CN102391410A - Inorganic nano particle modified composite waterproof emulsion and preparation method thereof - Google Patents
Inorganic nano particle modified composite waterproof emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention provides inorganic nano particle modified composite waterproof emulsion and a preparation method thereof and belongs to the technical field of preparation of an exterior wall water-based paint. The composite waterproof emulsion comprises the following components in percentage by mass: 2 to 3 percent of acrylic acid, 15 to 20 percent of methyl methacrylate, 12 to 16 percent of butyl acrylate, 1 to 3 percent of other monomers, 2.4 to 4.8 percent of modified nano particle mixture, 1.5 to 3 percent of complex emulsifying agent, 0.4 to 0.8 percent of initiator, 2.4 to 4.8 percent of organic silicone monomer, a right amount of pH regulator, 45 to 55 percent of deionized water and 0.3 to 0.7 percent of buffering agent. In the invention, the addition speed, the addition ratio and the stirring speed of nano particles are strictly controlled. Compared with emulsion which is not modified, the prepared emulsion provided by the invention has the advantage that the waterproofness, the mechanical strength, the self-cleaning property and the aging resistance of the emulsion are improved.
Description
Technical field
The invention belongs to the outer wall water-based coating preparing technical field, be specifically related to inorganic nano particle modified composite water-proof emulsion and preparation method thereof.
Background technology
Emulsion property is to the coating decisive role.Multiple water-borne coatings existing on the market has been applied to exterior finish; Wherein the defective of emulsion property makes that the coating abrasion resistance is poor, film adhesive difference and coating be not fine and close; Cause the not good and disbonding of coating property; The variegated phenomenon of wall can be found everywhere, and not only greatly influences attractive in appearancely, and has caused problems such as ample resources waste, living environment pollution.
For solving the quality problems of coating, investigators have proposed multiple solution, and wherein the reasonable method of effect is the inorganic nano-particle that in the emulsion building-up process, mixes, and improve emulsion property.Common nanoparticle joins in the water-proof emulsion can improve emulsion property; But because the restriction of consistency between inorganic particulate and the organic polymer; Shortcomings such as ubiquity poor stability, contamination resistance is poor, emulsion is faded, instability, these have limited the application of water-proof emulsion to a certain extent.Chinese patent CN1424353A adds unmodified nanometer SiO
2, TiO
2, ZnO, CaCO
3Etc. inorganic phase, adopt inverse emulsion polymerization/letex polymerization two-stage polymerization legal system to be equipped with organosilicon crylic acid latex.Chinese patent CN101967257A adopts silane coupling agent and oleic acid mixture to inorganic nano particle modified, and then has prepared inorganic nano particle modified pure-acrylic emulsion.Chinese patent CN1394888A adopts the preparation method of in-situ nano compounded silicone propyl emulsion, is nuclear with the nano level pure-acrylic emulsion, is shell with an organosilane monomer with (methyl) Acrylic Acid Monomer mixture, synthetic composite emulsion in water medium.Though the disclosed emulsion preparation method of above-mentioned patent has improved the stability to aging of emulsion, water resistance and the nanoparticle stability in emulsion, but ignored the wear resistance and the self-cleaning of emulsion.
Summary of the invention
The present invention is directed to existing emulsion water-proof, wear-resisting, stable, the existing problem of self-cleaning property, propose a kind of inorganic nano particle modified composite water-proof emulsion and preparation method thereof.
The composition and the mass percent of inorganic nano particle modified composite water-proof emulsion provided by the present invention are following:
Vinylformic acid 2～3%
TEB 3K 15～20%
Bing Xisuandingzhi 12～16%
Other monomer 1～3%
Modified Nano particles mixture 2.4～4.8%
Compound emulsifying agent 1.5～3%
Initiator 0.4～0.8%
An organosilane monomer 2.4～4.8%
The pH regulator agent is an amount of
Deionized water 45～55%
Buffer reagent 0.3～0.7%
The preparation process of inorganic nano particle modified composite water-proof emulsion provided by the present invention is specific as follows:
1, preparation modified Nano particles mixture:
The nanoparticle of getting certain mass is dissolved in the mixing solutions of alcohol-water (volume ratio is 1:1), and ultrasonic 1～1.5h gets the uniform nano particle dispersion liquid; Nanoparticle dispersion liquid is transferred in the there-necked flask of band prolong, be warming up to 80～90 ℃ under the magnetic agitation, using Glacial acetic acid min. 99.5 to regulate the pH value is 3～4; In there-necked flask, drip silane coupling agent (mol ratio of nanoparticle and silane coupling agent is 1: (8～10)), reaction 2h～2.5h is after reaction finishes; Suction filtration; Be washed till the filtrating clarification with ethanol, place 80～85 ℃ vacuum drying oven to dry 8～12h product after the washing, grind and obtain the modified Nano particles mixture.
2, the inorganic nano particle modified composite water-proof emulsion of preparation:
A: a certain amount of modified Nano particle is distributed in the acrylic monomer mixture, and machinery stirs 0.5h earlier, and ultrasonic again 1～2h is subsequent use;
B: in the four-hole boiling flask that TM, reflux condensing tube, whisking appliance and dropper are housed, add a certain amount of deionized water; Regulating bath temperature is 40～50 ℃; In reactor drum, add whole emulsifying agents, 2/3 initiator and a certain amount of buffer reagent; Dissolving back drips 1/2 an organosilane monomer, with warming-in-water to 80～90 ℃; Drip the monomer mixture that steps A obtains, in 3～4h, dropwise, add remaining an organosilane monomer and initiator subsequently, continue reaction 1～1.5h in 80～90 ℃ of water-baths; Emulsion is naturally cooled to 40～50 ℃, add the pH regulator agent, regulating emulsion pH is 8～9, and discharging obtains inorganic nano particle modified composite water-proof emulsion behind the stirring 1h.
Said modified Nano particles mixture is two or more the mixture in modified nano silicon oxide, modified Nano titanium oxide, modified nano zinc oxide and the modified Nano aluminum oxide, and the mass ratio of said modified nano silicon oxide, modified Nano titanium oxide, modified nano zinc oxide, modified Nano aluminum oxide is (1.0～1.2): (1.1～1.5): (0.4～1.2): (0.4～1.2).
The size of said nano silicon oxide, nano-titanium oxide, nano aluminium oxide, nano zine oxide is lower than 100nm.
Said other monomer is one or more the mixture in NSC 20956, ethyl propenoate, 2-EHA, the Isooctyl acrylate monomer.
Said silane coupling agent is one or more mixtures in γ-methacryloxypropyl trimethoxy silane (KH-570), γ-An Bingjisanyiyangjiguiwan (KH-550), the γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560).
Said compound emulsifying agent is the mixture of anionic emulsifier and nonionic emulsifier, and anionic emulsifier is a sodium lauryl sulphate, and nonionic emulsifier is OP-10, and the mass ratio of anionic emulsifier and nonionic emulsifier is 1:1.4.
Said an organosilane monomer is one or both mixtures in vinyltrimethoxy silane (A-171), the vinyltriethoxysilane (A-151).
Said pH regulator agent is the ammonia soln of mass concentration 25～28%.
Said initiator is a Potassium Persulphate.
Said buffer reagent is a sodium hydrogencarbonate.
To the technical problem that existing emulsion exists, add nanoparticle and improve:
Nano silicon oxide: nano silicon oxide has huge specific surface area, when coating is dry, has strengthened the intensity and the smooth finish of coating, has good automatically cleaning ability, water-repellancy and adhesive ability.
Nano zine oxide/titanium oxide: this nanoparticle well is dispersed in the emulsion, will greatly brings into play its modification function, improve the opacifying power and the tinting strength of emulsion greatly, also will improve the uvioresistant ability of emulsion simultaneously, improve stability to aging.
Nano aluminium oxide: nano aluminium oxide well is distributed in the emulsion, can greatly improves hardness, scratch resistance and the wear resistance of emulsion coating, meanwhile add the water-repellancy that more can strengthen emulsion behind the nano aluminium oxide.
In order to solve the scattering problem of inorganic nano-particle in high molecular polymer, the present invention designs silane coupling agent nanoparticle surface is handled.The nanometer particle-modified principle that relates to: the nanoparticle surface after water-dispersion contain hydroxyl (OH), can with silane coupling agent in-OCH
3React, thereby on nanoparticle surface connects, contain the group of " Si-O-Si-" key, make nanoparticle can form the dispersion system of high dispersingization, homogenizing and stabilization.
Characteristic of the present invention is the modified Nano particle that designs; No matter being on selection or properties-correcting agent, all is through strict investigation, through attempting its consumption, method of modifying and the combination of the ratio between them; Find optimum fiting ratio, remedied the defective of forefathers in this research.Compare before adding speed, additional proportion, the stirring velocity of strict control nanoparticle, the emulsion that makes and modification, well improved water-repellancy, physical strength, self-cleaning property, the resistance to deterioration of emulsion.
Property agent body, 2 bright spots of the present invention are: in emulsion; The inorganic modified nanoparticle that adds in proportion can be brought into play its surface-treated key effect preferably; Be connected among the polymkeric substance with more orderly structure; Reduce the interaction between each nanoparticle, made the nanoparticle that adds farthest to play a role, better improved the emulsion correlated performance.
Embodiment
Embodiment 1: the mass percent of inorganic nano particle modified composite water-proof emulsion is following:
Vinylformic acid 3%
TEB 3K 18%
Bing Xisuandingzhi 16%
Other monomer 1.3%
Modified Nano particles mixture 2.4%
Compound emulsifying agent 1.5%
Initiator 0.4%
An organosilane monomer 3.1%
The pH regulator agent is an amount of
Deionized water 52%
Sodium hydrogencarbonate 0.4%
The modified Nano particle that takes by weighing content in the prescription is distributed in the acrylic monomer mixture, and machinery stirs 0.5h, ultrasonic again 1h earlier.In the four-hole boiling flask that TM, reflux condensing tube, whisking appliance and dropper are housed, add a certain amount of deionized water; Regulating bath temperature is 40 ℃; In reactor drum, add whole emulsifying agents, 2/3 initiator and a certain amount of sodium hydrogencarbonate; Dissolving back drips 1/2 an organosilane monomer, with warming-in-water to 80 ℃; Drip monomer mixture, in 3h, dropwise, add remaining an organosilane monomer and initiator subsequently, continue reaction 1h in 80 ℃ of water-baths; Emulsion is naturally cooled to 40 ℃, add the pH regulator agent, regulating emulsion pH is 8～9, and discharging promptly gets inorganic nano particle modified composite water-proof emulsion behind the stirring 1h.
1. modified Nano mix particles amount proportioning:
Modified nano silicon oxide: modified Nano titanium oxide: modified nano zinc oxide: modified Nano aluminum oxide=1:1:1:1.
2. other monomer is that NSC 20956, ethyl propenoate, Isooctyl acrylate monomer are the mixture of 1:1:1 by mass ratio.
3. an organosilane monomer is vinyltrimethoxy silane (A-171).
Embodiment 2: the mass percent of inorganic nano particle modified composite water-proof emulsion is following:
Vinylformic acid 2.3%
TEB 3K 17%
Bing Xisuandingzhi 15%
Other monomer 1.8%
Modified Nano particles mixture 3.2%
Compound emulsifying agent 1.8%
Initiator 0.5%
An organosilane monomer 4.0%
The pH regulator agent is an amount of
Deionized water 50.5%
Sodium hydrogencarbonate 0.5%
The modified Nano particle that takes by weighing content in the prescription is distributed in the acrylic monomer mixture, and machinery stirs 0.5h, ultrasonic again 1.5h earlier.In the four-hole boiling flask that TM, reflux condensing tube, whisking appliance and dropper are housed, add a certain amount of deionized water; Regulating bath temperature is 45 ℃; In reactor drum, add whole emulsifying agents, 2/3 initiator and a certain amount of sodium hydrogencarbonate; Dissolving back drips 1/2 an organosilane monomer, with warming-in-water to 85 ℃; Drip monomer mixture, in 3.5h, dropwise, add remaining an organosilane monomer and initiator subsequently, continue reaction 1.5h in 85 ℃ of water-baths; Emulsion is naturally cooled to 45 ℃, add the pH regulator agent, regulating emulsion pH is 8～9, and discharging promptly gets inorganic nano particle modified composite water-proof emulsion behind the stirring 1h.
1. modified Nano mix particles amount proportioning:
Modified nano silicon oxide: modified Nano titanium oxide: modified nano zinc oxide=1:1:1.
2. other monomer is that NSC 20956,2-EHA, Isooctyl acrylate monomer are the mixture of 1:1:1 by mass ratio.
3. an organosilane monomer is vinyltriethoxysilane (A-151).
Embodiment 3: the mass percent of inorganic nano particle modified composite water-proof emulsion is following:
Vinylformic acid 2.6%
TEB 3K 19%
Bing Xisuandingzhi 16%
Other monomer 1.7%
Modified Nano particles mixture 3.5%
Compound emulsifying agent 2.0%
Initiator 0.6%
An organosilane monomer 3.4%
The pH regulator agent is an amount of
Deionized water 50%
Sodium hydrogencarbonate 0.7%
The modified Nano particle that takes by weighing content in the prescription is distributed in the acrylic monomer mixture, and machinery stirs 0.5h, ultrasonic again 2h earlier.In the four-hole boiling flask that TM, reflux condensing tube, whisking appliance and dropper are housed, add a certain amount of deionized water; Regulating bath temperature is 45 ℃; In reactor drum, add whole emulsifying agents, 2/3 initiator and a certain amount of sodium hydrogencarbonate; Dissolving back drips 1/2 an organosilane monomer, with warming-in-water to 90 ℃; Drip monomer mixture, in 4h, dropwise, add remaining an organosilane monomer and initiator subsequently, continue reaction 1.5h in 90 ℃ of water-baths; Emulsion is naturally cooled to 40 ℃, add the pH regulator agent, regulating emulsion pH is 8～9, and discharging promptly gets inorganic nano particle modified composite water-proof emulsion behind the stirring 1h.
1. modified Nano mix particles amount proportioning:
Modified nano silicon oxide: modified Nano titanium oxide: modified nano zinc oxide: modified Nano aluminum oxide=1:1:0.8:0.8.
2. other monomer is that NSC 20956, Isooctyl acrylate monomer are the mixture of 1:1 by mass ratio.
3. an organosilane monomer is that vinyltriethoxysilane (A-151), vinyltrimethoxy silane (A-171) are the mixture of 1:1 by mass ratio.
Embodiment 4: the mass percent of inorganic nano particle modified composite water-proof emulsion is following:
Vinylformic acid 2.8%
TEB 3K 17%
Bing Xisuandingzhi 17%
Other monomer 2.0%
Modified Nano particles mixture 2.8%
Compound emulsifying agent 1.8%
Initiator 0.8%
An organosilane monomer 3.2%
The pH regulator agent is an amount of
Deionized water 52%
Sodium hydrogencarbonate 0.6%
The modified Nano particle that takes by weighing content in the prescription is distributed in the acrylic monomer mixture, and machinery stirs 0.5h, ultrasonic again 1.5h earlier.In the four-hole boiling flask that TM, reflux condensing tube, whisking appliance and dropper are housed, add a certain amount of deionized water; Regulating bath temperature is 45 ℃; In reactor drum, add whole emulsifying agents, 2/3 initiator and a certain amount of sodium hydrogencarbonate; Dissolving back drips 1/2 an organosilane monomer, with warming-in-water to 88 ℃; Drip monomer mixture, in 3.5h, dropwise, add remaining an organosilane monomer and initiator subsequently, continue reaction 1.5h in 88 ℃ of water-baths; Emulsion is naturally cooled to 50 ℃, add the pH regulator agent, regulating emulsion pH is 8～9, and discharging promptly gets inorganic nano particle modified composite water-proof emulsion behind the stirring 1h.
1. modified Nano mix particles amount proportioning:
Modified nano silicon oxide: modified Nano titanium oxide: modified nano zinc oxide: modified Nano aluminum oxide=1.1:1:0.8:1.
2. other monomer is that NSC 20956, ethyl propenoate are the mixture of 1:1 by mass ratio.
3. an organosilane monomer is that vinyltriethoxysilane (A-151), vinyltrimethoxy silane (A-171) are the mixture of 1:1 by mass ratio.
Embodiment 5: the mass percent of inorganic nano particle modified composite water-proof emulsion is following:
Vinylformic acid 2.9%
TEB 3K 17%
Bing Xisuandingzhi 15%
Other monomer 2.0%
Modified Nano particles mixture 4.5%
Compound emulsifying agent 2.2 %
Initiator 0.6%
An organosilane monomer 3.1%
The pH regulator agent is an amount of
Deionized water 50%
Sodium hydrogencarbonate 0.3%
The modified Nano particle that takes by weighing content in the prescription is distributed in the acrylic monomer mixture, and machinery stirs 0.5h, ultrasonic again 1h earlier.In the four-hole boiling flask that TM, reflux condensing tube, whisking appliance and dropper are housed, add a certain amount of deionized water; Regulating bath temperature is 40 ℃; In reactor drum, add whole emulsifying agents, 2/3 initiator and a certain amount of sodium hydrogencarbonate; Dissolving back drips 1/2 an organosilane monomer, with warming-in-water to 84 ℃; Drip monomer mixture, in 3.5h, dropwise, add remaining an organosilane monomer and initiator subsequently, continue reaction 1.5h in 84 ℃ of water-baths; Emulsion is naturally cooled to 42 ℃, add the pH regulator agent, regulating emulsion pH is 8～9, and discharging promptly gets inorganic nano particle modified composite water-proof emulsion behind the stirring 1h.
1. modified Nano mix particles amount proportioning:
Modified nano silicon oxide: modified Nano titanium oxide: modified nano zinc oxide: modified Nano aluminum oxide=1.1:1.2:1:0.8.
2. other monomer is that NSC 20956, ethyl propenoate, 2-EHA, Isooctyl acrylate monomer are the mixture of 1:1:1:1 by mass ratio.
3. an organosilane monomer is that vinyltriethoxysilane (A-151), vinyltrimethoxy silane (A-171) are the mixture of 1:1 by mass ratio.
Claims (3)
1. inorganic nano particle modified composite water-proof emulsion is characterized in that the composition of said water-proof emulsion and mass percent thereof are following:
Vinylformic acid 2～3%
TEB 3K 15～20%
Bing Xisuandingzhi 12～16%
Other monomer 1～3%
Modified Nano particles mixture 2.4～4.8%
Compound emulsifying agent 1.5～3%
Initiator 0.4～0.8%
An organosilane monomer 2.4～4.8%
The pH regulator agent is an amount of
Deionized water 45～55%
Buffer reagent 0.3～0.7%
Said modified Nano particles mixture is two or more the mixture in modified nano silicon oxide, modified Nano titanium oxide, modified nano zinc oxide and the modified Nano aluminum oxide, and the mass ratio of said modified nano silicon oxide, modified Nano titanium oxide, modified nano zinc oxide, modified Nano aluminum oxide is (1.0～1.2): (1.1～1.5): (0.4～1.2): (0.4～1.2);
The size of said nano silicon oxide, nano-titanium oxide, nano aluminium oxide, nano zine oxide is lower than 100nm;
Said other monomer is one or more the mixture in NSC 20956, ethyl propenoate, 2-EHA, the Isooctyl acrylate monomer;
Said compound emulsifying agent is the mixture of anionic emulsifier and nonionic emulsifier, and anionic emulsifier is a sodium lauryl sulphate, and nonionic emulsifier is OP-10, and the mass ratio of anionic emulsifier and nonionic emulsifier is 1:1.4;
Said an organosilane monomer is one or both mixtures in vinyltrimethoxy silane (A-171), the vinyltriethoxysilane (A-151);
Said pH regulator agent is the ammonia soln of mass concentration 25～28%;
Said initiator is a Potassium Persulphate;
Described buffer reagent is a sodium hydrogencarbonate.
2. the preparation method of inorganic nano particle modified according to claim 1 composite water-proof emulsion is characterized in that these preparing method's concrete steps are following:
(1) preparation modified Nano particles mixture:
The nanoparticle of certain mass is dissolved in the mixing solutions of alcohol-water, and wherein the volume ratio of ethanol and water is 1:1, ultrasonic 1～1.5h; Get the uniform nano particle dispersion liquid, nanoparticle dispersion liquid is transferred in the there-necked flask of band prolong, be warming up to 80～90 ℃ under the magnetic agitation; Using Glacial acetic acid min. 99.5 to regulate the pH value is 3～4, in there-necked flask, drips silane coupling agent, and the mol ratio of said nanoparticle and silane coupling agent is 1: (8～10); Reaction 2h～2.5h, after reaction finishes, suction filtration; Be washed till the filtrating clarification with ethanol, place 80～85 ℃ vacuum drying oven to dry 8～12h product after the washing, grind and obtain the modified Nano particles mixture;
(2) the inorganic nano particle modified composite water-proof emulsion of preparation:
A: a certain amount of modified Nano particle is distributed in the acrylic monomer mixture, and machinery stirs 0.5h earlier, and ultrasonic again 1～2h is subsequent use;
B: in the four-hole boiling flask that TM, reflux condensing tube, whisking appliance and dropper are housed, add a certain amount of deionized water; Regulating bath temperature is 40～50 ℃; In reactor drum, add whole emulsifying agents, 2/3 initiator and a certain amount of buffer reagent; Dissolving back drips 1/2 an organosilane monomer, with warming-in-water to 80～90 ℃; Drip the monomer mixture that steps A obtains, in 3～4h, dropwise, add remaining an organosilane monomer and initiator subsequently, continue reaction 1～1.5h in 80～90 ℃ of water-baths; Emulsion is naturally cooled to 40～50 ℃, add the pH regulator agent, regulating emulsion pH is 8～9, and discharging obtains inorganic nano particle modified composite water-proof emulsion behind the stirring 1h.
3. preparation method according to claim 2 is characterized in that said silane coupling agent is one or more mixtures in γ-methacryloxypropyl trimethoxy silane (KH-570), γ-An Bingjisanyiyangjiguiwan (KH-550), the γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560).
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