2~1 hour.
Preferably, R described in S13For hydrogen-based, methyl, ethyl, phenyl, tolyl, naphthalene, benzyl or aminoethyl.
Preferably, X described in S1 be double triazine amino-stilbene classes, dibenzoxazine class, 3- phenyl coumarins class or
Bis-styrylbiphenyl class group.
Preferably, chemical formula described in S1（Ⅴ）Structural formula can be selected from 3- aminopropyl triethoxysilanes, N-（2- ammonia second
Base）- 3- aminopropyl front threes oxosilane, N-（2- aminoethyls）Three ethoxy silane of -3- aminopropyls, N- phenyl -3- aminopropyl trimethoxies
Base silane etc..
It is further preferred that chemical formula（Ⅴ）Structural formula is 3- aminopropyl triethoxysilanes.
Preferably, chemical formula described in S1（Ⅵ）The one kind of structural formula in following structural：
；
Preferably, R described in S21For substituted or non-substituted methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl,
Octyl, decyl, undecyl, dodecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, 19
Alkyl, eicosyl, vinyl, allyl, phenyl, tolyl, naphthalene, benzyl, phenethyl, cyclopenta, cyclohexyl or cycloheptyl
Base；The substituent group is selected from halogen, amino acryloxy, methacryloxy, epoxy group, glycidoxy or carboxyl.
Preferably, the formula（Ⅶ）For dimethyldimethoxysil,ne, dimethyl diethoxysilane, diethyl dimethoxy
Any one in base silane, diethyldiethoxysilane or Methylethyl diethoxy silane or its mixing.
Preferably, the formula（Ⅷ）For methyltrimethoxysilane, methyltriethoxysilane, ethyl trimethoxy silicon
Alkane, ethyl triethoxysilane, propyl trimethoxy silicane, isopropyltri-methoxysilane, propyl-triethoxysilicane, isopropyl
Ethyl triethoxy silicane alkane, butyl trimethoxy silane, trimethoxysilane, butyl triethoxysilane, isobutyl group three
Any one in Ethoxysilane, phenyltrimethoxysila,e or phenyl triethoxysilane or its mixing.
Preferably, the formula（Ⅸ）Preferably tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, four is different
Npropoxysilane or four（2- methoxy ethoxies）Any one in silane or its mixing.
Preferably, acidic catalyst described in S2 is inorganic acid.It is further preferred that the acidic catalyst be hydrochloric acid,
Sulfuric acid, nitric acid, acid iodide or phosphoric acid.It is most preferably hydrochloric acid as one kind most preferably scheme, acidic catalyst.
Dispersion stabilizer described in S3 is water-soluble polymer, is dispersed in system, can play maintenance particle
It is suspending stabilized, prevent the viscous effect simultaneously of particle encounter.It is the dosage that can reduce water that dispersion stabilizer, which also has another effect,
Improve the solid content of product reduces cost to improve production efficiency.
Preferably, the dispersion stabilizer is polyvinyl pyrrolidone, polyvinyl alcohol, polyacrylic acid and polymethylacrylic acid
Salt, polyoxyethylene, maleic anhydride-styrene copolymers, polyoxyethylene and polyoxybutylene block copolymer, gelatin, mosanom,
It is one or more in the cellulose derivatives such as methylcellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose.Further
Preferably, the dispersion stabilizer is methylcellulose.
Surfactant described in S3, refer to anion surfactant, cationic surfactant, amphoteric or it is non-from
Any one or a few in subtype surfactant, primarily serving prevents particle aggregation, the effect of stable dispersion lotion.
Preferably, the surfactant be anion surfactant, cationic surfactant, amphoteric or it is non-from
Any one or a few in subtype surfactant.
Preferably, the anion surfactant is preferably alkyl sulfate, polyoxyethylene ether sulfate, gathers
Oxygen ethylidene alkyl phenyl ether sulfate, N- acyl taurine salts, alkylbenzene sulfonate, polyoxyethylene phenyl ether sulfonic acid
Salt, alpha-alkene sulfonate, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonate, dialkyl sulfosuccinates, monoalkyl sulfo group amber
Amber hydrochlorate, polyoxyethylene sulfosuccinates, fatty acid salt, polyoxyethylene ether acetic acid salt, N- acyl group acyls
Amino acid salt, alkenyl succinate, alkylphosphonic, polyoxyethylene ether phosphate, poly styrene sulfonate, naphthalene sulfonic acids-
Formaline condensates, aromatic sulfonic acid-formaline condensates, carboxylic acid polyalcohol or styrene-oxygroup alkylidene-acid anhydrides are total
Polymers.
Preferably, the cationic surfactant is alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, polyoxy Asia second
Base alkyl dimethyl ammonium salt, two polyoxyethylene alkyl methyl ammonium salts, three polyoxyethylene alkylammonium salts, alkyl benzyl dimethyl
Ammonium salt, sheep alkylamine salt, monoalkyl amide amine salt or cationized cellulose.
Preferably, the amphoteric surfactant be alkyl dimethyl amine oxide, alkyl dimethyl carboxybetaine,
Alkylamido propyl group dimethyl carboxybetaine or alkyl hydroxy sulfobetaines.
Preferably, the nonionic surface active agent is alkyl phenol polyoxyethylene ether series, polyethylene glycol, polyoxyethylene
Anhydrosorbitol or fatty alcohol polyoxyethylene ether series.
It is further preferred that surfactant described in S3 is anion surfactant.Most preferably, table described in S3
Face activating agent is dodecyl sodium sulfate.
Preferably, basic catalyst described in S3 is amine, alkali metal hydroxide, alkaline earth metal hydroxide or alkali gold
Belong to carbonate.The amine can be ammonia, tetramethylammonium hydroxide, monomethyl amine, monoethylamine, single propyl amine, monobutyl amine,
Single amylamine, dimethylamine, diethylamine, trimethylamine, triethanolamine and ethylenediamine；The alkali metal hydroxide can be hydroxide
Sodium, potassium hydroxide or lithium hydroxide；The alkaline earth metal hydroxide can make barium hydroxide or calcium hydroxide；The alkali metal
Carbonate can be potassium carbonate or sodium carbonate.It is further preferred that basic catalyst described in S3 is ammonia.
Preferably, the additive amount of dispersion stabilizer described in S3 is calculated as 0.001~1 part with molar part.
Preferably, the additive amount of surfactant described in S3 is calculated as 0.01~5 part with molar part.
The polysiloxanes microballoon of the present invention can be also prepared by the following method, and specific implementation step is：
S1 and S2 is identical as the first preparation method；
S3. dispersion stabilizer is added in the silanol solution B of the silanol solution or part polycondensation that are obtained in S2 and surface is lived
Property agent, be added basic catalyst after mixing, pH is 8~12, stops stirring after being uniformly mixed, and keeps static condition,
Obtain including the milky white dispersion liquid of polysiloxanes microballoon；
S4. the poly- silica obtained in S3 is added in the oxysilane alcoholic solution A with fluorescent brightening group that will be obtained in S1
It in the dispersion liquid of alkane microballoon and stirs, product obtains microsphere surface and imitated with fluorescent brightening after being filtered, washed, drying, crush
The polysiloxanes microballoon of fruit.
Preferably, at 5~50 DEG C, mixing time is 0.5~10 minute for reaction temperature control in S3.
Preferably, reaction temperature control is at 5~50 DEG C in S4, mixing time at least 3 hours.
Other reactive materials and reaction condition are identical as the first preparation method.
The present invention also provides a kind of photodiffusion materials, and it includes the polysiloxanes microballoons of the present invention.In an embodiment
In, the photodiffusion material includes the polysiloxanes microballoon of the transparent resin and 0.05 ~ 10 parts by weight of 100 parts by weight.Preferably,
The average grain diameter of the polysiloxanes microballoon is preferably 0.5 ~ 5 micron.
Preferably, the transparent resin is makrolon, polystyrene, methacrylate-styrol copolymer, propylene
Acid esters-styrol copolymer, maleic anhydride-styrene copolymers, polymethyl methacrylate, methyl methacrylate-propylene
Acid ester copolymer, polypropylene, polycyclic alkene or cycloolefin-alpha olefin copolymer.
It is further preferred that the transparent resin is makrolon.
The photodiffusion material can be prepared by methods known to those skilled in the art.For example, the photodiffusion material
A kind of preparation method be, by transparent resin and polysiloxanes microballoon it is dry-mixed after, heating melting, then use extrusion moulding or
Injection moulding is molded, and obtains the photodiffusion material.For another example another preparation method of the photodiffusion material is, it will
After partially transparent resin and polysiloxanes microballoon are dry-mixed, it is molded with the transparent resin melt kneading of relatively small amount, partical is made
Masterbatch, then with transparent resin extrusion molding, obtain the photodiffusion material.
Compared with prior art, the present invention has the advantages that：Polysiloxanes microballoon provided by the invention not only ball
Degree is good, and particle diameter distribution is narrow, and has fluorescent brightening effect, and fluorescent brightening effect is strong, and fastness to light is high, and with excellent
Heat resistance and high chemical stability can absorb ultraviolet light, prevent product aging, be particularly suitable for the system of script yellowish
Product assign product bright white appearance, for that in colored article, colored article can be made more dazzlingly beautiful, are used for black system
The brightness of product can be increased in product.
Preparation method provided by the invention significantly more efficient can prepare polysiloxanes microballoon, pass through dispersion stabilizer and table
Face activating agent can prevent particulate nucleation stage, growth stage and post-processing stages from occurring to glue simultaneously, and can reduce the use of water
Amount improves production efficiency, reduces cost.Product microballoon relies on the protection of dispersion stabilizer and surfactant, makes nothing between particle
Adhesion, sphericity is good, uniform particle diameter.
The polysiloxanes microballoon mixing that the preparation method of the present invention is prepared is dispersed in the light diffusion materials in transparent resin
Material, with excellent whiteness, light diffusing（Mist degree）And transmittance（Total light transmittance）.
Description of the drawings
Fig. 1 is the grain size distribution of polysiloxanes microballoon prepared by embodiment 1.
Fig. 2 is the petrographic microscope photo of polysiloxanes microballoon prepared by embodiment 1.
Specific implementation mode
With reference to specific embodiment, present invention be described in more detail.Material of the present invention and method are unless spy
It does not mentionlet alone bright, is all the art conventional material and method.
In following embodiment, the FT-IR spectrum of sample use KBr pressed disc methods, are measured using Tenser27 infrared spectrometers.
Average grain diameter and standard deviation are by laser particle analyzer（OMEC Easysizer20）It measures.
Fluorescence spectrum is measured by Hitachi F-7000 type Fluorescence spectrophotometers.
Whiteness is measured according to GB2913-82 by the auspicious WSB-2 fluorescent whiteness of Shanghai sunrise.
The light diffusing of material：Because there is LED lamplight the directive property of height to need to control it when it is as light source
The transmission of point source of light, influences sense organ.The photodiffusion material flat samples of preparation are placed on the LED lamplight that 4 spacing are 2cm
At the 20mm height of source, covering of the observation material to light source, with ● it indicates the invisible LED light as light source, indicates visible mould
The point source of light of paste, zero indicates the visible LED light as light source.
The mist degree and light transmittance of material：According to GB/T 2410-1980, measured by upper Nereid section WGW photoelectricity mist degree instrument.
Embodiment 1
（1）In molar ratio, by the chemical formula of the 3-aminopropyltriethoxysilane of 0.25mol and 0.21mol：
After mixing, 4mol ethyl alcohol is added, is warming up to 80 DEG C, stirs lower reaction 4h, vacuum extracts low-boiling-point substance, obtains light yellow liquid
Body.Its reaction process can be represented by the formula：
+
+HCl
（2）At 25 DEG C, by 1.12mol methyltriethoxysilane, 0.04mol dimethyldimethoxysil,nes and
0.035 mole of tetramethoxy-silicane is added in the reaction kettle containing 11.2mol deionized waters and 0.001mol hydrochloric acid, under stirring
Adiabatic reaction 4 hours obtains transparent uniform hydrolyzate.
（3）By step（1）Acquired solution and step（2）Acquired solution is uniformly mixed, and is cooled to 20 DEG C, and 0.5mol first is added
Base cellulose and 0.005mol dodecyl sodium sulfates are added with stirring a concentration of 28% ammonia of 1 gram mass after it is uniformly dispersed
Water continues stirring 2 minutes, and pH is 9 at this time, after standing 0.25 hour, obtains the dispersion liquid for including polysiloxanes microballoon.By
Filter, washing obtain 68 grams of product powder, yield 94.1% at 250 DEG C after dry 10 hours and air-flow crushing.
Using laser particle analyzer（OMEC Easysizer20 ）The powder diameter distribution for measuring embodiment 1 is as shown in Figure 1.
Wherein average grain diameter is 2.16 microns, standard deviation 0.16.
It is as shown in Figure 2 that particle image is obtained using petrographic microscope.
Solid product has strong fluorescent effect, utilizes sepectrophotofluorometer（Hitachi F-7000）Product is measured in wavelength
Maximum excitation wavelength is generated when 370~400nm.
Embodiment 2
（1）In molar ratio, by the N- of 0.15mol（2- aminoethyls）The chemistry of -3- aminopropyls three ethoxy silane and 0.13mol
Formula
After mixing, 6mol ethyl alcohol is added, is warming up to 80 DEG C, stirs lower reaction 4h, vacuum extracts low-boiling-point substance, obtains yellow liquid
Body.Its reaction process can be indicated with following formula：
+
+HCl
（2）At 35 DEG C, by 1mol methyltriethoxysilane, 0.04mol dimethyldimethoxysil,nes and 0.01 4
Methoxy silane is added in the reaction kettle containing 20mol deionized waters and 0.001mol hydrochloric acid, and it is small to stir lower adiabatic reaction 3
When, obtain transparent uniform hydrolyzate.
（3）By step（1）Acquired solution and step（2）Acquired solution is uniformly mixed, and is cooled to 15 DEG C, and 0.5mol first is added
Base cellulose and 0.005mol dodecyl sodium sulfates are added with stirring a concentration of 28% ammonia of 2 gram masses after it is uniformly dispersed
Water continues stirring 2 minutes, and pH is 10 at this time, after standing 0.25 hour, obtains the dispersion liquid for including polysiloxanes microballoon.Through taking out
Filter, washing obtain 67.6 grams of product powder, yield 93.1% at 250 DEG C after dry 10 hours and air-flow crushing.
Using laser particle analyzer（OMEC Easysizer20 ）It is 3.46 microns to measure its average grain diameter of embodiment 2, standard
Deviation is 0.17.
Solid product has strong fluorescent effect, utilizes sepectrophotofluorometer（Hitachi F-7000）Product is measured in wavelength
Maximum excitation wavelength is generated when 350~390nm.
Embodiment 3
（1）In molar ratio, by the chemical formula of three ethoxy silane and 0.005mol of the 3- aminopropyls of 0.006mol
After mixing, 6mol ethyl alcohol is added, is warming up to 80 DEG C, stirs lower reaction 4h, vacuum extracts low-boiling-point substance, obtains light yellow liquid
Body.Sample is through FT-IR spectrum（KBr pressed disc methods）Test, structural formula are：
（2）At 25 DEG C, by 1mol methyltrimethoxysilane, 0.05mol dimethyldimethoxysil,nes and 0.1mol
Tetraethoxysilane is added in the reaction kettle containing 40mol deionized waters and 0.001mol hydrochloric acid, and it is small to stir lower adiabatic reaction 4
When, obtain transparent uniform hydrolyzate.
（3）By step（1）Acquired solution and step（2）Acquired solution is uniformly mixed, and is cooled to 15 DEG C, is added 0.5 gram and is gathered
Vinyl alcohol and 0.05 gram of dodecyl sodium sulfate are added with stirring a concentration of 28% ammonium hydroxide of 2 gram masses after it is uniformly dispersed, after
Continuous stirring 2 minutes, pH is 8 at this time, after standing 0.15 hour, obtains the dispersion liquid for including polysiloxanes microballoon.Through filtering, washing
It washs, obtain 65.1 grams of product powder, yield 94.4% after dry 10 hours and air-flow crushing at 250 DEG C.
Using laser particle analyzer（OMEC Easysizer20 ）It is 1.32 microns to measure its average grain diameter of embodiment 3, standard
Deviation is 0.11.
Solid product has weak fluorescent effect, utilizes sepectrophotofluorometer（Hitachi F-7000）Product is measured in wavelength
Maximum excitation wavelength is generated when 340~400nm.
Embodiment 4
（1）In molar ratio, by the chemical formula of three ethoxy silane and 0.08mol of the 3- aminopropyls of 0.01mol
After mixing, 10mol ethyl alcohol is added, is warming up to 80 DEG C, stirs lower reaction 4h, vacuum extracts low-boiling-point substance, obtains faint yellow
Liquid.Sample is through FT-IR spectrum（KBr pressed disc methods）Test, structural formula are：
（2）At 25 DEG C, by 1mol methyltriethoxysilane, 0.02mol dimethyldimethoxysil,nes and 0.02mol
Tetramethoxy-silicane is added in the reaction kettle containing 30mol deionized waters and 0.001mol hydrochloric acid, and it is small to stir lower adiabatic reaction 4
When, obtain transparent uniform hydrolyzate.
（3）By step（1）Acquired solution and step（2）Acquired solution is uniformly mixed, and is cooled to 15 DEG C, and it is poly- that 0.5mol is added
Vinyl pyrrolidone and 0.05mol dodecyl sodium sulfates are added with stirring 0.5 gram mass a concentration of 28% after it is uniformly dispersed
Ammonium hydroxide continues stirring 2 minutes, and pH is 9 at this time, after standing 0.35 hour, obtains the dispersion liquid for including polysiloxanes microballoon.By
Filter, washing obtain 64.2 grams of product powder, yield 93.8% at 250 DEG C after dry 10 hours and air-flow crushing.
Using laser particle analyzer（OMEC Easysizer20 ）It is 4.56 microns to measure its average grain diameter of embodiment 4, standard
Deviation is 0.46.
Solid product has weak fluorescent effect, utilizes sepectrophotofluorometer（Hitachi F-7000）Product is measured in wavelength
Maximum excitation wavelength is generated when 320~400nm.
Embodiment 5
Embodiment 3 is repeated, reaction process indicates according to the following formula：
+=
Solid product has weak fluorescent effect, utilizes sepectrophotofluorometer（Hitachi F-7000）Product is measured in wavelength
Maximum excitation wavelength is generated when 340~400nm.
Embodiment 6
（1）In molar ratio, by the chemical formula of three ethoxy silane and 0.27mol of the 3- aminopropyls of 0.3mol
After mixing, 10mol ethyl alcohol is added, is warming up to 80 DEG C, stirs lower reaction 4h, vacuum extracts low-boiling-point substance, obtains faint yellow
Liquid.Sample is through FT-IR spectrum（KBr pressed disc methods）Test, structural formula are：
（2）At 25 DEG C, 1mol methyltriethoxysilane is added to containing 30mol deionized waters and 0.001mol salt
In the reaction kettle of acid, lower adiabatic reaction 4 hours is stirred, transparent uniform hydrolyzate is obtained.
（3）By step（1）Acquired solution and step（2）Acquired solution is uniformly mixed, and is cooled to 15 DEG C, and it is poly- that 0.5mol is added
Vinyl pyrrolidone and 0.05mol dodecyl sodium sulfates are added with stirring a concentration of 28% ammonia of 1 gram mass after it is uniformly dispersed
Water continues stirring 2 minutes, and pH is 10 at this time, after standing 0.35 hour, obtains the dispersion liquid for including polysiloxanes microballoon.By
Filter, washing obtain 89.1 grams of product powder, yield 92.8% at 250 DEG C after dry 10 hours and air-flow crushing.
Using laser particle analyzer（OMEC Easysizer20 ）It is 3.56 microns to measure its average grain diameter of embodiment 4, standard
Deviation is 0.36.
Solid product has weak fluorescent effect, utilizes sepectrophotofluorometer（Hitachi F-7000）Product is measured in wavelength
Maximum excitation wavelength is generated when 320~400nm.
Embodiment 7
Repeat the step in embodiment 1（1）With（2）；
（3）Step（2）Acquired solution is cooled to 20 DEG C, and 0.5mol methylcellulose and 0.005mol dodecyl sulphurs is added
Sour sodium is added with stirring a concentration of 28% ammonium hydroxide of 1 gram mass after it is uniformly dispersed, and continues stirring 2 minutes, and pH is 9 at this time, quiet
After setting to 0 .25 hours, the dispersion liquid for including polysiloxanes microballoon is obtained.
（4）Take step（1）Middle resulting solution is added dropwise to step（3）In obtained dispersion liquid, temperature 50 C is kept, continues to stir
3 hours.Product obtains 49 grams of product powder, yield through being filtered, washed, at 250 DEG C after dry 10 hours and air-flow crushing
94.1%。
Using laser particle analyzer（OMEC Easysizer20 ）The powder average particle size for measuring embodiment 6 is 2.26 microns,
Standard deviation is 0.26.
Solid product has strong fluorescent effect, utilizes sepectrophotofluorometer（Hitachi F-7000）Product is measured in wavelength
Maximum excitation wavelength is generated when 370~400nm.
Embodiment 8
Repeat the step in embodiment 2（1）With（2）.（3）Step（2）Acquired solution is cooled to 15 DEG C, and 0.5mol first is added
Base cellulose and 0.005mol dodecyl sodium sulfates are added with stirring a concentration of 28% ammonia of 2 gram masses after it is uniformly dispersed
Water continues stirring 2 minutes, and pH is 10 at this time, after standing 0.25 hour, obtains the dispersion liquid for including polysiloxanes microballoon.
（4）Through taking step（1）Middle resulting solution is added dropwise to step（3）In obtained dispersion liquid, temperature 50 C is kept, continues to stir
It mixes 3 hours.Product obtains 38.6 grams of product powder, yield through being filtered, washed, at 250 DEG C after dry 10 hours and air-flow crushing
92.8%。
Using laser particle analyzer（OMEC Easysizer20 ）It is 3.76 microns to measure its average grain diameter of embodiment 2, standard
Deviation is 0.17.
The solid product has strong solid state fluorescence, utilizes sepectrophotofluorometer（Hitachi F-7000）Product is measured in wave
Maximum excitation wavelength is generated when long 350~390nm.
Embodiment 9
Repeat the step in embodiment 6（1）With（2）.（3）Step（2）Acquired solution is cooled to 15 DEG C, and 0.5mol is added
Polyvinyl pyrrolidone and 0.05mol dodecyl sodium sulfates are added with stirring 1 gram mass a concentration of 28% after it is uniformly dispersed
Ammonium hydroxide continues stirring 2 minutes, and pH is 10 at this time, after standing 0.35 hour, obtains the dispersion liquid for including polysiloxanes microballoon.
（4）Step（1）Middle resulting solution is added dropwise to step（3）In obtained dispersion liquid, temperature 60 C is kept, continues to stir
3.5 hour.Product obtains 86.1 grams of product powder, yield through being filtered, washed, at 250 DEG C after dry 10 hours and air-flow crushing
91.5%。
Using laser particle analyzer（OMEC Easysizer20 ）It is 3.62 microns to measure its average grain diameter of embodiment 4, standard
Deviation is 0.47.
Solid product has weak fluorescent effect, utilizes sepectrophotofluorometer（Hitachi F-7000）Product is measured in wavelength
Maximum excitation wavelength is generated when 320~400nm.
Comparative example 1
（1）At 15 DEG C, by 178 grams of methyltriethoxysilane and 3 grams of ethyl orthosilicates be added to containing 954 grams go from
In the reaction kettle of sub- water and hydrochloric acid, lower adiabatic reaction 6 hours is stirred, transparent uniform hydrolyzate is obtained.
（2）By step（1）Gained hydrolyzate is cooled to 10 DEG C, and it is 0.37% ammonium hydroxide to be added with stirring 32 gram mass scores, after
Continuous stirring 3 minutes, pH is 10 at this time, and after standing 6 minutes, hydrolyzate bleaches rapidly, and white opacity thing is full of in flask, stands 1
After hour, most of solid precipitates, by 200 mesh（Aperture 74um）Filtering finds the white wadding that product form is relaxation
Shape solid.Filtering after washing is dry, crushes.Obtain 42 grams of product, yield 91.7%, solid content 3.9%.
Under the microscope, particle is spherical shape to polarized light microscopy, but adhesion is serious each other, and there are more large granules.
Comparative example 2
At room temperature, 186 grams of methyltrimethoxysilane are added and are mixed with 500 grams of water, 5 grams of interfacial agents, 0.34 gram
In the reactor of polyvinyl pyrrolidone, and 0.01 gram of ammonium hydroxide is added.
Reaction carries out under adiabatic conditions, and under continuous stirring, solution is gradually milky white, eventually forms milky white liquid.Again
By being filtered, washed, dry and crushing, you can obtain 80 grams of product.Yield 88%, solid content 11.6%.
Observed under electron microscope, particle are spherical shape, and there are residual adhesions, and particle size distribution is wider, are had more super
Bulky grain.
Using laser particle analyzer（OMEC Easysizer20 ）Measure the powder diameter distribution dispersion of comparative example 2, centriole
Diameter is at 13 microns.
10 Application Example of embodiment
By the makrolon of 100 mass parts, 1 mass parts polysiloxanes microsphere sample, appropriate processing stabilizers, 250 to
270 DEG C of temperature are granulated with the double screw extruder that screw diameter is 65mm, obtain the partical blend for injection molding.
Using the pellet, with being molded as the flat type test sample that thickness is 2mm at 250 DEG C of injection molding machine, whiteness,
Light diffusivity, light transmittance and mist degree measurement result are listed in the table below in 1.
Table 1：
As shown in Table 1, the polysiloxanes spherical shape microballoon that Examples 1 to 9 is prepared by different process conditions expands as light
Powder, which is added in transparent resin, can obtain excellent fluorescent brightening and light diffusion effect.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (8)
1. a kind of method preparing fluorescent microsphere, includes the following steps：
S1. the mixture for the compound that compound chemical formula (V) indicated is indicated with chemical formula (VI) dissolves in ethanol,
Heating reaction, obtains the oxysilane alcoholic solution A with fluorescent brightening group；
S2. the compound of formula (VII) is hydrolyzed in the presence of acidic in deionized water, the silanol solution hydrolyzed
Or the silanol solution B of part polycondensation；
S3. above-mentioned solution A and B are mixed, dispersion stabilizer and surfactant is added, base catalysis is added after mixing
Agent stops stirring after being uniformly mixed, keep static condition, to obtain including the dispersion liquid of polysiloxanes microballoon, through filtering,
After washing, dry, crushing, the polysiloxanes microballoon with fluorescent brightening effect is obtained；
The chemical formula (V), (VI), (VII) are respectively
X-R5
(Ⅵ)；
R1Si(OR2)3
(Ⅶ)；
Wherein：
The n is 0,1,2 or 3；
The R1It is C to be independently selected from substituted or non-substituted carbon chain lengths1~20Linear or branched alkyl group, naphthenic base, alkenyl, virtue
Base, aralkyl；Substituent group is selected from halogen, amino acryloxy, methacryloxy, epoxy group, glycidoxy or carboxylic
Base；
The R2It is independently selected from C1~6Alkyl；
The R3For C1~10Aromatic amine or fatty amine, aryl, aralkyl or C1~6Alkyl；
The R4For hydrogen atom or C1~20Alkyl；
The R5For-COOH ,-COCl ,-Cl, or-OH group；
The X is the fluorescent brightening of diphenylethylene, Coumarins, pyrazolines, benzo oxygen nitrogen class or phthalimide class
Group；
The fluorescent microsphere grain size carries fluorescent brightening group at 0.1~10 micron, including：
The unit that 0~0.2 molfraction general formula (I) represents：[(R1)2SiO2/2] (I),
The unit that 0.01~0.99 molfraction general formula (II) represents：[R1SiO3/2] (II),
The unit that 0~0.2 molfraction general formula (III) represents：[SiO4/2] (III),
And 0.01~0.99 molfraction general formula (IV) represent unit, and work as the R5It is (IV) a for-Cl, or when-OH groups
Structure, as the R5To be (IV) b structures when-COOH or-COCl groups；
Wherein：
The R1It is C to be independently selected from substituted or non-substituted carbon chain lengths1~20Linear or branched alkyl group, naphthenic base, alkenyl, virtue
Base, aralkyl；The substituent group is selected from halogen, amino acryloxy, methacryloxy, epoxy group, glycidoxy
Or carboxyl；
The X is the fluorescence selected from diphenylethylene, Coumarins, pyrazolines, benzo oxygen nitrogen class or phthalimide class
Brighten group；
The R3For C1~10Aromatic amine or fatty amine, aryl, aralkyl or C1~6Alkyl；
The n is 0,1,2 or 3.
2. the method for preparing fluorescent microsphere according to claim 1, which is characterized in that the X is double triazine aminodiphenyl second
Alkenes, dibenzoxazine class, 3- phenyl coumarins class or bis-styrylbiphenyl class group.
3. the method for preparing fluorescent microsphere according to claim 1, which is characterized in that the R1For methyl.
4. according to the method for preparing fluorescent microsphere described in claims 1 to 3 any one, which is characterized in that the fluorescent brightening
Group uniformly or randomly intersperses among in polysiloxanes microballoon or its surface.
5. the method for preparing fluorescent microsphere according to claim 1, wherein in the step S2 by the compound of formula (VII) with
The compound of formula (VIII) and formula (Ⅸ) hydrolyzes in the presence of acidic in deionized water, the silanol solution that is hydrolyzed or
The silanol solution B of part polycondensation；
(R1)2Si(OR2)2
(Ⅷ)
Si(OR2)4
(Ⅸ)。
6. the method for preparing fluorescent microsphere according to claim 1, the wherein structural formula of chemical formula (VI) described in step S1 are selected
From one kind in following structural：
7. 1 or 5 methods for preparing fluorescent microsphere are wanted according to right, wherein the chemical formula (VII) is dimethylformamide dimethyl oxygroup
Any one in silane, dimethyl diethoxysilane or its mixing.
8. want 5 methods for preparing fluorescent microsphere according to right, wherein the chemical formula (VIII) be methyltrimethoxysilane,
Methyltriethoxysilane, in any one or its mixing；
The chemical formula (Ⅸ) is tetramethoxy-silicane, any one in tetraethoxysilane or its mixing.
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| CN106167546B (en) * | 2016-08-06 | 2018-02-09 | 福建师范大学泉港石化研究院 | A kind of preparation of polymer microballoon of the surface with amino, carboxyl and the multi-functional autofluorescence of hydroxyl |
| CN106279549A (en) * | 2016-08-09 | 2017-01-04 | 广州市新稀冶金化工有限公司 | A kind of Multifunction light diffusing agent and preparation method thereof |
| CN110945389B (en) * | 2017-07-28 | 2021-08-03 | 东丽株式会社 | Color conversion composition, color conversion film, and device comprising same |
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