CN102391410B - 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, not only greatly influence attractive in appearancely, and 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 mixes in the emulsion building-up process, 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 organosilane monomer and (methyl) Acrylic Acid Monomer mixture, synthetic composite emulsion in water medium.Though the emulsion preparation method of above-mentioned patent disclosure has improved the ageing resistance of emulsion, water resistance and the nanoparticle stability in emulsion, but ignored 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.
Composition and the mass percent of inorganic nano particle modified composite water-proof emulsion provided by the present invention are as follows:
Vinylformic acid 2~3%
Methyl methacrylate 15~20%
Butyl acrylate 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%
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), 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, regulating the pH value with Glacial acetic acid 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, after reaction finished, suction filtration was washed till the filtrate 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 1~2h is standby again;
B: in the four-hole boiling flask that thermometer, reflux condensing tube, agitator and dropper are housed, add a certain amount of deionized water, regulating bath temperature is 40~50 ℃, in reactor, add whole emulsifying agents, 2/3 initiator and a certain amount of buffer reagent, dissolving back drips 1/2 organosilane monomer, with warming-in-water to 80~90 ℃; Drip the monomer mixture that steps A obtains, in 3~4h, dropwise, add remaining 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.
Described 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 described 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 described nano silicon oxide, nano-titanium oxide, nano aluminium oxide, nano zine oxide is lower than 100nm.
Described other monomer is one or more the mixture in butyl methacrylate, ethyl propenoate, 2-EHA, the Isooctyl acrylate monomer.
Described 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).
Described compound emulsifying agent is the mixture of anionic emulsifier and nonionic emulsifier, and anionic emulsifier is sodium lauryl sulphate, and nonionic emulsifier is OP-10, and the mass ratio of anionic emulsifier and nonionic emulsifier is 1:1.4.
Described organosilane monomer is one or both mixtures in vinyltrimethoxy silane (A-171), the vinyltriethoxysilane (A-151).
Described pH regulator agent is the ammonia soln of mass concentration 25~28%.
Described initiator is Potassium Persulphate.
Described buffer reagent is sodium bicarbonate.
At the technical problem that existing emulsion exists, add nanoparticle and improve:
Nano silicon oxide: nano silicon oxide has huge specific surface area, has strengthened intensity and the smooth finish of coating when coating is dry, 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 opacifying power and the tinting strength of emulsion greatly, also will improve the uvioresistant ability of emulsion simultaneously, improve ageing resistance.
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
3Reaction, thus the group that contains " Si-O-Si-" key connected in nanoparticle surface, 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 the investigation through strictness, by 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 of Jia Ruing can be brought into play its surface modification key effect preferably in proportion, be connected among the polymkeric substance with more orderly structure, reduced the interaction between each nanoparticle, make the nanoparticle that adds farthest to play a role, better improve the emulsion correlated performance.
Embodiment
Embodiment 1: the mass percent of inorganic nano particle modified composite water-proof emulsion is as follows:
Vinylformic acid 3%
Methyl methacrylate 18%
Butyl acrylate 16%
Other monomer 1.3%
Modified Nano particles mixture 2.4%
Compound emulsifying agent 1.5%
Initiator 0.4%
Organosilane monomer 3.1%
The pH regulator agent is an amount of
Deionized water 52%
Sodium bicarbonate 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 1h more earlier.In the four-hole boiling flask that thermometer, reflux condensing tube, agitator and dropper are housed, add a certain amount of deionized water, regulating bath temperature is 40 ℃, in reactor, add whole emulsifying agents, 2/3 initiator and a certain amount of sodium bicarbonate, dissolving back drips 1/2 organosilane monomer, with warming-in-water to 80 ℃; Drip monomer mixture, in 3h, dropwise, add remaining 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 namely 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 butyl methacrylate, ethyl propenoate, Isooctyl acrylate monomer are the mixture of 1:1:1 by mass ratio.
3. organosilane monomer is vinyltrimethoxy silane (A-171).
Embodiment 2: the mass percent of inorganic nano particle modified composite water-proof emulsion is as follows:
Vinylformic acid 2.3%
Methyl methacrylate 17%
Butyl acrylate 15%
Other monomer 1.8%
Modified Nano particles mixture 3.2%
Compound emulsifying agent 1.8%
Initiator 0.5%
Organosilane monomer 4.0%
The pH regulator agent is an amount of
Deionized water 50.5%
Sodium bicarbonate 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 1.5h more earlier.In the four-hole boiling flask that thermometer, reflux condensing tube, agitator and dropper are housed, add a certain amount of deionized water, regulating bath temperature is 45 ℃, in reactor, add whole emulsifying agents, 2/3 initiator and a certain amount of sodium bicarbonate, dissolving back drips 1/2 organosilane monomer, with warming-in-water to 85 ℃; Drip monomer mixture, in 3.5h, dropwise, add remaining 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 namely 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 butyl methacrylate, 2-EHA, Isooctyl acrylate monomer are the mixture of 1:1:1 by mass ratio.
3. organosilane monomer is vinyltriethoxysilane (A-151).
Embodiment 3: the mass percent of inorganic nano particle modified composite water-proof emulsion is as follows:
Vinylformic acid 2.6%
Methyl methacrylate 19%
Butyl acrylate 16%
Other monomer 1.7%
Modified Nano particles mixture 3.5%
Compound emulsifying agent 2.0%
Initiator 0.6%
Organosilane monomer 3.4%
The pH regulator agent is an amount of
Deionized water 50%
Sodium bicarbonate 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 2h more earlier.In the four-hole boiling flask that thermometer, reflux condensing tube, agitator and dropper are housed, add a certain amount of deionized water, regulating bath temperature is 45 ℃, in reactor, add whole emulsifying agents, 2/3 initiator and a certain amount of sodium bicarbonate, dissolving back drips 1/2 organosilane monomer, with warming-in-water to 90 ℃; Drip monomer mixture, in 4h, dropwise, add remaining 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 namely 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 butyl methacrylate, Isooctyl acrylate monomer are the mixture of 1:1 by mass ratio.
3. 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 as follows:
Vinylformic acid 2.8%
Methyl methacrylate 17%
Butyl acrylate 17%
Other monomer 2.0%
Modified Nano particles mixture 2.8%
Compound emulsifying agent 1.8%
Initiator 0.8%
Organosilane monomer 3.2%
The pH regulator agent is an amount of
Deionized water 52%
Sodium bicarbonate 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 1.5h more earlier.In the four-hole boiling flask that thermometer, reflux condensing tube, agitator and dropper are housed, add a certain amount of deionized water, regulating bath temperature is 45 ℃, in reactor, add whole emulsifying agents, 2/3 initiator and a certain amount of sodium bicarbonate, dissolving back drips 1/2 organosilane monomer, with warming-in-water to 88 ℃; Drip monomer mixture, in 3.5h, dropwise, add remaining 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 namely 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 butyl methacrylate, ethyl propenoate are the mixture of 1:1 by mass ratio.
3. 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 as follows:
Vinylformic acid 2.9%
Methyl methacrylate 17%
Butyl acrylate 15%
Other monomer 2.0%
Modified Nano particles mixture 4.5%
Compound emulsifying agent 2.2 %
Initiator 0.6%
Organosilane monomer 3.1%
The pH regulator agent is an amount of
Deionized water 50%
Sodium bicarbonate 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 1h more earlier.In the four-hole boiling flask that thermometer, reflux condensing tube, agitator and dropper are housed, add a certain amount of deionized water, regulating bath temperature is 40 ℃, in reactor, add whole emulsifying agents, 2/3 initiator and a certain amount of sodium bicarbonate, dissolving back drips 1/2 organosilane monomer, with warming-in-water to 84 ℃; Drip monomer mixture, in 3.5h, dropwise, add remaining 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 namely 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 butyl methacrylate, ethyl propenoate, 2-EHA, Isooctyl acrylate monomer are the mixture of 1:1:1:1 by mass ratio.
3. 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 described water-proof emulsion and mass percent thereof are as follows:
Vinylformic acid 2~3%
Methyl methacrylate 15~20%
Butyl acrylate 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%
Organosilane monomer 2.4~4.8%
The pH regulator agent is an amount of
Deionized water 45~55%
Buffer reagent 0.3~0.7%
Described modified Nano particles mixture prepares by the following method:
The nanoparticle of certain mass is dissolved in the mixing solutions of alcohol-water, 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, regulating the pH value with Glacial acetic acid is 3~4, drips silane coupling agent in there-necked flask, and the mol ratio of described nanoparticle and silane coupling agent is 1:(8~10), reaction 2h~2.5h, after reaction finished, suction filtration was washed till the filtrate 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;
Described 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 described 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 described nano silicon oxide, nano-titanium oxide, nano aluminium oxide, nano zine oxide is lower than 100nm;
Described other monomer is one or more the mixture in butyl methacrylate, ethyl propenoate, 2-EHA, the Isooctyl acrylate monomer;
Described compound emulsifying agent is the mixture of anionic emulsifier and nonionic emulsifier, and anionic emulsifier is sodium lauryl sulphate, and nonionic emulsifier is OP-10, and the mass ratio of anionic emulsifier and nonionic emulsifier is 1:1.4;
Described organosilane monomer is one or both mixtures in vinyltrimethoxy silane (A-171), the vinyltriethoxysilane (A-151);
Described pH regulator agent is the ammonia soln of mass concentration 25~28%;
Described initiator is Potassium Persulphate;
Described buffer reagent is sodium bicarbonate.
2. the preparation method of inorganic nano particle modified composite water-proof emulsion according to claim 1 is characterized in that these preparation method's concrete steps are as follows:
A: a certain amount of modified Nano particle is distributed in the acrylic monomer mixture, and machinery stirs 0.5h earlier, and ultrasonic 1~2h is standby again;
B: in the four-hole boiling flask that thermometer, reflux condensing tube, agitator and dropper are housed, add a certain amount of deionized water, regulating bath temperature is 40~50 ℃, in reactor, add whole emulsifying agents, 2/3 initiator and a certain amount of buffer reagent, dissolving back drips 1/2 organosilane monomer, with warming-in-water to 80~90 ℃; Drip the monomer mixture that steps A obtains, in 3~4h, dropwise, add remaining 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 described 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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