CN102766241A - Core-shell structured nano-silica/polyacrylate emulsion and its preparation method - Google Patents
Core-shell structured nano-silica/polyacrylate emulsion and its preparation method Download PDFInfo
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Abstract
The invention provides a core-shell structured nano-silica/polyacrylate emulsion and simultaneously provides a method for preparing the emulsion by the adoption of an emulsion polymerisation method. The preparation method comprises the following steps of: firstly preparing monodispersed nano-silica by a sol-gel method, modifying the surface of the monodispersed nano-silica by the use of organosilicon silicyl oxide, dispersing the modified nano-silica into deionized water, using a seed emulsion with nano silica as the core structure and an acrylic acid ester mixed monomer to carry out polymerization encapsulation by an emulsion polymerisation method so as to form the core-shell structured nano-silica/polyacrylate emulsion. Micromorphology of emulsion particle is spherical and its structure is a core-shell structure, and nano-silica exists as the core structure.
Description
Technical field
The present invention relates to inorganic/polyacrylic ester Composite Preparation technology, be specifically related to a kind of preparation method of aqueous core shell structural nano silicon-dioxide/poly acrylate composite emulsion.
Technical background
The multipolymer of vinyl monomer such as propenoate, methacrylic ester is called acroleic acid resin.General as the filmogen in the coating.Acroleic acid resin because have good adhesion, film forming properties has a wide range of applications in paint field, yet there is the defective of aspects such as thermostability, bad mechanical property in it.Therefore, people have carried out multiple modification in the hope of improving performance to it.Because inorganic nano material has excellent mechanical property, performance such as ageing-resistant, the machinery through combining to improve acroleic acid resin with resin, performance such as ageing-resistant are so received more and more investigators' concern to the research of organic/inorganic composite material.The method for preparing organic/inorganic composite material has sol-gel method, interlayer interpolation, blending method, situ aggregation method etc.The inorganic particulate of participating in the preparation organic/inorganic composite material mainly contains nano-calcium carbonate, nano titanium oxide, nano silicon, nano zine oxide etc.; Special; Nano silicon is widely used in fields such as coating, medicine, agriculturals as a kind of organic/inorganic composite material inorganic materials commonly used for preparing.General, nano silicon is carried out surface-treated, help nano silicon and organism graft polymerization and form organic/inorganic composite material.For example Chinese patent CN 1654533A discloses a kind of nano silicon dioxide/acrylate composite emulsion and preparation method thereof; This preparation method is earlier with the surface treatment of nanometer silicon dioxide particle process coupling agent; Get through the in-situ polymerization preparation respectively again; The amount of nanoparticle accounts for 0.1～5% of acrylate monomer consumption in this method, but it carries out microcosmic to composite emulsion and characterize, not the relation of inorganic and organic phase in the illustrative organic/inorganic composite material.Chinese patent CN 1246346C discloses a kind of preparation method of carboxyl function type macromolecule/nano silicon-dioxide composite nanoparticle; What this method adopted is no soap suspension emulsion polymerization; But but it is higher not have in the soap suspension emulsion polymerization employed reactive emulsifier cost, has limited its widespread use.
Summary of the invention
The purpose of this invention is to provide a kind of nuclear shell structure nano silicon-dioxide/polyacrylate emulsion, and a kind of this nuclear shell structure nano silicon-dioxide/polyacrylate emulsion of emulsion polymerization preparation is provided.
At first, use the Prepared by Sol Gel Method monodisperse nano silicon dioxide, and use the organosilicon silicyl oxide it is carried out surface-treated, the nano silicon after the modification is dispersed in the deionized water; Adopting emulsion polymerization, is the seed emulsion of nuclear structure with the nano silicon, carries out polymerization with propenoate mixing monomer and coats, and forms the nano silicon/polyacrylate emulsion with nucleocapsid structure.
Concrete process step is following:
A. the preparation of modified manometer silicon dioxide particle:
The add-on of each component is by following volume parts metering
Preparation technology is: ethanol, deionized water and ammoniacal liquor are added in the reactor drum that condensing works is housed be heated to 40～60 ℃, after stirring, add tetraethoxy again; Make its reaction 4～24h; Continue to stir and adjust the temperature to 20～30 ℃, in system, add silane coupling agent then, keep whipping temp reaction 8～20h; Separate, use washing with alcohol 3～4 times again, obtain the nano-silicon dioxide particle of modification; It is scattered in to be made into the quality percentage composition in the deionized water be 3% nano silicon dispersion liquid, for use;
Described silane coupling agent is: CH
2=CH-Si (OR)
3, wherein the R base is C
1～C
2Carbalkoxy or alkyl, be preferably vinyl trimethoxy siloxanes or vinyl triethoxyl siloxanes;
The preparation of B, silicon-dioxide/polyacrylate emulsion
The add-on of each component is by following mass fraction metering
Preparation technology is: silica dispersions and deionized water adding are equipped with in the reactor drum of condensing works; Stir, add compound emulsifying agent and 1～5 part of acrylate monomer again, be heated to 70～90 ℃ and the rotating speed dispersed with stirring of 250～300rpm evenly after; Again remaining acrylate monomer is slowly added, adds initiator; Stir 70～90 ℃ of thermotonus 3～7h of maintenance down, be cooled to room temperature, promptly obtain nano silicon/polyacrylate emulsion;
Described acrylate monomer is that propenoate hard monomer, propenoate soft monomer and functional monomer are the mixture of forming at 50: 47: 3 by mass ratio; Wherein the propenoate hard monomer is: one or more in TEB 3K, methacrylic tert-butyl acrylate, the acrylic amide; The propenoate soft monomer is: in Bing Xisuandingzhi, acrylic acid-2-ethyl ester, the Hydroxyethyl acrylate one or more; Functional monomer is: a kind of in vinylformic acid, the methylacrylic acid;
Described compound emulsifying agent is: the mixture that anionic emulsifier and nonionic emulsifying agent are made into by 2: 1 quality, and wherein anionic emulsifier is X 2073 or X 2073; Nonionic emulsifying agent is TX10 or octyl phenyl Soxylat A 25-7 emulsifying agent;
Described initiator is: the aqueous solution of Potassium Persulphate, ammonium persulphate or Sodium Persulfate, its mass concentration are 2～3%.
The emulsion that step B is obtained characterizes, and the result sees Fig. 1-3
Visible by Fig. 1, the chemical feature group of composition emulsion glued membrane: at 2956cm
-1And 2873cm
-1There is methyl CH at the place
3, methylene radical CH
2The absorption peak of stretching vibration; At 1729cm
-1The place is the stretching vibration absorption peak of the C=O in the propenoate; At 1620-1680cm
-1Absorption peak does not appear in the place, thereby the two keys of no C=C in the multipolymer can be described; Explain also that simultaneously acrylate monomer all participated in copolymerization.The position that the appearance of peak, centre is inhaled in the anti-stretching vibration absorption peak of Si-O-Si, stretching vibration absorption peak, flexural vibration is respectively 1100cm
-1, 800cm
-1, 470cm
-1The vicinity explains to have propenoate and nano silicon.
The microscopic pattern of the provable emulsion particle of Fig. 2 is spherical;
Fig. 3 can explain that the structure of emulsion particle is a nucleocapsid structure, and wherein nano silicon is present in the emulsion as nuclear structure.
Beneficial effect: adopt the nano silicon polyacrylate emulsion particle of the nucleocapsid structure that this method prepares to have characteristics such as low emulsifying agent, nucleocapsid structure is obvious, proterties is stable; Simultaneously, compare with other polymerization method, the preparation method is simple, the economic advantages of the cheap widespread use of equipment cost but this method also has.
Description of drawings
Fig. 1 is the infrared light spectrum figure of nano silicon/polyacrylate emulsion, and wherein a is the spectrogram of embodiment 1 sample; B is the spectrogram of embodiment 2 samples; C is the spectrogram of embodiment 3 samples;
Fig. 2 is ESEM (SEM) figure of nano silicon/polyacrylate emulsion among the embodiment 2;
Fig. 3 is transmission electron microscope (TEM) figure of nano silicon/polyacrylate emulsion among the embodiment 2;
Embodiment
Embodiment 1
A, 820ml ethanol, 30ml deionized water, 70ml ammoniacal liquor added in the reactor drum that condensing works is housed be heated to 50 ℃, after stirring, add the 40ml tetraethoxy; After making its reaction 24h; Continuously stirring also adjusts the temperature to 35 ℃, in system, adds 32ml vinyl trimethoxy silane then, keeps whipping temp reaction 12h; After reaction finishes; Separate the nano-silicon dioxide particle after the modification, be scattered in the deionized water after using washing with alcohol four times, obtain mass concentration and be 2.5% nano silicon dispersion liquid.
B, 10g silica dispersions in the steps A is added in the reactor drum that condensing works is housed; Add the 60g deionized water again, after stirring, add compound emulsifying agent and 0.3g acrylate monomer that 0.09g X 2073 and TX10 are formed; Be heated to 78 ℃ and the rotating speed dispersed with stirring of 270rpm evenly after; In system, slowly add the 9.7g acrylate monomer respectively, mass concentration is 2% ammonium persulfate aqueous solution 20ml, add finish after, behind the insulation reaction 5h; Reaction system is cooled to room temperature, can obtains nano silicon/polyacrylate emulsion.
Embodiment 2
A, 850ml ethanol, 30ml deionized water, 75ml ammoniacal liquor added in the reactor drum that condensing works is housed be heated to 50 ℃, after stirring, add the 45ml tetraethoxy; After making its reaction 22h; Continuously stirring also adjusts the temperature to 30 ℃, in system, adds 40ml vinyl three ethoxy silane then, keeps whipping temp reaction 13h; After reaction finishes; Separate the nano-silicon dioxide particle after the modification, be scattered in the deionized water after using washing with alcohol four times, obtain mass concentration and be 2.3% nano silicon dispersion liquid.
B, 20g silica dispersions in the steps A is added in the reactor drum that condensing works is housed; Add the 55g deionized water again, after stirring, add compound emulsifying agent and 0.4g acrylate monomer that 0.09g sodium laurylsulfonate and octyl phenyl Soxylat A 25-7 are formed; Be heated to 80 ℃ and the rotating speed dispersed with stirring of 300rpm evenly after; In system, slowly add the 9.6g acrylate monomer respectively, mass concentration is 3% persulfate aqueous solution 20ml, add finish after, behind the insulation reaction 5h; Reaction system is cooled to room temperature, can obtains nano silicon/polyacrylate emulsion.
Embodiment 3
A, 870ml ethanol, 40ml deionized water, 77ml ammoniacal liquor added in the reactor drum that condensing works is housed be heated to 50 ℃, after stirring, add the 50ml tetraethoxy, make its reaction 10h after, obtain nano-silicon dioxide particle; After the monodisperse nano silicon dioxide particle preparation is accomplished; Continuously stirring also adjusts the temperature to 30 ℃, in system, adds 20ml vinyl trimethoxy silane then, keeps whipping temp reaction 13h; After reaction finishes; Separate the nano-silicon dioxide particle after the modification, be scattered in the deionized water after using washing with alcohol four times, obtain mass concentration and be 2.9% nano silicon dispersion liquid.
B, 26g silica dispersions in the steps A is added in the reactor drum that condensing works is housed; Add the 54g deionized water again, after stirring, add compound emulsifying agent and 0.4g acrylate monomer that 0.09g X 2073 and octyl phenyl Soxylat A 25-7 are formed; Be heated to 83 ℃ and the rotating speed dispersed with stirring of 280rpm evenly after; In system, slowly add 9.6g acrylate monomer, mass concentration respectively and be 2% persulfuric acid and receive aqueous solution 20ml, add finish after, behind the insulation reaction 6h; Reaction system is cooled to room temperature, can obtains nano silicon/polyacrylate emulsion.
Claims (3)
1. the preparation method of a nuclear shell structure nano silicon-dioxide/polyacrylate emulsion, concrete process step is following:
A. the preparation of modified manometer silicon dioxide particle:
The add-on of each component is by following volume parts metering
Preparation technology is: ethanol, deionized water and ammoniacal liquor are added in the reactor drum that condensing works is housed be heated to 40～60 ℃, after stirring, add tetraethoxy again; Make its reaction 4～24h; Continue to stir and adjust the temperature to 20～30 ℃, in system, add silane coupling agent then, keep whipping temp reaction 8～20h; Separate, use washing with alcohol 3～4 times again, obtain the nano-silicon dioxide particle of modification; It is scattered in to be made into the quality percentage composition in the deionized water be 3% nano silicon dispersion liquid, for use; Described silane coupling agent is: CH
2=CH-Si (OR)
3, wherein the R base is C
1～C
2Carbalkoxy or alkyl;
The preparation of B, silicon-dioxide/polyacrylate emulsion
The add-on of each component is by following mass fraction metering
Preparation technology is: silica dispersions and deionized water adding are equipped with in the reactor drum of condensing works; Stir, add compound emulsifying agent and 1～5 part of acrylate monomer again, be heated to 70～90 ℃ and the rotating speed dispersed with stirring of 250～300rpm evenly after; Again remaining acrylate monomer is slowly added, adds initiator; Stir 70～90 ℃ of thermotonus 3～7h of maintenance down, be cooled to room temperature, promptly obtain nano silicon/polyacrylate emulsion;
Described acrylate monomer is that propenoate hard monomer, propenoate soft monomer and functional monomer are the mixture of forming at 50: 47: 3 by mass ratio; Wherein the propenoate hard monomer is: one or more in TEB 3K, methacrylic tert-butyl acrylate, the acrylic amide; The propenoate soft monomer is: in Bing Xisuandingzhi, acrylic acid-2-ethyl ester, the Hydroxyethyl acrylate one or more; Functional monomer is: a kind of in vinylformic acid, the methylacrylic acid;
Described compound emulsifying agent is: the mixture that anionic emulsifier and nonionic emulsifying agent are made into by 2: 1 quality, and wherein anionic emulsifier is X 2073 or X 2073; Nonionic emulsifying agent is TX10 or octyl phenyl Soxylat A 25-7 emulsifying agent;
Described initiator is: the aqueous solution of Potassium Persulphate, ammonium persulphate or Sodium Persulfate, its mass concentration are 2～3%.
2. the preparation method of nuclear shell structure nano silicon-dioxide/polyacrylate emulsion according to claim 1 is characterized in that the described silane coupling agent of steps A is vinyl trimethoxy siloxanes or vinyl triethoxyl siloxanes;
3. the nuclear shell structure nano silicon-dioxide/polyacrylate emulsion of a method according to claim 1 preparation, the microscopic pattern of emulsion particle be a sphere, wherein nano silicon is present in the emulsion as nuclear structure.
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Application publication date: 20121107 |