CN105777978A - Preparation method of monodisperse polymer/SiO2 nano composite particles - Google Patents
Preparation method of monodisperse polymer/SiO2 nano composite particles Download PDFInfo
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Abstract
The invention provides a preparation method of monodisperse polymer/SiO2 nano composite particles. The method comprises the following steps of (1) dissolving a water-soluble non-ionic emulsifier into water so as to obtain an emulsifier aqueous solution; (2) dispersing hydrophobic SiO2 nano particles into part of monomers, and adding a co-stabilizer and residual monomers, thereby obtaining a monodisperse solution of the SiO2 nano particles, wherein the monomers are selected from at least one of styrene and acrylic ester compounds as shown in a formula (I); (3) adding the monodisperse solution of SiO2 into the non-ionic emulsifier aqueous solution, stirring for pre-emulsification so as to obtain a crude emulsion, performing ultrasonic treatment in an ice-water bath so as to obtain a monomer miniemulsion, adding a water-soluble ionic emulsifier into the monomer miniemulsion, introducing nitrogen to remove oxygen, and reacting in the protection of nitrogen so as to obtain the monodisperse polymer/SiO2 nano composite particles, wherein an initiator can be added through the following two modes: adding an oil-soluble initiator into the monodisperse solution of the SiO2 nano particles or adding a water-soluble initiator into the monomer miniemulsion. The formula I is as shown in the specification.
Description
(1) technical field
The preparation method that the present invention relates to a kind of nano-complex particle, is specifically related to one and utilizes mini-emulsion polymerization technology, and preparation good sphericity, size are controlled, polymer and the high monodisperse polymer/SiO of inorganic particle recombination rate2The method of nano-complex particle.
(2) background technology
The polymer/inorganic granule nano composite material being composited under nanoscale can farthest play the synergisticing performance of polymer and inorganic material, drawing abillity, mechanical performance and hot property can not only be greatly improved, can also give that material is optical, electrical, the function such as magnetic and catalysis so that it is have broad application prospects in high-end fields such as Aero-Space, biological medicine, catalysis.As the important representative of nano composite material, with SiO2Nano-particle is dispersion phase, and polymer is the polymer/SiO of matrix2One of the preparation and the applied research focus being always up this field of nano-complex particle.
At present, have been developed in and multiple prepare polymer/SiO2The method of nano-complex particle.These preparation methoies generally include two steps: (1) SiO2Nano grain surface hydrophobically modified；(2) the heterogeneous polymerization modes such as emulsion polymerization, micro-emulsion polymerization or mini-emulsion polymerization are utilized to prepare polymer/SiO2Nano-complex particle.Such as this seminar Zeng Xianyong silane coupler (methacrylic acid 3-trimethoxy silicon propyl ester) containing vinyl modifies Nano-meter SiO_22Particle, prepares Punica granatum L. shaped polymer/SiO again through in-situ emulsion polymerization2Nano-complex particle [ColloidPolym.Sci.2015,293,463-471；ColloidsSurf., A2016,489,265-274.].Xu et al., then in micro-emulsion polymerization system, utilizes the polyreaction of methyl methacrylate, the SiO that coated by hydrophobic is modified2Nanoparticle, prepares the polymer/SiO being smaller in size than 100nm2Nano-complex particle [ColloidPolym.Sci.2006,284,755-762].
Polymer/SiO that emulsion polymerization prepares2In nano-complex particle, highly cross-linked between inorganic particulate, it is present in inside nano-complex particle with the form of particle string, skewness, and also the useful load of inorganic particulate is not high.Though micro-emulsion polymerization can prepare undersized nano-complex particle, but build microemulsion reaction system and need to use a large amount of emulsifying agent, it is unfavorable for the application of nano-complex particle.
Miniemulsion is with monomer droplet for dispersion phase, and water is the heterogeneous polymerization system [Adv.Polym.Sci.2005,175,129-255] of continuous phase.Mini-emulsion polymerization forms polymer particle in droplet nucleation mode, and therefore monomer droplet is the storage place of monomer, is again reacting environment.In theory, the previously-introduced monomer droplet of inorganic particulate of cladding will be intended, again through polyreaction, the efficient cladding to inorganic particulate can be realized, prepare nano-complex particle [Adv.ColloidInterfaceSci.2014,211,47-62.].
Military favorable to the people et al. once with sodium lauryl sulphate for emulsifying agent, successfully it is coated with by mini-emulsion polymerization mode with the SiO of methacrylic acid 3-trimethoxy silicon propyl ester finishing2Nanoparticle, has prepared the polystyrene/SiO of variform2Nano-complex particle [Langmuir2005,21,2124-2128].Although mini-emulsion polymerization prepares polymer/SiO2The method of nano-complex particle is simple, but made nano-complex particle distribution of sizes is wider, and this limits this materials application to a certain extent and is worth.
Monodisperse spherical particle, because of its controlled size, homogeneous distribution of sizes and regular form, can form orderly package assembly, photonic crystal, the preparation of three-dimensional ordered polyporous material, macroporous catalyst the field such as preparation have important using value.At present, have and add ethanol, the method synthesizing monodisperse polymer nanoparticle to mini-emulsion polymerization reaction system, but the method exists following defect: (1) need to additionally use organic solvent；(2) after introducing ethanol, add the monomer dissolubility in continuous phase, easily cause secondary nucleation and form blank polymer particle, reduce the combined efficiency of inorganic particle and polymer.
(3) summary of the invention
It is desirable to provide a kind of new emulsifying agent using method, make mini-emulsion polymerization technology can prepare monodisperse polymer/SiO simply, efficiently2Nano-complex particle, obtained monodisperse polymer/SiO2Nano-complex particle possesses that form is regular, monodispersity good, polymer and SiO2Combined efficiency advantages of higher.
For achieving the above object, the technical solution used in the present invention is:
A kind of monodisperse polymer/SiO2The preparation method of nano-complex particle, said method comprising the steps of:
(1) by soluble in water for water-soluble nonionic emulsifying agent, the aqueous solution of emulsifying agent is obtained, wherein quality consumption is water quality consumption the 0.01%～10% of nonionic emulsifier；Described water-soluble nonionic emulsifying agent is selected from following at least one: twain series emulsifier, OP series emulsifying agent, MOA series emulsifying agent；
(2) by hydrophobic SiO2Nano-particle is scattered in partial monosomy, after adding co-stabilizer and residual monomer, obtains SiO2The monomer dispersion liquid of nano-particle, wherein hydrophobic SiO2The quality consumption of nano-particle is the 1%～30% of monomer gross mass consumption, and the quality consumption of co-stabilizer is the 2%～10% of monomer gross mass consumption；
Described monomer is selected from following at least one: the acrylic ester compound shown in styrene, formula (I)；
In formula (I), R1For H or CH3；R2For the fatty straight or branched alkyl of C1～C10, ethoxy, dimethylaminoethyl, trifluoroethyl or-(CH2)3-Si(OCH3)3；
Described co-stabilizer is selected from the fatty alcohol of the fatty straight or branched alkane of following at least one: C14～C22, C14～C22；
(3) SiO that step (2) is obtained2Monomer dispersion liquid be added in the aqueous solution of the nonionic emulsifier that step (1) obtains so that monomer gross mass consumption is the 1%～40% of water quality consumption, stirring pre-emulsification obtain thick emulsion；Will be equipped with the container of thick emulsion again and be placed in ice-water bath, supersound process 0.5min～60min under the power of 25W～950W, prepare monomer miniemulsion；Water-soluble ionic-type emulsifying agent is added to monomer miniemulsion, described water-soluble ionic-type emulsifying agent is selected from following at least one: alkylsulfonate emulsifying agent, alkylbenzenesulfonate emulsifying agent, alkyl sulfate emulsifier, alkyl carboxylate's emulsifying agent, alkylpolyoxyethylene emulsifying agent, glycine betaine emulsifying agent, aminoacid emulsifying agent, amine-oxides emulsifying agent, wherein the quality consumption of water-soluble ionic-type emulsifying agent is the 0.5%～100% of water-soluble nonionic emulsifying agent quality consumption, stirs 1min～45min；Letting nitrogen in and deoxidizing, is adjusted to temperature 35 DEG C～95 DEG C, and reacts 0.5h～24h under nitrogen protection, prepares monodisperse polymer/SiO2Nano-complex particle；
Further, initiator is introduced by following manner a or mode b:
Mode a: in step (2), toward SiO2Adding oil-soluble initiator in the monomer dispersion liquid of nano-particle, wherein the quality consumption of oil-soluble initiator is the 0.05%～5% of monomer gross mass consumption；
Mode b: in step (3), after monomer miniemulsion adds water-soluble ionic-type emulsifying agent and is uniformly mixed, adding water soluble starter to monomer miniemulsion, wherein the quality consumption of water soluble starter is the 0.05%～5% of monomer gross mass consumption.
In step of the present invention (1), twain series emulsifier can be the combination of one or more in tween 20, Tween-40, Tween-60 or tween 80；OP series emulsifying agent can be the combination of one or more in OP-7, OP-10, OP-15 or OP-20；MOA series emulsifying agent can be the combination of one or more in MOA-3, MOA-7 and MOA-9.Considering size and the distribution thereof of monomer droplet, at least one in the described preferred tween 20 of water-soluble nonionic emulsifying agent, OP-10 and MOA-9, its consumption is preferably the 0.4%～8% of water quality consumption.
In step of the present invention (2), described hydrophobic SiO2The size range of nano-particle is 10nm～100nm, and its hydrophobicity coupling density is stated, and coupling density is defined as the SiO of per unit square metre2The mole of the hydrophobic modifier that particle surface is modified, unit is a μm ol (m2SiO2)-1, wherein coupling density range for 0.5 μm of ol (m2SiO2)-1～4.0 μm of ol (m2SiO2)-1.Described hydrophobic SiO2Nano-particle can be prepared by existing method, for instance: (1) is usedMethod synthesis particle diameter is at the SiO of 10nm～100nm2SiO in nano-particle or directly purchase this particle size range commercially available2Nano-particle；(2) according to the method for bibliographical information to SiO2Nano-particle carries out hydrophobically modified [ColloidPolym.Sci.2015,293,463-471；Langmuir2005,21,2124-2128】.Wherein hydrophobic modifier can be at least one in following commercially available siloxanes: methacrylic acid 3-trimethoxy silicon propyl ester, VTES, octyltri-ethoxysilane, octyl group trimethoxy silane, dodecyltrimethoxysilane, hexadecyl trimethoxy silane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercapto hydroxypropyl methyl dimethoxysilane.
In step of the present invention (2), described monomeric compound is preferably at least one in styrene, methyl methacrylate, butyl acrylate.Considering the stability of drop, co-stabilizer is preferably the fatty straight or branched alkane of C16～C22, more preferably hexadecane.
In step of the present invention (2), described oil-soluble initiator is selected from following at least one: azodiisobutyronitrile, AMBN, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, lauroyl peroxide.
In step of the present invention (3), alkylsulfonate emulsifying agent can be R1-SO3M, wherein R1For the aliphatic chain of C10～C20, M is Na+Or K+；Alkylbenzenesulfonate emulsifying agent can be R2-C6H4-SO3M, wherein R2For the aliphatic chain of C10～C18, M is Na+Or K+；But alkyl sulfate emulsifier R3-OSO3M, wherein R3For the aliphatic chain of C10～C20, M is Na+Or K+；Alkyl carboxylate's emulsifying agent can be R4-COOM, wherein R4For the aliphatic chain of C9～C21, M is Na+Or K+；But alkylpolyoxyethylene emulsifying agent R5N+(CH3)3X-, wherein R5For the aliphatic chain of C12～C20, X is Cl or Br；Glycine betaine emulsifying agent can be carboxylic acid group glycine betaine (R6N+(CH3)2CH2COO-, wherein R6Aliphatic chain for C12～C18), sulfonic group glycine betaine (R7N+(CH3)2CH2CH2SO3 -Or R8N+(CH3)2CH2CH2CH2SO3 -, wherein R7And R8Aliphatic chain for C12～C18)；Aminoacid emulsifying agent can be dodecyl alanine；Amine oxide emulsifying agent can be octadecyl dihydroxy ethyl amine oxide, myristyl dihydroxy ethyl amine oxide, stearamide propyl group amine oxide or dodecanamide propyl amine oxide.Consider the stability of particle in polymerization process, at least one in the preferred alkylsulfonate emulsifying agent of water-soluble ionic-type emulsifying agent, alkylbenzenesulfonate emulsifying agent, alkyl sulfate emulsifier, alkylpolyoxyethylene emulsifying agent and sulfonic group glycine betaine, more preferably sodium lauryl sulphate, cetyl trimethylammonium bromide, at least one in dodecyl dimethyl hydroxypropyl sulfonic acid base glycine betaine, its quality consumption is preferably the 1%～36% of water-soluble nonionic emulsifying agent quality consumption.
In step of the present invention (3), described water soluble starter is selected from following at least one: 2, the redox system that 2 '-azo dibutyl amidine dihydrochloride, persulfate, oxidant and reducing agent are constituted；Described reducing agent is sulphite, thiosulfate, bisulfites, oxalic acid, tertiary amine alcohol or primary amine class；Described oxidant is hydrogen peroxide, persulfate or hydroperoxides.Described persulfate is generally Ammonium persulfate. or potassium peroxydisulfate.
In step of the present invention (3), it is contemplated that the initiation temperature of initiator, polymeric reaction temperature is preferably 40 DEG C～85 DEG C；Response time preferred 3h～12h.
In described step (3), for preventing miniemulsion in ultrasonic procedure overheated, the container filling thick emulsion is placed in ice-water bath and carries out supersound process.Ultrasonic power is 60～500W preferably, the preferred 5min～45min of ultrasonic time.
About the present invention, inventor finds through further investigation, and the stability of mini-emulsion polymerization system and size and the distribution thereof of prepared nano-complex particle are had material impact by emulsifier type, consumption and using method.It is used alone nonionic emulsifier, after ultrasonic homogenizing processes, the monomer miniemulsion that droplets size distribution is homogeneous, the size of monomer droplet and emulsifier type and consumption, ultrasonic power and time correlation can be prepared.Use the strong emulsifying agent of emulsifying capacity, improve emulsifier, improve ultrasonic power, extend ultrasonic time and can reduce the size of drop.It is noted that be used alone ionic emulsifying agent cannot obtain the monomer miniemulsion that droplets size distribution is homogeneous, monodispersed polymer/inorganic granule nano-complex particle also cannot be obtained.
When carrying out polyreaction with the monomer miniemulsion that nonionic emulsifier is stable, when the consumption of nonionic emulsifier is low, system is unstable, the precipitation of bulk easily occurs.System occurs that the reason of unstability is that the colloid protective capability of nonionic emulsifier itself is weak, consumption hour, it is impossible to be effectively prevented from the coalescence of particle.During nonionic emulsifier consumption height, system colloidal stability is good, but the distribution of sizes width of the final nano-complex particle prepared, and containing more blank polymer particle in product.The reason of appearance blank polymer particle is to occur homogeneous nucleation in polymerization process.Under suitable nonionic emulsifier consumption and ultrasonic homogenization conditions, after preparing the monomer miniemulsion that droplets size distribution is homogeneous, add a small amount of ionic emulsifying agent again, in polymerization process, the colloidal stability of system significantly improves, and the appearance of blank polymer particle can be effectively prevented from, final prepare mono-dispersed nano compound particle.This is because after adding a small amount of ionic emulsifying agent, except vertical structure stably except, introduce again electrostatic protective function, drastically increase the colloidal stability of particle.
Present invention firstly provides in the framework of mini-emulsion polymerization technology, prepare, for independent deflocculant, the monomer miniemulsion that droplets size distribution is homogeneous with nonionic emulsifier, then add ionic emulsifying agent and improve the New-type emulsifier using method of particle stability in mini-emulsion polymerization process, successfully prepare good sphericity, monodispersed polymer/SiO2Nano-complex particle.The preparation technology of the present invention is essentially identical with conventional mini-emulsion polymerization technique, only after prepared monomer miniemulsion, need to add a small amount of ionic emulsifying agent, stir, and is not apparent from increasing the complexity of technique.Mini-emulsion polymerization system is constituted and preparation process is simple, and colloid-stabilised interval is big, product favorable reproducibility, and easily industry is amplified；Monomeric species enriches, and can be used for preparing all kinds of polymer nano-particle；The advantages such as the inorganic nano material compound with polymeric matrix can be realized efficiently by modes such as cladding or chemical grafts all can embody well in the present invention.
Compared with prior art, the beneficial effects are mainly as follows: it is an object of the invention in the framework of mini-emulsion polymerization technology, by adopting a kind of novel emulsifying agent using method, improve polymer/SiO2The controllability of nano-complex particle synthesis.The advantage of the method is: (1) can regulate and control polymer/SiO effectively2The size of nano-complex particle and distribution thereof, prepare mono-dispersed nano compound particle；(2)SiO2Nano-particle is high with the combined efficiency of polymer, substantially without blank polymer particle in product；(3) system constitutes simple with preparation technology, easy industrial implementation.Monodisperse polymer/SiO that the present invention obtains2Nano-complex particle photonic crystal, chromatographic isolation, ordered porous materials the field such as synthesis have important using value.
(4) accompanying drawing explanation
Fig. 1 is monodisperse polymer/SiO that embodiment 1 prepares2The transmission electron microscope picture of nano-complex particle.
Fig. 2 is monodisperse polymer/SiO that embodiment 1 prepares2The scanning electron microscope (SEM) photograph of nano-complex particle.
(5) detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited to this:
Embodiment 1:
Nonionic emulsifier selects tween 20, weighs 1.25g, is dissolved in 125g water, obtains the aqueous solution of tween 20.
First by 8gSiO2(15nm, coupling density is 3.5 μm of ol (m to nano-particle2SiO2)-1) pre-dispersed in 32g methyl methacrylate, then add 13.6g styrene and 2.2g hexadecane, obtain SiO2The monomer dispersion liquid of nano-particle.
By SiO2The monomer dispersion liquid of nano-particle is added in the aqueous solution of tween 20, obtains thick emulsion after pre-emulsification, will be equipped with the container of thick emulsion and is placed in ice-water bath, and supersound process 15min under the power of 200W obtains stable monomer miniemulsion.Weigh 0.013g dodecyl dimethyl hydroxypropyl sulfobetaines again, be added in monomer miniemulsion, stir 15min; then adding 0.7g water soluble starter potassium peroxydisulfate, letting nitrogen in and deoxidizing, temperature rises to 75 DEG C; react 3h under nitrogen protection, prepare monodispersed polymer/SiO2Nano-complex particle.
By the size of transmission electron microscope observation nano-complex particle and form, result display nano-complex particle is regular spheroidal particle, and number average bead diameter is 216 ± 8nm, and distribution of sizes is homogeneous；Point rate of nano-complex particle is 98%.A point rate for nano-complex particle is defined as containing SiO2The particle of nano-particle accounts for point rate of all particles.
Embodiment 2:
Nonionic emulsifier selects OP-10, weighs 10g, is dissolved in 125g water, obtains the aqueous solution of OP-10.
First by 1.5gSiO2(30nm, coupling density is 2.5 μm of ol (m to nano-particle2SiO2)-1) pre-dispersed in 13.5g methyl methacrylate, then add 5g methacrylic acid 3-trimethoxy silicon propyl ester and 1.48g hexadecane, obtain SiO2The monomer dispersion liquid of nano-particle.
By SiO2The monomer dispersion liquid of nano-particle is added in the aqueous solution of OP-10, obtains thick emulsion after pre-emulsification, will be equipped with the container of thick emulsion and is placed in ice-water bath, and ultrasonic 5min under the ultrasonic power of 500W obtains stable monomer miniemulsion.Weigh 1.13g cetyl trimethylammonium bromide again, be added in monomer miniemulsion, stir 30min; then 0.19g water soluble starter 2,2 '-azo dibutyl amidine dihydrochloride, letting nitrogen in and deoxidizing are added; temperature rises to 65 DEG C, reacts 5h under nitrogen protection, prepares monodispersed polymer/SiO2Nano-complex particle.
By the size of transmission electron microscope observation nano-complex particle and form, result display nano-complex particle is regular spheroidal particle, and number average bead diameter is about 130 ± 4nm, and distribution of sizes is homogeneous；Point rate of nano-complex particle is 90%.
Embodiment 3:
Nonionic emulsifier selects MOA-9, weighs 0.5g, is dissolved in 125g water, obtains the aqueous solution of MOA-9.
First by 0.2gSiO2(50nm, coupling density is 2.0 μm of ol (m to nano-particle2SiO2)-1) pre-dispersed in 7.3g methyl methacrylate, then add 2.5g butyl acrylate and 0.3g hexadecane, obtain SiO2The monomer dispersion liquid of nano-particle.
By SiO2The monomer dispersion liquid of nano-particle is added in the aqueous solution of MOA-9, obtains thick emulsion after pre-emulsification, will be equipped with the container of thick emulsion and is placed in ice-water bath, and ultrasonic 45min under the ultrasonic power of 60W obtains stable monomer miniemulsion.Weigh 0.18g sodium lauryl sulphate again, be added in monomer miniemulsion, stir 30 minutes; first adding 0.03g sodium sulfite, letting nitrogen in and deoxidizing in above-mentioned monomer miniemulsion, temperature rises to 40 DEG C; add 0.05g Ammonium persulfate. again, react 8h under nitrogen protection, prepare monodispersed polymer/SiO2Nano-complex particle.
By the size of transmission electron microscope observation nano-complex particle and form, result display nano-complex particle is regular spheroidal particle, and number average bead diameter is 290 ± 10nm, and distribution of sizes is homogeneous；Point rate of nano-complex particle is 45%.
Embodiment 4:
Nonionic emulsifier selects tween 20, weighs 1.25g, is dissolved in 125g water, obtains the aqueous solution of tween 20.
First by 8gSiO2(15nm, coupling density is 3.5 μm of ol (m to nano-particle2SiO2)-1) pre-dispersed in 32g methyl methacrylate, then add 13.6g styrene, 2.2g hexadecane and 0.46g oil-soluble initiator azodiisobutyronitrile, obtain SiO2The monomer dispersion liquid of nano-particle.
By SiO2The monomer dispersion liquid of nano-particle is added in the aqueous solution of tween 20, obtains thick emulsion after pre-emulsification, will be equipped with the container of thick emulsion and is placed in ice-water bath, and supersound process 15min under the power of 200W obtains stable monomer miniemulsion.Weighing 0.013g dodecyl dimethyl hydroxypropyl sulfobetaines again, be added in monomer miniemulsion, stir 15min, letting nitrogen in and deoxidizing, temperature rises to 65 DEG C, reacts 6h under nitrogen protection, prepares monodispersed polymer/SiO2Nano-complex particle.
By the size of transmission electron microscope observation nano-complex particle and form, result display nano-complex particle is regular spheroidal particle, and number average bead diameter is 230 ± 6nm, and distribution of sizes is homogeneous；Point rate of nano-complex particle is 98%.
Embodiment 5:
Nonionic emulsifier selects OP-10, weighs 10g, is dissolved in 125g water, obtains the aqueous solution of OP-10.
First by 1.5gSiO2(30nm, coupling density is 2.5 μm of ol (m to nano-particle2SiO2)-1) pre-dispersed in 13.5g methyl methacrylate, then add 5g methacrylic acid 3-trimethoxy silicon propyl ester, 1.48g hexadecane and and 0.74g oil-soluble initiator dibenzoyl peroxide, obtain SiO2The monomer dispersion liquid of nano-particle.
By SiO2The monomer dispersion liquid of nano-particle is added in the aqueous solution of OP-10, obtains thick emulsion after pre-emulsification, will be equipped with the container of thick emulsion and is placed in ice-water bath, and ultrasonic 5min under the ultrasonic power of 500W obtains stable monomer miniemulsion.Weighing 1.13g cetyl trimethylammonium bromide again, be added in monomer miniemulsion, stir 30min, letting nitrogen in and deoxidizing, temperature rises to 85 DEG C, reacts 10h under nitrogen protection, prepares monodispersed polymer/SiO2Nano-complex particle.
By the size of transmission electron microscope observation nano-complex particle and form, result display nano-complex particle is regular spheroidal particle, and number average bead diameter is about 145 ± 5nm, and distribution of sizes is homogeneous；Point rate of nano-complex particle is 92%.
Embodiment 6:
Nonionic emulsifier selects MOA-9, weighs 0.5g, is dissolved in 125g water, obtains the aqueous solution of MOA-9.
First by 0.2gSiO2(50nm, coupling density is 2.0 μm of ol (m to nano-particle2SiO2)-1) pre-dispersed in 7.3g methyl methacrylate, then add 2.5g butyl acrylate, 0.3g hexadecane and 0.01g oil-soluble initiator 2,2'-Azobis(2,4-dimethylvaleronitrile), obtain SiO2The monomer dispersion liquid of nano-particle.
By SiO2The monomer dispersion liquid of nano-particle is added in the aqueous solution of MOA-9, obtains thick emulsion after pre-emulsification, will be equipped with the container of thick emulsion and is placed in ice-water bath, and ultrasonic 45min under the ultrasonic power of 60W obtains stable monomer miniemulsion.Weighing 0.18g sodium lauryl sulphate again, be added in monomer miniemulsion, stir 30 minutes, letting nitrogen in and deoxidizing, temperature rises to 60 DEG C, reacts 12h under nitrogen protection, prepares monodispersed polymer/SiO2Nano-complex particle.
By the size of transmission electron microscope observation nano-complex particle and form, result display nano-complex particle is regular spheroidal particle, and number average bead diameter is 305 ± 10nm, and distribution of sizes is homogeneous；Point rate of nano-complex particle is 47%.
The above embodiment of the present invention is the description of the invention and can not limit the present invention, is in that any change in implication that claims of the present invention are suitable and scope, is all considered as being included in the scope of claims.
Claims (10)
1. monodisperse polymer/SiO2The preparation method of nano-complex particle, said method comprising the steps of:
(1) by soluble in water for water-soluble nonionic emulsifying agent, the aqueous solution of emulsifying agent is obtained, wherein quality consumption is water quality consumption the 0.01%～10% of nonionic emulsifier；Described water-soluble nonionic emulsifying agent is selected from following at least one: twain series emulsifier, OP series emulsifying agent, MOA series emulsifying agent；
(2) by hydrophobic SiO2Nano-particle is scattered in partial monosomy, after adding co-stabilizer and residual monomer, obtains SiO2The monomer dispersion liquid of nano-particle, wherein hydrophobic SiO2The quality consumption of nano-particle is the 1%～30% of monomer gross mass consumption, and the quality consumption of co-stabilizer is the 2%～10% of monomer gross mass consumption；
Described monomer is selected from following at least one: the acrylic ester compound shown in styrene, formula (I)；
In formula (I), R1For H or CH3；R2For the fatty straight or branched alkyl of C1～C10, ethoxy, dimethylaminoethyl, trifluoroethyl or-(CH2)3-Si(OCH3)3；
Described co-stabilizer is selected from the fatty alcohol of the fatty straight or branched alkane of following at least one: C14～C22, C14～C22；
(3) SiO that step (2) is obtained2Monomer dispersion liquid be added in the aqueous solution of the nonionic emulsifier that step (1) obtains so that monomer gross mass consumption is the 1%～40% of water quality consumption, stirring pre-emulsification obtain thick emulsion；Will be equipped with the container of thick emulsion again and be placed in ice-water bath, supersound process 0.5min～60min under the power of 25W～950W, prepare monomer miniemulsion；Water-soluble ionic-type emulsifying agent is added to monomer miniemulsion, described water-soluble ionic-type emulsifying agent is selected from following at least one: alkylsulfonate emulsifying agent, alkylbenzenesulfonate emulsifying agent, alkyl sulfate emulsifier, alkyl carboxylate's emulsifying agent, alkylpolyoxyethylene emulsifying agent, glycine betaine emulsifying agent, aminoacid emulsifying agent, amine-oxides emulsifying agent, wherein the quality consumption of water-soluble ionic-type emulsifying agent is the 0.5%～100% of water-soluble nonionic emulsifying agent quality consumption, stirs 1min～45min；Letting nitrogen in and deoxidizing, is adjusted to temperature 35 DEG C～95 DEG C, and reacts 0.5h～24h under nitrogen protection, prepares monodisperse polymer/SiO2Nano-complex particle；
Further, initiator is introduced by following manner a or mode b:
Mode a: in step (2), toward SiO2Adding oil-soluble initiator in the monomer dispersion liquid of nano-particle, wherein the quality consumption of oil-soluble initiator is the 0.05%～5% of monomer gross mass consumption；
Mode b: in step (3), after monomer miniemulsion adds water-soluble ionic-type emulsifying agent and is uniformly mixed, adding water soluble starter to monomer miniemulsion, wherein the quality consumption of water soluble starter is the 0.05%～5% of monomer gross mass consumption.
2. monodisperse polymer/SiO as claimed in claim 12The preparation method of nano-complex particle, it is characterised in that: described water-soluble nonionic emulsifying agent at least one in tween 20, OP-10 and MOA-9, its consumption is the 0.4%～8% of water quality consumption.
3. monodisperse polymer/SiO as claimed in claim 12The preparation method of nano-complex particle, it is characterised in that: in step (2), described hydrophobic SiO2The size range of nano-particle is 10nm～100nm, coupling density range for 0.5 μm of ol (m2SiO2)-1～4.0 μm of ol (m2SiO2)-1。
4. monodisperse polymer/SiO as claimed in claim 12The preparation method of nano-complex particle, it is characterised in that: in step (2), described monomeric compound is at least one in styrene, methyl methacrylate, butyl acrylate；Co-stabilizer is the fatty straight or branched alkane of C16～C22.
5. monodisperse polymer/SiO as claimed in claim 12The preparation method of nano-complex particle, it is characterised in that: in step (2), described oil-soluble initiator is selected from following at least one: azodiisobutyronitrile, AMBN, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, lauroyl peroxide.
6. monodisperse polymer/SiO as claimed in claim 12The preparation method of nano-complex particle, it is characterized in that: water-soluble ionic-type emulsifying agent at least one in alkylsulfonate emulsifying agent, alkylbenzenesulfonate emulsifying agent, alkyl sulfate emulsifier, alkylpolyoxyethylene emulsifying agent and sulfonic group glycine betaine, its quality consumption is the 1%～36% of water-soluble nonionic emulsifying agent quality consumption.
7. monodisperse polymer/SiO as claimed in claim 62The preparation method of nano-complex particle, it is characterised in that: water-soluble ionic-type emulsifying agent at least one in sodium lauryl sulphate, cetyl trimethylammonium bromide, dodecyl dimethyl hydroxypropyl sulfonic acid base glycine betaine.
8. monodisperse polymer/SiO as claimed in claim 12The preparation method of nano-complex particle, it is characterized in that: in step (3), described water soluble starter is selected from following at least one: 2, the redox system that 2 '-azo dibutyl amidine dihydrochloride, persulfate, oxidant and reducing agent are constituted；Described reducing agent is sulphite, thiosulfate, bisulfites, oxalic acid, tertiary amine alcohol or primary amine class；Described oxidant is hydrogen peroxide, persulfate or hydroperoxides.
9. monodisperse polymer/SiO as claimed in claim 12The preparation method of nano-complex particle, it is characterised in that: in step (3), polymeric reaction temperature is 40 DEG C～85 DEG C, and the response time is 3h～12h.
10. monodisperse polymer/SiO as claimed in claim 12The preparation method of nano-complex particle, it is characterised in that: in step (3), ultrasonic power is 60～500W, and ultrasonic time is 5min～45min.
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