CN102030873A - Method for preparing nano silicon/polyacrylate composite emulsion - Google Patents
Method for preparing nano silicon/polyacrylate composite emulsion Download PDFInfo
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Abstract
The invention discloses a method for preparing nano silicon/polyacrylate composite emulsion. The method comprises the following steps of: adding the adding hydrochloric solution and an emulsifier into de-ionized water, mixing the mixed solution and tetraethoxysilane, a silane coupling agent and acrylate monomers and pre-emulsifying to obtain modified nano silicon pre-emulsion; heating, adding an initiator, and preparing the nano silicon/polyacrylate composite emulsion by adopting an in-situ emulsion polymerization and seed emulsion polymerization combined method. The method has a simple process, solves the problem of 'secondary aggregation' of the traditional nano silicon during emulsion polymerization and effectively guarantees the stable proceeding of a polymerization reaction, the prepared nano silicon/polyacrylate composite emulsion has high stability, and the film of the nano silicon/polyacrylate composite emulsion has high heat resistance.
Description
Technical field
The present invention relates to poly acrylate composite emulsion, particularly relate to a kind of preparation method of nano silicon/poly acrylate composite emulsion.
Technical background
The organic/inorganic nano composite emulsion was risen in late 1980s, it not only combines the good film-forming properties of macromolecular material, the transparency, snappiness, workability etc. and inorganic materials wear resistance, high rigidity, scratch resistance, ultraviolet-resistent property etc. preferably, but also have characteristics such as asepsis environment-protecting, reaction conditions gentleness, become the focus of current research.
Polyacrylate dispersion has excellent gloss retention, tint retention, weathering resistance, be a kind of matrix resin that is widely used in coating, sizing agent, fabric finishing agent, but the hardness of its existence low, wear no resistance, drawbacks limit such as solvent resistance deficiency its further application.Nano silicon is because its wide material sources, cheap also have the good reinforcing effect of nanoparticle simultaneously, now by compound to improve the use properties of emulsion with polyacrylate dispersion morely.
At present, along with the development of emulsion polymerization technology, the preparation method of nano silicon/poly acrylate composite emulsion is developed by the direction of traditional physical blending normal direction in-situ emulsion polymerization.For example, Chinese invention patent CN 1908022A (application number: 200610037040.9) disclose the utilization tetraethoxy and in ethanol, prepared nano silicon, and use silane coupling agent to its surface modification, will make surface modification silicon-dioxide then and be distributed to again and carry out in-situ emulsion polymerization in the acrylate monomer and obtain nano-silicon dioxide modified acrylic ester emulsion.Zhu etc. are dispersed in aerosil in the toluene, use silane coupling agent it is carried out surface modification, with gained improved silica redispersion in water, and the adding acrylate monomer carries out nano silicon/poly acrylate composite emulsion (Zhu A. that in-situ emulsion polymerization obtains excellent property, Cai A., Yu Z., et al.Film characterization of poly (styrene-butylacrylate-acrylic acid)-silica nanocomposite[J] .Journal of Colliod and Interface Science, 2008,322 (1): 51-58).Adopt the in-situ emulsion polymerization method nano silicon of surface modification can be scattered in the polymkeric substance comparatively equably, and can improve its physical and mechanical properties to a certain extent.But the technology more complicated for preparing nano silicon/poly acrylate composite emulsion by this method, and modified manometer silicon dioxide easy generation secondary agglomeration in preparation and dispersive process, thereby influence the reaction stability of letex polymerization.
Summary of the invention
The objective of the invention is to overcome the in-situ emulsion polymerization method and prepare shortcomings such as the existing complex process of nano silicon/poly acrylate composite emulsion, the easy reunion of nano silicon, a kind of agglomeration traits of avoiding nano silicon is provided, polymerization process is stable, and the preparation method of the simple nano silicon/poly acrylate composite emulsion of preparation technology.
The present invention is in the pre-emulsion of acrylate monomer and emulsifying agent formation, tetraethoxy and silane coupling agent be hydrolytic condensation under the catalysis of hydrochloric acid, directly obtain stable modified manometer silicon dioxide pre-emulsion, then pre-emulsion is heated up and the adding initiator, the method that adopts in-situ emulsion polymerization to combine with seeded emulsion polymerization makes nano silicon/poly acrylate composite emulsion.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of nano silicon/poly acrylate composite emulsion may further comprise the steps:
(1) at room temperature, hydrochloric acid soln 0.01-0.03 part and emulsifying agent 0.6-3.15 part are added in 10-50 part deionized water, and mix with 1.5-10 part tetraethoxy, 0.1-1 part silane coupling agent and 5-50 part acrylate monomer, pre-emulsification 10-15min, stirring reaction 8-24h obtains the modified manometer silicon dioxide pre-emulsion then;
(2) be under 65-75 ℃ in temperature, the modified manometer silicon dioxide pre-emulsion is added drop-wise in 10-50 part deionized water, the aqueous solution that adds 0.05-0.3 part initiator, insulation reaction 20-40min, add 0.35-2.9 part emulsifying agent, 5-50 part acrylate monomer and 10-50 part deionized water, pre-emulsification 5-10min, obtain the acrylate pre-emulsion, the aqueous solution that is made into by 0.05-0.3 part initiator and 5-10 part deionized water is added drop-wise in the described acrylate pre-emulsion, continue to be warming up to 80-90 ℃ and insulation reaction 1.0-2.5h, reduce to room temperature, obtain nano silicon/poly acrylate composite emulsion;
Described silane coupling agent is γ-methacryloxypropyl trimethoxy silane (KH-570), vinyltrimethoxy silane (A-171) or vinyltriethoxysilane (A-151);
Described emulsifying agent is one or both in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, allyloxy hydroxypropyl azochlorosulfonate acid sodium, allyloxy nonyl phenolic ether, alkylphenol polyoxyethylene and the fatty alcohol-polyoxyethylene ether;
Described initiator is Potassium Persulphate or ammonium persulphate;
Described acrylate monomer is one or more in methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid-2-ethylhexyl, hydroxyethyl methylacrylate, Rocryl 410, methacrylic acid, methyl acrylate, ethyl propenoate, butyl acrylate, ethyl acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate and the vinylformic acid.
For further realizing the object of the invention, the mass concentration of described hydrochloric acid soln is preferably 36-38%.
Described modified manometer silicon dioxide pre-emulsion preferably is added drop-wise in 10-50 part deionized water with the speed of 0.4-0.6g/min.
The described aqueous solution that is made into by 0.05-0.3 part initiator and 5-10 part deionized water preferably is added drop-wise to described acrylate pre-emulsion with the speed of 0.06-0.12g/min.
Described acrylate monomer is preferably methyl methacrylate, butyl methacrylate, methacrylic acid-2-ethylhexyl, Rocryl 410, methacrylic acid, butyl acrylate, Propylene glycol monoacrylate and/or vinylformic acid.
Compared with prior art, the present invention has following advantage:
(1) in the acrylate pre-emulsion, prepares the modified manometer silicon dioxide dispersion liquid by sol-gel method, has good dispersiveness, can directly apply to home position polymerization reaction, simplify technology, avoided modified manometer silicon dioxide in preparation and application process, to produce the problem of " secondary agglomeration ".
(2) method that adopts in-situ emulsion polymerization and seeded emulsion polymerization to combine, guaranteed steadily carrying out of polymerization process, polyacrylic ester can successful clad nano silicon-dioxide, prepared nano silicon/poly acrylate composite emulsion has satisfactory stability, the fine heat-resisting performance that it is filmed.
Description of drawings
Fig. 1 is the total reflection infrared spectrum of nano silicon/polyacrylic ester composite emulsion film.
Fig. 2 is the transmission electron microscope photo of pure third latex particle (a) and nano silicon/polyacrylic ester composite emulsion particle (b), and wherein the content of nano silicon is 4% in the composite emulsion particle.
Fig. 3 is that pure-acrylic emulsion is filmed (a) and the film thermogravimetric analysis figure of (b) of nano silicon/poly acrylate composite emulsion, and wherein the content of nano silicon is 4% in the composite emulsion.
Specific embodiments
The invention will be further described below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
2.0g allyloxy nonylphenol propyl alcohol polyoxyethylene ether ammonium sulfate (DNS-86) and 0.013g concentrated hydrochloric acid (mass concentration 36%) are added in the 25g deionized water, and with the pre-emulsification 10min of the mixed solution that contains 10g butyl acrylate, 10g methyl methacrylate, 5.5g tetraethoxy and 0.5g KH-570, on magnetic stirring apparatus, stir 12h, make the modified manometer silicon dioxide pre-emulsion.
In temperature is under 75 ℃, the modified manometer silicon dioxide emulsion is added drop-wise in 1.5h in the 35g deionized water, and to add the 10g weight concentration is 1.5% persulfate aqueous solution insulation 30min.
Simultaneously, with the pre-emulsification 5min of 0.4g DNS-86,10g butyl acrylate, 10g methyl methacrylate, 1.6g vinylformic acid and 20g deionized water, make the acrylate pre-emulsion, in 2h, drip acrylate pre-emulsion and 15g mass concentration then and be 1% persulfate aqueous solution.Be warming up to 80 ℃ after dripping off, and insulation reaction 2h.
At last, reduce to room temperature, obtain nano silicon/poly acrylate composite emulsion.
Fig. 1 is the composite emulsion film total reflection infrared spectrum of present embodiment.Among Fig. 1,2958cm
-1Be the stretching vibration absorption peak of c h bond, 1733cm
-1The place is the stretching vibration peak of carbonyl, 1166cm
-1The place is the asymmetrical stretching vibration absorption peak of C-O-C, and 1070cm
-1And 809cm
-1The place is the stretching vibration peak of Si-O-Si key, has shown that acrylate monomer is grafted on the nano silicon at nano-silica surface generation in-situ polymerization.The preparation of pure-acrylic emulsion is according to prescription and the technology of embodiment 1, and difference is not add tetraethoxy and KH-570 in the prescription.
Fig. 2 is this example and pure polyacrylic ester latex particle transmission electron microscope photo, and a and b in the comparison diagram 2 can find that composite polymer particle that the present invention makes is the nucleocapsid structure of polyacrylic ester clad nano silicon-dioxide.The polyacrylic ester latex particle transmission electron microscope photo of following embodiment is similar to Fig. 2.Fig. 3 is the thermogravimetric analysis curve of this example and virgin pp acid esters latex film.Can get from Fig. 3, the maximum heat weight loss rate temperature of virgin pp acid esters latex film is 407 ℃, and the maximum heat weight loss rate temperature of composite emulsion film is 417 ℃, has improved 10 ℃.As seen prepared the filming of composite emulsion of the present invention is improved on resistance toheat.The thermogravimetric analysis curve of following embodiment is similar substantially to present embodiment, does not list one by one.
Embodiment 2
1.3g DNS-86 and 0.01g concentrated hydrochloric acid (mass concentration 36%) are added in the 25g deionized water, and with the pre-emulsification 10min of the mixed solution that contains 5g methacrylic acid-2-ethylhexyl, 5g methyl acrylate, 1.5g tetraethoxy and 0.1gKH-570, on magnetic stirring apparatus, stir 8h, make the modified manometer silicon dioxide pre-emulsion.Under 75 ℃, the modified manometer silicon dioxide emulsion is added drop-wise in the 35g deionized water, and to add the 5g weight concentration be 1% persulfate aqueous solution insulation 20min in 1h.Simultaneously, with the pre-emulsification 5min of 0.2g DNS-86,10g butyl acrylate, 10g methyl methacrylate, 0.6g vinylformic acid and 20g deionized water, make the acrylate pre-emulsion, in 2h, drip acrylate pre-emulsion and 5g mass concentration then and be 1% persulfate aqueous solution.Be warming up to 80 ℃ after dripping, and insulation reaction 2h.At last, reduce to room temperature, obtain nano silicon/poly acrylate composite emulsion.
Embodiment 3
With 1.5g DNS-86,0.8g allyloxy nonylphenol propyl alcohol polyoxyethylene (ANPEO
10) and 0.03g concentrated hydrochloric acid (mass concentration 36%) add in the 30g deionized water, and with the pre-emulsification 15min of the mixed solution that contains 15g butyl acrylate, 10g tetraethoxy and 1gA-171, on magnetic stirring apparatus, stir 24h, make the modified manometer silicon dioxide pre-emulsion.Under 70 ℃, the modified manometer silicon dioxide emulsion is added drop-wise in the 35g deionized water, and to add the 10g weight concentration be 1.5% persulfate aqueous solution insulation 40min in 1.5h.Simultaneously, with 0.4g DNS-86,0.2g ANPEO
10, 7.5g butyl acrylate, 7.5g methyl methacrylate, 0.5g methacrylic acid, 0.5g Hydroxyethyl acrylate and the pre-emulsification 5min of 15g deionized water, make the acrylate pre-emulsion, in 1.5h, drip acrylate pre-emulsion and 15g mass concentration then and be 1% persulfate aqueous solution.Be warming up to 85 ℃ after dripping, and insulation reaction 2.5h.At last, reduce to room temperature, obtain nano silicon/poly acrylate composite emulsion.
Embodiment 4
1.5g sodium lauryl sulphate, 0.8g nonyl phenol polyethenoxy ether and 0.01g concentrated hydrochloric acid (mass concentration 38%) are added in the 25g deionized water, and with the pre-emulsification 15min of the mixed solution that contains 20g butyl acrylate, 10g methyl acrylate, 3g tetraethoxy and 0.3gA-151, on magnetic stirring apparatus, stir 24h, make the modified manometer silicon dioxide pre-emulsion.Under 75 ℃, the modified manometer silicon dioxide emulsion is added drop-wise in the 35g deionized water, and to add the 10g weight concentration be 1.5% persulfate aqueous solution insulation 30min in 1.5h.Simultaneously, with 0.4g sodium lauryl sulphate, 0.2g nonyl phenol polyethenoxy ether, 20g butyl acrylate, 10g methyl methacrylate, 1.6g vinylformic acid and the pre-emulsification 10min of 20g deionized water, make the acrylate pre-emulsion, in 2h, drip acrylate pre-emulsion and 15g mass concentration then and be 1% persulfate aqueous solution.Be warming up to 85 ℃ after dripping, and insulation reaction 2.5h.At last, reduce to room temperature, obtain nano silicon/poly acrylate composite emulsion.
Embodiment 5
2.5g 3-allyloxy-2-hydroxyl-1-propane sulfonic acid sodium and 0.01g concentrated hydrochloric acid (mass concentration 36%) are added in the 20g deionized water, and with the pre-emulsification 15min of the mixed solution that contains 15g butyl methacrylate, 5.5g tetraethoxy and 0.5gKH-570, on magnetic stirring apparatus, stir 12h, make the modified manometer silicon dioxide pre-emulsion.Under 75 ℃, the modified manometer silicon dioxide emulsion is added drop-wise in 1h in the 35g deionized water, and to add the 10g weight concentration be 1.5% persulfate aqueous solution, be incubated 20min again.Simultaneously, with 0.5g3-allyloxy-2-hydroxyl-1-propane sulfonic acid sodium, 20g butyl acrylate, 20g ethyl acrylate, 8g methyl methacrylate, 1g vinylformic acid, 1g Rocryl 410 and the pre-emulsification 10min of 30g deionized water, make the acrylate pre-emulsion, in 2.5h, drip acrylate pre-emulsion and 15g mass concentration then and be 1% persulfate aqueous solution.Be warming up to 80 ℃ after dripping, and insulation reaction 2.5h.At last, reduce to room temperature, obtain nano silicon/poly acrylate composite emulsion.
Claims (5)
1. the preparation method of a nano silicon/poly acrylate composite emulsion is characterized in that may further comprise the steps:
(1) at room temperature, hydrochloric acid soln 0.01-0.03 part and emulsifying agent 0.6-3.15 part are added in 10-50 part deionized water, and mix with 1.5-10 part tetraethoxy, 0.1-1 part silane coupling agent and 5-50 part acrylate monomer, pre-emulsification 10-15min, stirring reaction 8-24h obtains the modified manometer silicon dioxide pre-emulsion then;
(2) be under 65-75 ℃ in temperature, the modified manometer silicon dioxide pre-emulsion is added drop-wise in 10-50 part deionized water, the aqueous solution that adds 0.05-0.3 part initiator, insulation reaction 20-40min, add 0.35-2.9 part emulsifying agent, 5-50 part acrylate monomer and 10-50 part deionized water, pre-emulsification 5-10min, obtain the acrylate pre-emulsion, the aqueous solution that is made into by 0.05-0.3 part initiator and 5-10 part deionized water is added drop-wise in the described acrylate pre-emulsion, continue to be warming up to 80-90 ℃ and insulation reaction 1.0-2.5h, reduce to room temperature, obtain nano silicon/poly acrylate composite emulsion;
Described silane coupling agent is γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane or vinyltriethoxysilane;
Described emulsifying agent is one or both in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, allyloxy hydroxypropyl azochlorosulfonate acid sodium, allyloxy nonyl phenolic ether, alkylphenol polyoxyethylene and the fatty alcohol-polyoxyethylene ether;
Described initiator is Potassium Persulphate or ammonium persulphate;
Described acrylate monomer is one or more in methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid-2-ethylhexyl, hydroxyethyl methylacrylate, Rocryl 410, methacrylic acid, methyl acrylate, ethyl propenoate, butyl acrylate, ethyl acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate and the vinylformic acid.
2. the preparation method of nano silicon/poly acrylate composite emulsion according to claim 1, it is characterized in that: the mass concentration of described hydrochloric acid soln is 36-38%.
3. the preparation method of nano silicon/poly acrylate composite emulsion according to claim 1, it is characterized in that: described modified manometer silicon dioxide pre-emulsion is added drop-wise in 10-50 part deionized water with the speed of 0.4-0.6g/min.
4. the preparation method of nano silicon/poly acrylate composite emulsion according to claim 1 is characterized in that: the described aqueous solution that is made into by 0.05-0.3 part initiator and 5-10 part deionized water is that the speed with 0.06-0.12g/min is added drop-wise to described acrylate pre-emulsion.
5. the preparation method of nano silicon/poly acrylate composite emulsion according to claim 1, it is characterized in that: described acrylate monomer is methyl methacrylate, butyl methacrylate, methacrylic acid-2-ethylhexyl, Rocryl 410, methacrylic acid, butyl acrylate, Propylene glycol monoacrylate and/or vinylformic acid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944479A (en) * | 2006-10-24 | 2007-04-11 | 河北工业大学 | Poly acrylate composite emulsion for pressure' sensitive adhesive and its preparing and using method |
| CN1986582A (en) * | 2006-12-08 | 2007-06-27 | 陕西科技大学 | Emulsion polymerization process for in-situ preparing nano SiO2/acrylate resin composite paint |
| CN101735412A (en) * | 2009-12-01 | 2010-06-16 | 陕西科技大学 | Method for preparing organosilicon and nano-silicon dioxide modified acrylic resin soap-free emulsion |
-
2010
- 2010-10-27 CN CN201010524511A patent/CN102030873B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944479A (en) * | 2006-10-24 | 2007-04-11 | 河北工业大学 | Poly acrylate composite emulsion for pressure' sensitive adhesive and its preparing and using method |
| CN1986582A (en) * | 2006-12-08 | 2007-06-27 | 陕西科技大学 | Emulsion polymerization process for in-situ preparing nano SiO2/acrylate resin composite paint |
| CN101735412A (en) * | 2009-12-01 | 2010-06-16 | 陕西科技大学 | Method for preparing organosilicon and nano-silicon dioxide modified acrylic resin soap-free emulsion |
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