CN1204192C - Organic sillicon modified acrylic ester/inorganic nano composite emulsion and its preparation - Google Patents
Organic sillicon modified acrylic ester/inorganic nano composite emulsion and its preparation Download PDFInfo
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- CN1204192C CN1204192C CN 02158210 CN02158210A CN1204192C CN 1204192 C CN1204192 C CN 1204192C CN 02158210 CN02158210 CN 02158210 CN 02158210 A CN02158210 A CN 02158210A CN 1204192 C CN1204192 C CN 1204192C
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Abstract
The present invention relates to organic silicon modified acrylic ester/inorganic nanometer composite emulsion and a preparation method thereof. The emulsion is prepared by that inorganic phases of nanometer SiO2, TiO2, ZnO, CaCO3, etc. are contained in particles of silicone acrylic emulsion by a method of two-step polymerization of inverse emulsion polymerization/emulsion polymerization. Because the inorganic nanometer particles have a micro size effect, a surface effect, a quantum effect, a filling effect and a catalytic characteristic, the mechanical performance, the anti-pollution performance, self-cleaning performance, the antistatic performance, etc. of the silicone acrylic emulsion paint can be effectively enhanced. Because the grafting polymerization is realized on the surfaces of the inorganic nanometer particles by using an in-situ polymerization technique, the interaction between polymers and the inorganic nanometer particles is strengthened. Compared with the physical mixing, the present invention not only improves the emulsion stability and but also simultaneously endows excellent performance for the silicone acrylic emulsion. The emulsion can be used as paint, adhesive agents polishing agents and cement modifiers, particularly water paint with high performance.
Description
Technical field
The present invention relates to a kind of water-borne coatings, relate to organosilicon-modified acrylate/inorganic nano combined emulsion and preparation method thereof specifically.
Background technology
Along with the development of the high stratification of modern architecture, maximization, people are more and more higher to the requirement of building coating, and are particularly more outstanding to the requirement of the resistance to deterioration of coating, anti-staining property and self-cleaning performance.For long-term exposure decoration of exterior wall and the outdoor decoration that is difficult to repair, Highrise buildings out of doors, wish the mechanical property of coating, anti-ly stain performance, it is best that ageing resistance, self-cleaning performance and over-all properties reach.Organosilicon-modified acrylate emulsion coating (be called for short organosilicon crylic acid latex coating) is though can satisfy the demand in some aspects, and it is in ageing resistance, self-cleaning performance, and aspects such as mechanical property exist not enough.In addition, modern environmental regulation requires green building material, not only require new coating that human body and environment are not had any harm, and strong adhesion, antibiotic, purify air, can also decompose and eliminate stain, dust, and harmful component such as formaldehyde, simple organosilicon crylic acid latex emulsified material is difficult to satisfy simultaneously above requirement.
Nanoparticle is owing to have characteristics such as particle diameter little (less than 100nm) specific surface area is big, also has unique catalytic activity simultaneously, therefore, nano composite material has many particular performances, learns performance, mechanical property, magnetic performance etc. as optical property, electric property, pad.The nano composite polymeric material is to develop frontier very rapidly in the material science, at present, nanoparticle mainly adopts two kinds of methods in the application of emulsion coatings, the one, nanoparticle is dispersed in traditional emulsion coatings to promote the performance of coating, because nanoparticle has higher surface energy, adopt its stability of nano composite dope of physical blending method preparation relatively poor relatively, improvement to coating property is very limited, another method is to be that seed carries out letex polymerization and makes with the inorganic nano-particle, because most of inorganic nano-particles are the strongly hydrophilic material, it is very difficult to carry out letex polymerization, must carry out hydrophobically modified to the inorganic nano-particle sub-surface, operating procedure is loaded down with trivial details like this, and production cost is higher, is difficult to carry out scale operation.
Summary of the invention
The object of the present invention is to provide a kind of organosilicon-modified acrylate/inorganic nano combined emulsion of excellent property and prepare the method for this emulsion.
Organosilicon-modified acrylate of the present invention/inorganic nano combined emulsion comprises following component:
1) organosilicon acrylic resin with solid content meter, accounts for the 30-50% of emulsion total amount;
2) inorganic nano-particle by weight percentage, accounts for the 1-20% of organosilicon acrylic resin solid amount.
Prepare organosilicon-modified acrylate of the present invention/inorganic nano combined emulsion, adopt the two-stage polymerization method of inverse emulsion polymerization/letex polymerization, be external phase at first with the acrylate monomer that in water, has certain solubility, in the presence of inorganic nano bunch composite initiator, cause water-soluble monomer and carry out inverse emulsion polymerization, pass through in-situ grafting polymerization, the inorganic nano-particle of preparation polyacrylic ester parcel, add emulsifier aqueous solution then, carry out anti-phase, carry out conventional emulsion polymerization, the synthetic organosilicon crylic acid latex that includes inorganic nano-particle.
Method of the present invention specifically may further comprise the steps:
1) concentration that by weight inorganic nano-particle of 1-20% is distributed to 5-20% is 10% H
2O
2The aqueous solution, the persulfate initiator of 0.1-2%, the concentration of 1-5% is 10% base catalysis agent solution, in the mixing solutions that the dispersion agent of 0.1-5% and the water of 40-60% are formed, is uniformly dispersed, and leaves standstill 2-48 hour, the summation of above-mentioned each component is 100%;
2) by weight percentage, will be by the step 1) gains of 10-30%, water soluble propene's acid mono of 1-10%, the mixture that the acrylate monomer that has certain solubility in water of 60-80% is formed stirred 0.5-5 hour, be uniformly dispersed, get the inverse emulsion polymerization system;
3) above-mentioned inverse emulsion polymerization system is warmed up to 65-85 ℃, perhaps to the reduction initiator that wherein adds as redox initiation system, inverse emulsion polymerization is carried out in initiation reaction, and insulation reaction 6 hours;
4) by weight percentage, will be by the step 3) products therefrom of 10-30%, the anionic emulsifier of 0.5-5%, the nonionic emulsifying agent of 2-10%, the mixture that the water of 40-60%, 0.1-2%pH buffer reagent are formed, stir fast, carry out anti-phasely, add the 10-30% acrylate monomer again, the 0.1-10% organosilane monomer, stir, make emulsion polymerization systems;
5) above-mentioned emulsion polymerization systems is warmed up to 75-85 ℃, adds the 0.1-0.5% persulfate initiator, conventional emulsion polymerization is carried out in initiation reaction, and is incubated polymerization 2-6 hour;
6) with the emulsion polymer cooling of step 5) gained, add the ammoniacal liquor neutralization, filter discharging, obtain organosilicon-modified acrylate/inorganic nano combined emulsion by 1: 1 volume ratio.
Among the present invention, said inorganic nano-particle can be nanometer SiO
2, TiO
2, ZnO, CaCO
3In a kind of or its mixture, preferred nanometer SiO
2, TiO
2, its median size can be between 1-100nm, preferred 1-50nm.In the preparation process of the present invention, the described dispersion agent of its step 1) is selected from OP series, and tween series or this coil serial emulsifying agent, and described basic catalyst is a sodium hydroxide, potassium hydroxide, a kind of or its mixture in the ammoniacal liquor.
In order to guarantee that the inorganic nano-particle surface enrichment has the initiator of q.s, in step 1), inorganic nano-particle is distributed in the mixing solutions, it is essential leaving standstill 2-48 hour, and if desired, the method for available ultra-sonic dispersion is handled.
Step 2 of the present invention) the water soluble propene's acid mono described in is a vinylformic acid, methacrylic acid, methacrylic acid hydroxyl ester, a kind of or its mixture in the dimethylaminoethyl methacrylate, described acrylate monomer is a methyl acrylate, ethyl propenoate, methyl methacrylate, methacrylic acid hydroxyl ester, a kind of or its mixture in the dimethylaminoethyl methacrylate.
Step 1) of the present invention, the persulfate initiator described in the step 5) is selected from Sodium Persulfate, Potassium Persulphate or ammonium persulphate.
Reduction initiator described in the step step 3) of the present invention is selected from sodium formaldehyde sulfoxylate, sulfurous acid ammonia sodium, a kind of in the ferrous sulfate.
Anionic emulsifier described in the step 4) of the present invention is selected from sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, a kind of in the vinylbenzenesulfonic acid sodium.Described nonionic emulsifying agent can adopt OP series emulsifying agent.Described pH buffer reagent can adopt sodium bicarbonate, yellow soda ash, sodium-acetate or sodium hydrogen phosphate etc.Described acrylate monomer is selected from butyl acrylate, Isooctyl acrylate monomer, butyl methacrylate, methyl methacrylate, ethyl propenoate, vinylformic acid, at least a or its mixture in the methacrylic acid.Described organosilane monomer is selected from vinyltrimethoxy silane, methacryloxypropyl trimethoxy silane, tetramethyl divinyl disiloxane, at least a or its mixture in the methyl ethylene cyclosiloxane, perhaps wherein a kind of with the hydroxyl polysiloxane, the hydrolytic condensate of organopolysiloxane.
The inventive method is safe and simple, easy handling, owing to adopt in-situ polymerization technology, strengthened inorganic nano-particle with the interaction between the organosilicon acrylic resin polymkeric substance, improved the stability of emulsion system, not only make the organosilicon-modified acrylate/inorganic nano combined emulsion coatings that makes have good tensile strength, hardness, snappiness, scratch resistance, and give many excellent properties such as coating ageing resistance, erosion resistance, wear resistance, heat-insulation and heat-preservation, static electricity resistance, spatter property, anti-staining property.This emulsion can be used as coating, tackiness agent, lustering agent, cement modifier, especially can be used as high-performance water-based coating.
Embodiment
Below by embodiment, the invention will be further described.
Embodiment 1:
Take by weighing the nanometer SiO of median size 15nm
21.0g join Potassium Persulphate, 0.5gOP-10, the H of 5g10% by 0.1g
2O
2Solution, in the mixing solutions of the NaOH solution composition of 5g10%, high-speed stirring 2 hours adds the 2g methacrylic acid, stirs 30 minutes.Add the 43g methyl methacrylate, stir, preparation reversed-phase emulsion system, be warmed up to 65 ℃ and carry out inverse emulsion polymerization, 6 hours postcooling to 40 ℃ are carried out in reaction, add by the 2g sodium lauryl sulphate 0.5g yellow soda ash in system, 5.5gOP-10 and the mixing solutions of 140g water composition, high-speed stirring is carried out anti-phase, adds the 52g butyl acrylate then, 2g γ-(methacryloxy) propyl trimethoxy silicane, emulsification 30 minutes, be warmed up to 75 ℃, adding is dissolved in the initiator that 10g water is formed, initiation reaction by the 0.4g Potassium Persulphate, carry out conventional emulsion polymerization, insulation reaction 3 hours is reduced to room temperature, with the ammoniacal liquor neutralization of 1: 1 (volume ratio), filter discharging, promptly get silicone-modified polyacrylate/nanometer SiO
2Composite emulsion.
Embodiment 2
Take by weighing the nano-TiO of median size 40nm
21.0g join Potassium Persulphate, 0.5gOP-10, the H of 5g 10% by 0.1g
2O
2Solution, in the mixing solutions of the NaOH solution composition of 5g10%, high-speed stirring 2 hours, standing over night adds the 2g hydroxyethyl methylacrylate, stirs 30 minutes, adds the 43g methyl methacrylate, stirs preparation reversed-phase emulsion system.Be warmed up to 65 ℃, add the sodium formaldehyde sulfoxylate solution of 2g1%, inverse emulsion polymerization is carried out in initiation reaction.After reaction is carried out 6 hours, be cooled to 40 ℃, in system, add by the 2g sodium lauryl sulphate, 0.5g yellow soda ash, the mixing solutions that 5.5gOP-10 and 140g water are formed, high-speed stirring is carried out anti-phase, add the 52g butyl acrylate then, contain the macromole silicon monomer 5g of two keys, emulsification 30 minutes.Be warmed up to 75 ℃, adding is dissolved in the initiator that 10g water is formed, initiation reaction by the 0.4g Potassium Persulphate, carry out letex polymerization, insulation polyase 13 hour is reduced to room temperature, with the ammoniacal liquor neutralization of 1: 1 (volume ratio), filtration, discharging promptly get silicone-modified polyacrylate/nano-TiO
2Composite emulsion.
Claims (6)
1. the preparation method of organosilicon-modified acrylate/inorganic nano combined emulsion is characterized in that adopting the two-stage polymerization method preparation of inverse emulsion polymerization/letex polymerization, and realizes by following steps:
1) concentration that by weight inorganic nano-particle of 1-20% is distributed to 5-20% is 10% H
2O
2The aqueous solution, the persulfate initiator of 0.1-2%, the concentration of 1-5% is 10% base catalysis agent solution, in the mixing solutions that the dispersion agent of 0.1-5% and the water of 40-60% are formed, is uniformly dispersed, and leaves standstill 2-48 hour, the summation of above-mentioned each component is 100%;
2) by weight percentage, will be by the step 1) gains of 10-30%, water soluble propene's acid mono of 1-10%, the mixture that the acrylate monomer that has certain solubility in water of 60-80% is formed stirred 0.5-5 hour, be uniformly dispersed, get the inverse emulsion polymerization system;
3) above-mentioned inverse emulsion polymerization system is warmed up to 65-85 ℃, perhaps to the reduction initiator that wherein adds as redox initiation system, inverse emulsion polymerization is carried out in initiation reaction, and insulation reaction 6 hours;
4) by weight percentage, will be by the step 3) products therefrom of 10-30%, the anionic emulsifier of 0.5-5%, the nonionic emulsifying agent of 2-10%, the mixture that the water of 40-60%, 0.1-2%pH buffer reagent are formed, stir fast, carry out anti-phasely, add the 10-30% acrylate monomer again, the 0.1-10% organosilane monomer, stir, make emulsion polymerization systems;
5) above-mentioned emulsion polymerization systems is warmed up to 75-85 ℃, adds the 0.1-0.5% persulfate initiator, conventional emulsion polymerization is carried out in initiation reaction, and is incubated polymerization 2-6 hour;
6) with the emulsion polymer cooling of step 5) gained, add the ammoniacal liquor neutralization, filter discharging, obtain organosilicon-modified acrylate/inorganic nano combined emulsion by 1: 1 volume ratio.
2. press the preparation method of the described organosilicon-modified acrylate of claim 1/inorganic nano combined emulsion, it is characterized in that the dispersion agent described in the step 1) is selected from OP series, tween series or this coil serial emulsifying agent, described basic catalyst is a sodium hydroxide, potassium hydroxide, a kind of or its mixture in the ammoniacal liquor.
3. press the preparation method of the described organosilicon-modified acrylate of claim 1/inorganic nano combined emulsion, it is characterized in that step 2) described in water soluble propene's acid mono be vinylformic acid, methacrylic acid, methacrylic acid hydroxyl ester, a kind of or its mixture in the dimethylaminoethyl methacrylate, described acrylate monomer is a methyl acrylate, ethyl propenoate, methyl methacrylate, methacrylic acid hydroxyl ester, a kind of or its mixture in the dimethylaminoethyl methacrylate.
4. by the preparation method of the described organosilicon-modified acrylate of claim 1/inorganic nano combined emulsion, it is characterized in that step 1), the persulfate initiator described in the step 5) is selected from Sodium Persulfate, Potassium Persulphate or ammonium persulphate.
5. by the preparation method of the described organosilicon-modified acrylate of claim 1/inorganic nano combined emulsion, it is characterized in that the reduction initiator described in the step 3) is selected from sodium formaldehyde sulfoxylate, sulfurous acid ammonia sodium, a kind of in the ferrous sulfate.
6. press the preparation method of the described organosilicon-modified acrylate of claim 1/inorganic nano combined emulsion, it is characterized in that the anionic emulsifier described in the step 4) is selected from sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, a kind of in the vinylbenzenesulfonic acid sodium, described nonionic emulsifying agent OP series emulsifying agent, described pH buffer reagent sodium bicarbonate, yellow soda ash, sodium-acetate, sodium hydrogen phosphate, described acrylate monomer is selected from butyl acrylate, Isooctyl acrylate monomer, butyl methacrylate, methyl methacrylate, ethyl propenoate, vinylformic acid, at least a or its mixture in the methacrylic acid, described organosilane monomer is selected from vinyltrimethoxy silane, methacryloxypropyl trimethoxy silane, tetramethyl divinyl disiloxane, at least a or its mixture in the methyl ethylene cyclosiloxane, perhaps wherein a kind of with the hydroxyl polysiloxane, the hydrolytic condensate of organopolysiloxane.
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| CN 02158210 CN1204192C (en) | 2002-12-19 | 2002-12-19 | Organic sillicon modified acrylic ester/inorganic nano composite emulsion and its preparation |
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