CN1944476A - Process for preparing fluorin, silicon, epoxide modified low surface energy acrylate emulsion for heavy anti-corrosion paint - Google Patents
Process for preparing fluorin, silicon, epoxide modified low surface energy acrylate emulsion for heavy anti-corrosion paint Download PDFInfo
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- CN1944476A CN1944476A CNA2006101248071A CN200610124807A CN1944476A CN 1944476 A CN1944476 A CN 1944476A CN A2006101248071 A CNA2006101248071 A CN A2006101248071A CN 200610124807 A CN200610124807 A CN 200610124807A CN 1944476 A CN1944476 A CN 1944476A
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Abstract
The present invention discloses preparation process of fluorine, silicon and epoxide modified low surface energy acrylate emulsion for heavy anti-corrosive paint. The modified acrylate emulsion is prepared with one or more of styrene, methyl methacylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, etc as the main monomer and through introducing modifying fluorine, silicon and epoxide. The process of the present invention has simple operation and high yield, and the prepared emulsion has high water tolerance, high solvent tolerance, high acid and alkali resistance, high stability and capacity of forming film with surface energy as low as 15.5 mN/m.
Description
Technical field
The invention belongs to the preparation that is used for heavy-duty coating, specifically, is the preparation method of a kind of heavy-duty coating with fluorine, silicon, epoxide modified low surface energy acrylate emulsion.
Background technology
Develop rapidly along with industry, especially recent two decades comes the development of petrochemical enterprise, the progress of oceanology, some more harsh corrosive environments have been produced: chemical environment (chemical medium, chemical atmosphere) and ocean environment (oceanic climate, seawater) etc., to the marine structure under this harsh corrosive environment, bridge, boats and ships, generating set, electric power pylon, chemical industry equipment, basin, the protection of pipeline and platform etc. is had higher requirement, in this case, approximately since the sixties in 20th century, in order to distinguish protective system in the past, heavy duty system arises at the historic moment.Emulsion has remarkable influence as one of key ingredient of coating to its performance.Acrylic resin has good photostabilization, weathering resistance, ultraviolet resistance irradiation, erosion resistance, have good resistance to deterioration, gloss retention and tint retention with its acrylic coating of making, they can obtain the character of different hardness, suppleness and other requirement through the adjusting of prescription simultaneously.But also there is shortcoming in acrylic acid esters co-polymer, as poor water resistance, low temperature easily become fragile, high temperature become sticky lose strong, easily after tack, physical strength are poor slightly, thereby influenced its use value.Up to now, the scheme that still finds no solves this type of problem.
Summary of the invention
The objective of the invention is in order to solve the deficiency of above-mentioned background technology, propose a kind of preparation method that can be applicable to the heavy-duty coating under the harsh corrosive environment with fluorine, silicon, epoxide modified low surface energy acrylate emulsion.
At above-mentioned purpose, the present invention adopts ground preparing acrylate emulsion method with above as main monomer to choose any one kind of them in vinylbenzene, methyl methacrylate, n-butylacrylate, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, propenoic acid beta-hydroxy ethyl ester, propenoic acid beta-hydroxy propyl ester, ethylene glycol diacrylate, ethyl propenoate, ethyl acrylate, (methyl) acrylic acid hydroxy alkyl ester, with main monomer is a mass unit, according to the prescription of following table, concrete preparation process is as follows:
| Factor | Quality |
| Epoxy monomer | 3％～30％ |
| Fluorine monomer | 5％～30％ |
| Silicon monomer | 0.5％～5％ |
| Initiator | 0.5％～0.8％ |
| Emulsifying agent | 4％～10％ |
| Sodium bicarbonate | 0％～1％ |
| Water | 120％～171.4％ |
% is the mass percent that accounts for total main monomer
1. in reaction vessel, add 0.5%～1% nonionic emulsifying agent, 0.5%～1.5% anionic emulsifier and 30g water, be warming up to bath temperature and reach 82 ± 2 ℃, add 0.1%～0.4% initiator;
2. behind 10～30min, with main monomer, 3%～15% epoxy monomer, remaining nonionic emulsifying agent and anionic emulsifier, half of the pre-emulsion that 0.05%～0.15% initiator and 25g water are formed adds in the reaction vessel in 1h～1.5h, described anionic emulsifier is alkyl vinylformic acid-2-ethanesulfonic acid sodium, 2-acrylamide-2,2 dimethyl ethyl sulfonic acid sodium, sodium p styrene sulfonate, the combination of one or more in the maleic acid higher alcohols monoesters sodium, nonionic emulsifying agent is a polyoxyethylene nonyl phenol acrylate, the allyloxy polyoxyethylene nonylphenol ether, the combination of one or more in the polyoxyethylene aryl phenol acrylate, wherein, remaining nonionic emulsifying agent 1.0%～3.0%, remaining anionic emulsifier 2.0%～4.5%;
3. in remaining pre-emulsion, add all fluorine monomer, silicon monomer and residual epoxide monomer, emulsification, and in 1h～1.5h, add in the reaction vessel, add the solution of forming by residue initiator and pH damping fluid sodium bicarbonate simultaneously, and make to add behind its several minutes after all monomers addings and finish;
4. temperature is remained on 82 ± 2 ℃ of reaction 1.5h～2h and obtain product.
Entire reaction course adds solvent and adopts the method that drips in reaction vessel.Whole polymerization process reaction is very steady, and the latex stability that finally makes is fine, and transformation efficiency all can reach more than 90%.
Used fluorine monomer is fluorinated acrylic ester monomer methacrylic acid ten difluoro heptyl esters, dodecafluorhe-ptylacrylate, a kind of in vinylformic acid 19 fluorine esters, trifluoroethyl methacrylate, methacrylic acid hexafluoro butyl ester, the perfluoro capryl ethyl propenoate.
Used silicon monomer is a kind of in γ-methacryloxypropyl three (trimethyl silicon based) silane γ-methacryloxypropyl triethoxyl silane, γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-methacryloxypropyl three isopropoxy silane, vinyl silane triisopropoxide, the vinyl tri-tert silane.
Used epoxy monomer is a glycidyl methacrylate, glycidyl acrylate, a kind of in glytidyl methacrylate, the isobornyl methacrylate.Used initiator is one or more the combination in ammonium persulphate, Potassium Persulphate, Potassium Persulphate-Potassium hydrogen sulfite or the Potassium Thiosulphate.
Used emulsifying agent is the moon/non-ionic composite polymerisable emulsifier, makes the emulsion that makes more stable.
Compared with prior art, the present invention adopts fluorine, silicon, epoxy simultaneously acrylate to be carried out modification, latex that makes and film thereof not only have excellent elasticity and resistance to cracking, also can improve pollution resistance, water and oil-resistant, weather-proof erosion resistance and the resistance to deterioration of filming simultaneously.
The present invention has the following advantages: with fluorine, silicon, epoxy monomer acrylate is carried out modification simultaneously, not only can reduce cost to a certain extent, and because the crosslinked action of silane coupling agent and epoxy monomer, make the polymer formation reticulated structure, effectively improved the corrosion resistance nature of polymkeric substance; Adopt drip entirely mode, whole polymerization process reaction is very steady, and the latex stability that finally makes is fine, transformation efficiency all can reach more than 90%; Adopt the moon/non-ionic composite polymerisable emulsifier, make the emulsion that makes more stable; With water as solvent, environmental protection, safe and inexpensive.
Embodiment
Following prior art and do not adopt technology of the present invention and the present invention to make comparisons fully is further described the present invention.The percentage composition of each material is the mass percent that accounts for total main monomer among comparative example and the embodiment.
Below reach the comparative example that does not use technology of the present invention fully for prior art:
Comparative example 1
1. in being housed, the 250ml four-hole boiling flask of electric mixer, prolong and thermometer adds 0.5%～1% nonionic emulsifying agent, 0.5%～1.5% anionic emulsifier and 30g water, be warming up to bath temperature and reach 82 ± 2 ℃, add 0.1%～0.4% initiator;
2. behind 10～30min, with main monomer, remaining nonionic emulsifying agent and anionic emulsifier, in 2h～3h, being added drop-wise in the reaction flask of the pre-emulsion that 0.05%～0.15% initiator and 25g water are formed;
3. after pre-emulsion drips 1h～1.5h, begin to drip the solution of forming by residue initiator and pH damping fluid sodium bicarbonate, and drip off after making its several minutes after all monomers drip off;
4. temperature is remained on 82 ± 2 ℃ of reaction 1.5h～2h and promptly get product.
Comparative example 2
1. in the 250ml four-hole boiling flask of electric mixer, prolong and thermometer is housed, add 1%～2.5% emulsifying agent and 30g water, be warming up to bath temperature and reach 82 ± 2 ℃, add 0.1%～0.4% initiator;
2. behind 10～30min, with main monomer, 3%～15% epoxy monomer glycidyl methacrylate, remaining emulsifying agent, half of the pre-emulsion that 0.05%～0.15% initiator and 25g water are formed is added drop-wise in the reaction flask in 1h～1.5h;
3. in remaining pre-emulsion, add all silicon monomer vinyltriethoxysilanes and residual epoxide monomer glycidyl methacrylate, emulsification, and in 1h～1.5h, be added drop-wise in the reaction flask, drip the solution of forming by residue initiator and pH damping fluid sodium bicarbonate simultaneously, and drip off after making its several minutes after all monomers drip off;
4. temperature is remained on 82 ± 2 ℃ of reaction 1.5h～2h and promptly get product.
Comparative example 3
1. in being housed, the 250ml four-hole boiling flask of electric mixer, prolong and thermometer adds 0.5%～1% nonionic emulsifying agent, 0.5%～1.5% anionic emulsifier and 30g water, be warming up to bath temperature and reach 82 ± 2 ℃, add 0.1%～0.4% initiator;
2. behind 10～30min, with main monomer, 3%～15% epoxy monomer glycidyl methacrylate, remaining nonionic emulsifying agent and anionic emulsifier, half of the pre-emulsion that 0.05%～0.15% initiator and 25g water are formed is added drop-wise in the reaction flask in 1h～1.5h;
3. in remaining pre-emulsion, add all fluorine monomer dodecafluorhe-ptylacrylates and residual epoxide monomer glycidyl methacrylate, emulsification, and in 1h～1.5h, be added drop-wise in the reaction flask, drip the solution of forming by residue initiator and pH damping fluid sodium bicarbonate simultaneously, and drip off after making its several minutes after all monomers drip off;
4. temperature is remained on 82 ± 2 ℃ of reaction 1.5h～2h and promptly get product.
Comparative example 4
1. in being housed, the 250ml four-hole boiling flask of electric mixer, prolong and thermometer adds 0.5%～1% nonionic emulsifying agent, 0.5%～1.5% anionic emulsifier and 30g water, be warming up to bath temperature and reach 82 ± 2 ℃, add 0.1%～0.4% initiator;
2. behind 10～30min, with main monomer, remaining nonionic emulsifying agent and anionic emulsifier, half of the pre-emulsion that 0.05%～0.15% initiator and 25g water are formed is added drop-wise in the reaction flask in 1h～1.5h;
3. in remaining pre-emulsion, add all fluorine monomer dodecafluorhe-ptylacrylates and silicon monomer vinyltriethoxysilane, emulsification, and in 1h～1.5h, be added drop-wise in the reaction flask, drip the solution of forming by residue initiator and pH damping fluid sodium bicarbonate simultaneously, and drip off after making its several minutes after all monomers drip off;
4. temperature is remained on 82 ± 2 ℃ of reaction 1.5h～2h and promptly get product.
Below be embodiments of the invention:
Embodiment 1
Main monomer is the compound main monomer that n-butyl acrylate 25～30g, methyl methacrylate 5～10g and vinylbenzene 5～10g form.
1. in being housed, the 250ml four-hole boiling flask of electric mixer, prolong and thermometer adds 0.5%～1% nonionic emulsifying agent allyloxy polyoxyethylene nonylphenol ether, 0.5%～1.5% anionic emulsifier alkyl vinylformic acid-2-ethanesulfonic acid sodium and 30g water, be warming up to bath temperature and reach 82 ± 2 ℃, add 0.1%～0.4% initiator ammonium persulfate;
2. behind 10～30min, compound main monomer with main monomer n-butyl acrylate 25～30g, methyl methacrylate 5～10g and vinylbenzene 5～10g composition, 3%～15% epoxy monomer glycidyl methacrylate, remaining nonionic emulsifying agent and anionic emulsifier, half of the pre-emulsion that 0.05%～0.15% initiator and 25g water are formed is added drop-wise in the reaction flask in 1h～1.5h, wherein, remaining nonionic emulsifying agent 1.0%～3.0%, remaining anionic emulsifier 2.0%～4.5%;
3. in remaining pre-emulsion, add all fluorine monomer dodecafluorhe-ptylacrylates, silicon monomer vinyltriethoxysilane and residual epoxide monomer glycidyl methacrylate, emulsification, and in 1h～1.5h, be added drop-wise in the reaction flask, drip the solution of forming by residue initiator and pH damping fluid sodium bicarbonate simultaneously, and drip off after making its several minutes after all monomers drip off;
4. temperature is remained on 82 ± 2 ℃ of reaction 1.5h～2h and promptly get product.
Embodiment 2
Main monomer is the compound monomer that n-butyl acrylate 25～30g and vinylbenzene 10～20g form.
1. in being housed, the 250ml four-hole boiling flask of electric mixer, prolong and thermometer adds 0.5%～1% nonionic emulsifying agent polyoxyethylene aryl phenol acrylate, 0.5%～1.5% anionic emulsifier alkyl vinylformic acid-2-ethanesulfonic acid sodium and 30g water, be warming up to bath temperature and reach 82 ± 2 ℃, add 0.1%～0.4% initiator potassium persulfate;
2. behind 10～30min, compound monomer with main monomer n-butyl acrylate 25～30g and vinylbenzene 10～20g composition, 3%～15% epoxy monomer glycidyl methacrylate, remaining nonionic emulsifying agent and anionic emulsifier, half of the pre-emulsion that 0.05%～0.15% initiator and 25g water are formed is added drop-wise in the reaction flask in 1h～1.5h, wherein, remaining nonionic emulsifying agent 1.0%～3.0%, remaining anionic emulsifier 2.0%～4.5%;
3. in remaining pre-emulsion, add all fluorine monomer vinylformic acid 19 fluorine heptyl esters, silicon monomer vinyltriethoxysilane and residual epoxide monomer glycidyl methacrylate, emulsification, and in 1h～1.5h, be added drop-wise in the reaction flask, drip the solution of forming by residue initiator and pH damping fluid sodium bicarbonate simultaneously, and drip off after making its several minutes after all monomers drip off;
4. temperature is remained on 82 ± 2 ℃ of reaction 1.5h～2h and promptly get product.
Embodiment 3
Main monomer is the compound monomer that n-butyl acrylate 25～30g and methyl methacrylate 10～20g form,
1. in being housed, the 250ml four-hole boiling flask of electric mixer, prolong and thermometer adds 0.5%～1% nonionic emulsifying agent polyoxyethylene aryl phenol acrylate, 0.5%～1.5% anionic emulsifier sodium p styrene sulfonate and 30g water, be warming up to bath temperature and reach 82 ± 2 ℃, add 0.1%～0.4% initiator potassium persulfate;
2. behind 10～30min, compound monomer with main monomer n-butyl acrylate 25～30g, methyl methacrylate 10～20g composition, 3%～15% epoxy monomer glycidyl methacrylate, remaining nonionic emulsifying agent and anionic emulsifier, half of the pre-emulsion that 0.05%～0.15% initiator and 25g water are formed is added drop-wise in the reaction flask in 1h～1.5h, wherein, remaining nonionic emulsifying agent 1.0%～3.0%, remaining anionic emulsifier 2.0%～4.5%;
3. in remaining pre-emulsion, add all fluorine monomer methacrylic acid ten difluoro heptyl esters, silicon monomer γ-methacryloxypropyl trimethoxy silane and residual epoxide monomer glycidyl methacrylate, emulsification, and in 1h～1.5h, be added drop-wise in the reaction flask, drip the solution of forming by residue initiator and pH damping fluid sodium bicarbonate simultaneously, and drip off after making its several minutes after all monomers drip off;
4. temperature is remained on 82 ± 2 ℃ of reaction 1.5h～2h and promptly get product.
Embodiment 4
Main monomer is the compound monomer that methyl methacrylate 25～30g and vinylbenzene 10～20g form.
1. in being housed, the 250ml four-hole boiling flask of electric mixer, prolong and thermometer adds 0.5%～1% nonionic emulsifying agent allyloxy polyoxyethylene nonylphenol ether, 0.5%～1.5% anionic emulsifier 2-acrylamide-2,2 dimethyl ethyl sulfonic acid sodium and 30g water, be warming up to bath temperature and reach 82 ± 2 ℃, add 0.1%～0.4% initiator Potassium Thiosulphate;
2. behind 10～30min, compound monomer with main monomer methyl methacrylate 25～30g, vinylbenzene 10～20g composition, 3%～15% epoxy monomer glytidyl methacrylate, remaining nonionic emulsifying agent and anionic emulsifier, half of the pre-emulsion that 0.05%～0.15% initiator and 25g water are formed is added drop-wise in the reaction flask in 1h～1.5h, wherein, remaining nonionic emulsifying agent 1.0%～3.0%, remaining anionic emulsifier 2.0%～4.5%;
3. in remaining pre-emulsion, add all fluorine monomer methacrylic acid ten difluoro heptyl esters, silicon monomer vinyltriethoxysilane and residual epoxide monomer glytidyl methacrylate, emulsification, and in 1h～1.5h, be added drop-wise in the reaction flask, drip the solution of forming by residue initiator and pH damping fluid sodium bicarbonate simultaneously, and drip off after making its several minutes after all monomers drip off;
4. temperature is remained on 82 ± 2 ℃ of reaction 1.5h～2h and promptly get product.
Embodiment 5
Main monomer is the compound monomer that cyclohexyl acrylate 25～30g and vinylbenzene 10～20g form.
1. in being housed, the 250ml four-hole boiling flask of electric mixer, prolong and thermometer adds 0.5%～1% nonionic emulsifying agent polyoxyethylene nonyl phenol acrylate, 0.5%～1.5% anionic emulsifier alkyl vinylformic acid-2-ethanesulfonic acid sodium and 30g water, be warming up to bath temperature and reach 82 ± 2 ℃, add 0.1%～0.4% initiator ammonium persulfate;
2. behind 10～30min, compound monomer with main monomer cyclohexyl acrylate 25～30g, vinylbenzene 10～20g composition, 3%～15% epoxy monomer glytidyl methacrylate, remaining nonionic emulsifying agent and anionic emulsifier, half of the pre-emulsion that 0.05%～0.15% initiator and 25g water are formed is added drop-wise in the reaction flask in 1h～1.5h, wherein, remaining nonionic emulsifying agent 1.0%～3.0%, remaining anionic emulsifier 2.0%～4.5%;
3. in remaining pre-emulsion, add all fluorine monomer methacrylic acid ten difluoro heptyl esters, silicon monomer vinyl silane triisopropoxide and residual epoxide monomer glytidyl methacrylate, emulsification, and in 1h～1.5h, be added drop-wise in the reaction flask, drip the solution of forming by residue initiator and pH damping fluid sodium bicarbonate simultaneously, and drip off after making its several minutes after all monomers drip off;
4. temperature is remained on 82 ± 2 ℃ of reaction 1.5h～2h and promptly get product.
Embodiment 6
Main monomer is the compound main monomer formed of ethyl propenoate 15～25g and ethylene glycol diacrylate 15～25g totally 30～50g.
1. in being housed, the 250ml four-hole boiling flask of electric mixer, prolong and thermometer adds 0.5%～1% nonionic emulsifying agent polyoxyethylene aryl phenol acrylate, 0.5%～1.5% anionic emulsifier sodium p styrene sulfonate and 30g water, be warming up to bath temperature and reach 82 ± 2 ℃, add 0.1%～0.4% initiator potassium persulfate;
2. behind 10～30min, the compound monomer that main monomer ethyl propenoate 15～25 and ethylene glycol diacrylate 15～25 formed is totally 30～50g, 3%～15% epoxy monomer glytidyl methacrylate, remaining nonionic emulsifying agent and anionic emulsifier, half of the pre-emulsion that 0.05%～0.15% initiator and 25g water are formed is added drop-wise in the reaction flask in 1h～1.5h, wherein, remaining nonionic emulsifying agent 1.0%～3.0%, remaining anionic emulsifier 2.0%～4.5%;
3. in remaining pre-emulsion, add all fluorine monomer vinylformic acid 19 fluorine heptyl esters, silicon monomer vinyl tri-tert silane and residual epoxide monomer glycidyl methacrylate, emulsification, and in 1h～1.5h, be added drop-wise in the reaction flask, drip the solution of forming by residue initiator and pH damping fluid sodium bicarbonate simultaneously, and drip off after making its several minutes after all monomers drip off;
4. temperature is remained on 82 ± 2 ℃ of reaction 1.5h～2h and promptly get product.
Embodiment 7
Main monomer is the compound main monomer formed of ethylene glycol diacrylate 15～20g and cyclohexyl acrylate 20～30g totally 30～50g.
1. in being housed, the 250ml four-hole boiling flask of electric mixer, prolong and thermometer adds 0.5%～1% nonionic emulsifying agent polyoxyethylene nonyl phenol acrylate, 0.5%～1.5% anionic emulsifier sodium p styrene sulfonate and 30g water, be warming up to bath temperature and reach 82 ± 2 ℃, add 0.1%～0.4% initiator ammonium persulfate;
2. behind 10～30min, with main monomer is the compound main monomer that can form of ethylene glycol diacrylate 15～20 gram and cyclohexyl acrylate 20～30 totally 30～50g, 3%～15% epoxy monomer glytidyl methacrylate, remaining nonionic emulsifying agent and anionic emulsifier, half of the pre-emulsion that 0.05%～0.15% initiator and 25g water are formed is added drop-wise in the reaction flask in 1h～1.5h, wherein, remaining nonionic emulsifying agent 1.0%～3.0%, remaining anionic emulsifier 2.0%～4.5%;
3. in remaining pre-emulsion, add all fluorine monomer methacrylic acid ten difluoro heptyl esters, silicon monomer vinyl silane triisopropoxide and residual epoxide monomer glytidyl methacrylate, emulsification, and in 1h～1.5h, be added drop-wise in the reaction flask, drip the solution of forming by residue initiator and pH damping fluid sodium bicarbonate simultaneously, and drip off after making its several minutes after all monomers drip off;
4. temperature is remained on 82 ± 2 ℃ of reaction 1.5h～2h and promptly get product.
Embodiment 8
The compound monomer that n-butylacrylate 10～30g and ethyl propenoate 15～20g form is totally 30～50g.
1. in being housed, the 250ml four-hole boiling flask of electric mixer, prolong and thermometer adds 0.5%～1% nonionic emulsifying agent allyloxy polyoxyethylene nonylphenol ether, 0.5%～1.5% anionic emulsifier maleic acid higher alcohols monoesters sodium and 30g water, be warming up to bath temperature and reach 82 ± 2 ℃, add 0.1%～0.4% initiator potassium persulfate;
2. behind 10～30min, with main monomer is the compound monomer totally 30～50g of n-butylacrylate 10～30 gram and ethyl propenoate 15～20 gram compositions, 3%～15% epoxy monomer glytidyl methacrylate, remaining nonionic emulsifying agent and anionic emulsifier, half of the pre-emulsion that 0.05%～0.15% initiator and 25g water are formed is added drop-wise in the reaction flask in 1h～1.5h, wherein, remaining nonionic emulsifying agent 1.0%～3.0%, remaining anionic emulsifier 2.0%～4.5%;
3. in remaining pre-emulsion, add all fluorine monomer methacrylic acid ten difluoro heptyl esters, silicon monomer vinyltriethoxysilane and residual epoxide monomer glycidyl methacrylate, emulsification, and in 1h～1.5h, be added drop-wise in the reaction flask, drip the solution of forming by residue initiator and pH damping fluid sodium bicarbonate simultaneously, and drip off after making its several minutes after all monomers drip off;
4. temperature is remained on 82 ± 2 ℃ of reaction 1.5h～2h and promptly get product.
To use prior art and not use the product of technology gained of the present invention to carry out performance test fully, the product that the inventive method is made carries out performance test then, and the two performance perameter of testing gained is listed as follows:
| Latex film | Solvent resistance, swelling ratio (%) | Acid resistance, swelling ratio (%) | Alkali resistance, swelling ratio (%) | Surface free energy, γ s(mN/m) |
| Comparative example 1 | 28.69 | 15.97 | 19.39 | 42.5 |
| Comparative example 2 | 15.36 | 3.07 | 3.22 | 18.4 |
| Comparative example 3 | 14.21 | 1.76 | 2.96 | 20.7 |
| Comparative example 4 | 18.79 | 3.15 | 3.34 | 19.4 |
| The embodiment parameter mean | 12.45 | 1.90 | 2.14 | 15.5 |
By the comparison to parameter, as can be seen, along with the adding of fluorine monomer, silicon monomer and epoxy monomer, swelling ratio all has the trend that reduces, and the solvent resistance of latex film, resistance to acids and bases strengthen; And the surface free energy of copolymer latices film reduces along with the adding of fluorine monomer, silicon monomer and epoxy monomer.And use the inventive method, when introducing fluorine monomer, silicon monomer and epoxy monomer simultaneously in latex film, its solvent resistance, resistance to acids and bases are the strongest, and surface energy is minimum, and our measured minimum surface free energy is 15.5mN/m.
Claims (7)
1 one kinds of heavy-duty coatings are with the preparation method of fluorine, silicon, epoxide modified low surface energy acrylate emulsion, above to choose any one kind of them in vinylbenzene, methyl methacrylate, n-butylacrylate, isobutyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, propenoic acid beta-hydroxy ethyl ester, propenoic acid beta-hydroxy propyl ester, ethylene glycol diacrylate, ethyl propenoate, ethyl acrylate, (methyl) acrylic acid hydroxy alkyl ester as main monomer, with main monomer is a mass unit, the according to the form below prescription, concrete implementation step is as follows:
Factor Quality
Epoxy monomer 3％～30％
Fluorine monomer 5％～30％
Silicon monomer 0.5％～5％
Initiator 0.5％～0.8％
Emulsifying agent 4％～6％
Sodium bicarbonate 0％～1％
Water 120％～171.4％
% is the mass percent that accounts for total main monomer
1. in reaction vessel, add 0.5%～1% nonionic emulsifying agent, 0.5%～1.5% anionic emulsifier and 30g water, be warming up to bath temperature and reach 82 ± 2 ℃, add 0.1%～0.4% initiator;
2. behind 10～30min, with main monomer, 3%～15% epoxy monomer, remaining nonionic emulsifying agent and anionic emulsifier, half of the pre-emulsion that 0.05%～0.15% initiator and 25g water are formed adds in the reaction vessel in 1h～1.5h, described anionic emulsifier is alkyl vinylformic acid-2-ethanesulfonic acid sodium, 2-acrylamide-2,2 dimethyl ethyl sulfonic acid sodium, sodium p styrene sulfonate, the combination of one or more in the maleic acid higher alcohols monoesters sodium, nonionic emulsifying agent is a polyoxyethylene nonyl phenol acrylate, the allyloxy polyoxyethylene nonylphenol ether, the combination of one or more in the polyoxyethylene aryl phenol acrylate, wherein, remaining nonionic emulsifying agent 1.0%～3.0%, remaining anionic emulsifier 2.0%～4.5%;
3. in remaining pre-emulsion, add all fluorine monomer, silicon monomer and residual epoxide monomer, emulsification, and in 1h～1.5h, add in the reaction vessel, add the solution of forming by residue initiator and pH damping fluid sodium bicarbonate simultaneously, and make to add behind its several minutes after all monomers addings and finish;
4. temperature is remained on 82 ± 2 ℃ of reaction 1.5h～2h and obtain product.
2. the preparation method of heavy-duty coating according to claim 1 fluorine, silicon, epoxide modified low surface energy acrylate emulsion is characterized in that: entire reaction course adds solvent and adopts the method that drips in reaction vessel.
3. the preparation method of heavy-duty coating according to claim 1 fluorine, silicon, epoxide modified low surface energy acrylate emulsion, it is characterized in that: used fluorine monomer is fluorinated acrylic ester monomer methacrylic acid ten difluoro heptyl esters, dodecafluorhe-ptylacrylate, a kind of in vinylformic acid 19 fluorine esters, trifluoroethyl methacrylate, methacrylic acid hexafluoro butyl ester, the perfluoro capryl ethyl propenoate.
4. heavy-duty coating according to claim 1 is characterized in that with the preparation method of fluorine, silicon, epoxide modified low surface energy acrylate emulsion: used silicon monomer is a kind of in γ-methacryloxypropyl three (trimethyl silicon based) silane γ-methacryloxypropyl triethoxyl silane, γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-methacryloxypropyl three isopropoxy silane, vinyl silane triisopropoxide, the vinyl tri-tert silane.
5. the preparation method of heavy-duty coating according to claim 1 fluorine, silicon, epoxide modified low surface energy acrylate emulsion, it is characterized in that: used epoxy monomer is a glycidyl methacrylate, glycidyl acrylate, a kind of in glytidyl methacrylate, the isobornyl methacrylate.
6. heavy-duty coating according to claim 1 is characterized in that with the preparation method of fluorine, silicon, epoxide modified low surface energy acrylate emulsion: used initiator is one or more the combination in ammonium persulphate, Potassium Persulphate, Potassium Persulphate-Potassium hydrogen sulfite or the Potassium Thiosulphate.
7. the preparation method of heavy-duty coating according to claim 1 fluorine, silicon, epoxide modified low surface energy acrylate emulsion, it is characterized in that: used emulsifying agent is the moon/non-ionic composite polymerisable emulsifier.
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| CNA2006101248071A CN1944476A (en) | 2006-10-19 | 2006-10-19 | Process for preparing fluorin, silicon, epoxide modified low surface energy acrylate emulsion for heavy anti-corrosion paint |
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