CN101348595B - Fluorine-silicon modified self-crosslinking acrylic ester emulsion preparation method - Google Patents
Fluorine-silicon modified self-crosslinking acrylic ester emulsion preparation method Download PDFInfo
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Abstract
The invention provides a fluorine-silicon modified self-crosslinking acrylic ester emulsion and a preparation method thereof, belonging to the technical field of polymer synthesis. The emulsion is a product formed by organosilicon monomers, fluoride-containing acrylic monomers, (methyl) acrylic monomers and self-crosslinking monomers through core-shell emulsion polymerization. The preparation method adopts a core-shell emulsion polymerization method, thereby ensuring that the fluoride-containing acrylic monomers tend to surface polymerization, and fluorine atoms tend to polymer surface in emulsion film forming process; moreover, the monomers capable of self-crosslinking is added to a shell layer, so as to utilize the crosslinking of the monomers to fixedly limit the migration of the fluorine atoms towards the inside of latex particles, as well as the swing of chains, thereby ensuring that the performances of the fluoride-containing emulsion are completely embodied. The preparation method improves the water resistance, stain resistance, solvent resistance, weather resistance and other comprehensive performances of the emulsion. The fluorine-silicon modified self-crosslinking acrylic ester emulsion prepared through the preparation method can be widely applied to high-grade building paint, industrial paint and wooden ware varnish. Moreover, the preparation method has the characteristics of simple manufacturing process, easy reaction condition control, good emulsion stability and environment-friendly property.
Description
Technical field
The present invention relates to a kind of fluorine-silicon modified self-crosslinking acrylic ester emulsion and preparation method thereof, belong to the macromolecule synthesising technology field.This fluorine-silicon modified self-crosslinking acrylic ester emulsion is mainly used in fields such as top-grade building exterior coating, industrial coating, woodwork coating, varnish.
Background technology
Along with the reinforcement of people to environmental consciousness, environment-friendly type aqueous emulsion paint is used widely architectural having obtained of interior exterior wall.Yet along with the rise of top-grade building, people are also more and more higher to the performance requriements of emulsion paint.Should environmental pollution little, have excellent weathering resistance, winter hardiness, water tolerance, resistance to soiling, tint retention again.Now on the market, main still based on benzene emulsion, pure-acrylic emulsion and organosilicon crylic acid latex.Benzene emulsion is owing to have the phenyl ring of conjugated link(age) in the system, the ability of ultraviolet-resistant aging is the poorest, generally is not suitable for external wall of building.Pure-acrylic emulsion will be better than benzene emulsion greatly on ultraviolet-resistant aging, but other over-all propertieies and the benzene emulsion of pure-acrylic emulsion also are more or less the same.Organosilicon crylic acid latex is an organosilicon radical in the grafting in acrylic emulsion.And the bond energy of C-Si key is greater than the C-C key, aspect water-fast, anti-pollution characteristic bigger improvement arranged.But organosilyl content can not be too high in the organosilicon crylic acid latex, otherwise can cause the decline of stability of emulsion, and this just makes certain influence aspect modified effect.
Putting before this, more the exploitation of high-performance emulsion is arisen at the historic moment.Method is exactly to introduce fluorine-containing class monomer in ACRYLIC EMULSION.As everyone knows, the C-F key has the surface energy that bigger bond energy (451-485kj/mol) can reduce the fluorine acrylic emulsion greatly.Fluorine acrylic emulsion polymkeric substance is all had greatly improved in many-sides such as water-fast, resistant, UV resistant, weathering resistancies.Therefore, in recent years, the fluorine acrylic emulsion has become the research and development focus of emulsion and coating, and is subjected to people's generally attention.
Summary of the invention
The object of the present invention is to provide a kind of fluorine-silicon modified self-crosslinking acrylic ester emulsion with self-crosslinking network structure, the water-based exterior wall paint of preparing with this emulsion has performances such as excellent water-fast, weather-proof, anti-contamination, UV resistant.
The present invention also provides a kind of method that adopts the core-shell emulsion polymerization mode to prepare above-mentioned fluorine-silicon modified self-crosslinking acrylic ester emulsion, its mentality of designing is: make fluorine atom be enriched in shell as much as possible, embody the performance of fluorine-containing latex to greatest extent, and can reduce the consumption of fluorine monomer, reduce raw materials cost.But because fluoropolymer has bigger hydrophobicity, can be slowly to the emulsion particle internal migration, finally can cause the decline of over-all properties.Another novel thinking of the present invention is exactly: introduce self-cross linking monomer in system, utilize its crosslinked swing that fixes the restriction fluorine atom to emulsion particle internal migration and chain, make the performance of fluorine-containing latex obtain maximum embodiment.
Fluorine-silicon modified self-crosslinking acrylic ester emulsion of the present invention is the product that is formed by core-shell emulsion polymerization by organosilane monomer, fluorine-containing class monomer, (methyl) acrylic monomer and self-cross linking monomer;
Wherein, organosilane monomer is one or more the mixture in vinyltrimethoxy silane, vinyltriethoxysilane, (methyl) acryloxy propyl trimethoxy silicane;
Fluorine-containing class monomer is one or more the mixture in (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid hexafluoro butyl ester, vinylformic acid perfluor alkyl ethide ester, (methyl) vinylformic acid heterochain fluorine ester;
(methyl) acrylic monomer is one or more the mixture in vinylformic acid, methacrylic acid, methyl methacrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, glycol diacrylate, the 1,4 butanediol diacrylate;
Self-cross linking monomer is one or both the mixture in diacetone-acryloamide(DAA), the vinylformic acid acetoacetyl oxygen ethyl ester.
Solidifying agent is a kind of in carbonic acid hydrazides, succinic acid hydrazide ii, the adipic dihydrazide.
The preparation method of fluorine-silicon modified self-crosslinking acrylic ester emulsion of the present invention comprises following two steps:
The first step: the preparation of nuclear emulsion
Part deionized water, partial emulsifier, initiator, PH buffer reagent is rebasing, (methyl) acrylic monomer carries out pre-emulsification by remaining another part deionized water and another part emulsifying agent, dripped 2-4 hour at 70-90 ℃, make the nuclear emulsion, wherein each component concentration is as follows:
Deionized water 100-180 part
Emulsifying agent 1-4 part
Initiator 0.2-1.0 part
PH buffer reagent 0.2-1.0 part
(methyl) acrylic monomer 80-120 part;
Second step: the preparation of core-shell emulsion
Deionized water, emulsifying agent, initiator and organosilane monomer, fluorine-containing class monomer, (methyl) acrylic monomer and self-cross linking monomer are carried out pre-emulsification, make the shell pre-emulsion; Under 70-90 ℃, described shell pre-emulsion is splashed in the above-mentioned nuclear emulsion, carry out letex polymerization, 2-4 hour dropping time, after reacting completely, add solidifying agent and PH conditioning agent, make the fluorine-silicon modified self-crosslinking acrylic ester emulsion with nucleocapsid structure, wherein each component concentration is as follows:
Deionized water 30-60 part
Emulsifying agent 0.5-3 part
Initiator 0.1-0.5 part
Organosilane monomer 1-10 part
(methyl) acrylic monomer 60-100 part
Fluorine-containing class monomer 2-20 part
Self-cross linking monomer 1-10 part
Solidifying agent 0.3-5 part
PH conditioning agent 0.2-2 part.
In the present invention, described organosilane monomer is one or more the mixture in vinyltrimethoxy silane, vinyltriethoxysilane, (methyl) acryloxy propyl trimethoxy silicane.
In the present invention, described fluorine-containing class monomer is one or more the mixture in (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid hexafluoro butyl ester, vinylformic acid perfluor alkyl ethide ester, (methyl) vinylformic acid heterochain fluorine ester.
In the present invention, described (methyl) acrylic monomer is one or more the mixture in vinylformic acid, methacrylic acid, methyl methacrylate, ethyl propenoate, butyl acrylate, the Isooctyl acrylate monomer.
In the present invention, described self-cross linking monomer is one or both the mixture in diacetone-acryloamide(DAA), the vinylformic acid acetoacetyl oxygen ethyl ester.
In the present invention, described emulsifying agent is one or more the mixture in alkylphenol polyoxyethylene ammonium sulfate, alkylphenol polyoxyethylene, allyl group alkylphenol polyoxyethylene, allyl group alkylphenol polyoxyethylene ammonium sulfate, the fluorine-containing emulsifier.
In the present invention, described initiator is a kind of in ammonium persulphate, the Potassium Persulphate.
In the present invention, described solidifying agent is a kind of in carbonic acid hydrazides, succinic acid hydrazide ii, the adipic dihydrazide.
Wherein, described PH buffer reagent is a kind of in SODIUM PHOSPHATE, MONOBASIC, the sodium bicarbonate.
In the present invention, described PH conditioning agent is a kind of in sodium hydroxide, potassium hydroxide, ammoniacal liquor, the 2-methyl 2-aminopropanol.
It is simple that fluorine-silicon modified self-crosslinking acrylic ester emulsion of the present invention has preparation technology, and reaction conditions is easy to control, good emulsion stability, and environmental friendliness gets characteristics, can be widely used in top-grade building coating, and industrial coating is in the woodenware lacquer.
Embodiment
Below in conjunction with embodiment the present invention is described in detail, but be not used for limiting the present invention.
Embodiment 1:
With 120 parts of deionized waters, 1.8 parts in alkylphenol polyoxyethylene ammonium sulfate (58% content, as follows), 0.4 part of alkylphenol polyoxyethylene, sodium bicarbonate part joins in the reactor for 0.4 part, and heated and stirred is fully dissolved it.Temperature remains on 75 ± 2 ℃.
With 35 parts of deionized waters, 0.6 part in alkylphenol polyoxyethylene ammonium sulfate, 0.12 part of dissolving of Potassium Persulphate adds pre-newborn still, slowly add monomer: 41 parts of methyl methacrylates, 30 parts of Isooctyl methacrylates, 1.5 parts in vinylformic acid, 1,1 part of 4-butylene glycol diacrylate, vigorous stirring must be examined pre-emulsion in 30 minutes, and this nuclear pre-emulsion slowly is added dropwise to reactor, time spent 2-4 hour, 75 ± 2 ℃ of temperature dropwise back insulation 1 hour.
With 35 parts of deionized waters, 0.6 part in alkylphenol polyoxyethylene ammonium sulfate, 0.22 part of fluorine-containing emulsifier, 0.2 part in allyl group alkylphenol polyoxyethylene ammonium sulfate, 0.12 part of dissolving of Potassium Persulphate adds pre-newborn still, slowly add following monomer: 55 parts of methyl methacrylates, 22 parts of Isooctyl methacrylates, 1.5 parts in vinylformic acid, 1,1 part of 4-butylene glycol diacrylate, 2 parts of methacrylic acid hexafluoro butyl esters, 4 parts of vinylformic acid acetoacetyl oxygen ethyl esters.Vigorous stirring got the shell pre-emulsion in 30 minutes, and this shell pre-emulsion slowly is added dropwise to aforesaid reaction vessel, when dripping residue 30% left and right sides, added 2 parts of vinyltrimethoxy silanes in the shell pre-emulsion, stirred and continued dropping in 5 minutes.Total time spent 2-4 hour, 75 ± 2 ℃ of temperature dropwised 2-3 hour postcooling of back insulation.
After system is cooled to room temperature, the system pH value is adjusted to 7, adds 2 parts of adipic dihydrazides, a small amount of defoamer, mould inhibitor with strong aqua.Filter discharging with 200 mesh filter screens, promptly get fluorine-silicon modified self-crosslinking acrylic ester emulsion with self-crosslinking structure.
Embodiment 2:
With 120 parts of deionized waters, 1 part in alkylphenol polyoxyethylene ammonium sulfate (58% content, as follows), 0.18 part of alkylphenol polyoxyethylene, sodium bicarbonate part joins in the reactor for 0.4 part, and heated and stirred is fully dissolved it.Temperature remains on 80 ± 2 ℃.
With 35 parts of deionized waters, 0.6 part in alkylphenol polyoxyethylene ammonium sulfate, 0.12 part of dissolving of ammonium persulphate adds pre-newborn still, slowly add monomer: 50 parts of methyl methacrylates, 23 parts of Isooctyl methacrylates, 2 parts in vinylformic acid, 1,1 part of 4-butylene glycol diacrylate, vigorous stirring must be examined pre-emulsion in 30 minutes, and this nuclear pre-emulsion slowly is added dropwise to reactor, time spent 2-4 hour, 80 ± 2 ℃ of temperature dropwise back insulation 1 hour.
With 35 parts of deionized waters, 0.56 part in alkylphenol polyoxyethylene ammonium sulfate, 0.28 part of fluorine-containing emulsifier, 0.2 part in allyl group alkylphenol polyoxyethylene ammonium sulfate, 0.12 part of dissolving of ammonium persulphate adds pre-newborn still, slowly add following monomer: 55 parts of methyl methacrylates, 22 parts of Isooctyl methacrylates, 2 parts in vinylformic acid, 1,1 part of 4-butylene glycol diacrylate, 7.5 parts of vinylformic acid heterochain fluorine esters, 4 parts of diacetone-acryloamide(DAA)s.Vigorous stirring got the shell pre-emulsion in 30 minutes, and this shell pre-emulsion slowly is added dropwise to aforesaid reaction vessel, when dripping residue 30% left and right sides, added 2 parts of vinyltriethoxysilanes in the shell pre-emulsion, stirred and continued dropping in 5 minutes.Total time spent 2-4 hour, 80 ± 2 ℃ of temperature dropwised 2-3 hour postcooling of back insulation.
After system is cooled to room temperature, the system pH value is adjusted to 7, adds 2.4 parts of succinic acid hydrazide iis, a small amount of defoamer, mould inhibitor with sodium hydroxide.Filter discharging with 200 mesh filter screens, promptly get fluorine-silicon modified self-crosslinking acrylic ester emulsion with self-crosslinking structure.
Embodiment 3:
With 120 parts of deionized waters, 1.4 parts in alkylphenol polyoxyethylene ammonium sulfate (58% content, as follows), 0.2 part of alkylphenol polyoxyethylene, sodium bicarbonate part joins in the reactor for 0.4 part, and heated and stirred is fully dissolved it.Temperature remains on 85 ± 2 ℃.
With 35 parts of deionized waters, 0.6 part in alkylphenol polyoxyethylene ammonium sulfate, 0.12 part of dissolving of ammonium persulphate adds pre-newborn still, slowly adds monomer: 41 parts of methyl methacrylates, 30 parts of Isooctyl methacrylates, 1.5 parts in vinylformic acid, 0.8 part of glycol diacrylate, vigorous stirring must be examined pre-emulsion in 30 minutes, this nuclear pre-emulsion slowly is added dropwise to reactor, time spent 2-4 hour, 85 ± 2 ℃ of temperature dropwised back insulation 1 hour.
With 35 parts of deionized waters, 0.56 part in alkylphenol polyoxyethylene ammonium sulfate, 0.28 part of fluorine-containing emulsifier, 0.2 part in allyl group alkylphenol polyoxyethylene ammonium sulfate, 0.12 part of dissolving of ammonium persulphate adds pre-newborn still, slowly add following monomer: 60 parts of methyl methacrylates, 17 parts of Isooctyl methacrylates, 1.5 parts in vinylformic acid, 0.8 part of glycol diacrylate, 15 parts of vinylformic acid trifluoro ethyl esters, 3 parts of diacetone-acryloamide(DAA)s.Vigorous stirring got the shell pre-emulsion in 30 minutes, and this shell pre-emulsion slowly is added dropwise to aforesaid reaction vessel, when dripping residue 30% left and right sides, added 2 parts of vinyltrimethoxy silanes in the shell pre-emulsion, stirred and continued dropping in 5 minutes.Total time spent 2-4 hour, 85 ± 2 ℃ of temperature dropwised 2-3 hour postcooling of back insulation.
After system is cooled to room temperature, the system pH value is adjusted to 7, adds 1.5 parts of carbonic acid hydrazides, a small amount of defoamer, mould inhibitor with potassium hydroxide.Filter discharging with 200 mesh filter screens, promptly get fluorine-silicon modified self-crosslinking acrylic ester emulsion with self-crosslinking structure.
Embodiment 4:
With 120 parts of deionized waters, 1.8 parts in alkylphenol polyoxyethylene ammonium sulfate (58% content, as follows), 0.4 part of alkylphenol polyoxyethylene, sodium bicarbonate part joins in the reactor for 0.4 part, and heated and stirred is fully dissolved it.Temperature remains on 80 ± 2 ℃.
With 35 parts of deionized waters, 0.6 part in alkylphenol polyoxyethylene ammonium sulfate, 0.12 part of dissolving of ammonium persulphate adds pre-newborn still, slowly add monomer: 44 parts of methyl methacrylates, 29 parts of Isooctyl methacrylates, 2 parts in vinylformic acid, 1,1 part of 4-butylene glycol diacrylate, vigorous stirring must be examined pre-emulsion in 30 minutes, and this nuclear pre-emulsion slowly is added dropwise to reactor, time spent 2-4 hour, 80 ± 2 ℃ of temperature dropwise back insulation 1 hour.
With 35 parts of deionized waters, 0.56 part in alkylphenol polyoxyethylene ammonium sulfate, 0.28 part of fluorine-containing emulsifier, 0.2 part in allyl group alkylphenol polyoxyethylene ammonium sulfate, 0.12 part of dissolving of ammonium persulphate adds pre-newborn still, slowly add following monomer: 55 parts of methyl methacrylates, 22 parts of Isooctyl methacrylates, 2 parts in vinylformic acid, 1,1 part of 4-butylene glycol diacrylate, 5 parts of perfluoroalkyl acrylate, 4 parts of diacetone-acryloamide(DAA)s.Vigorous stirring got the shell pre-emulsion in 30 minutes, and this shell pre-emulsion slowly is added dropwise to aforesaid reaction vessel, when dripping residue 30% left and right sides, added 4 parts of (methyl) acryloxy propyl trimethoxy silicanes in the shell pre-emulsion, stirred and continued dropping in 5 minutes.Total time spent 2-4 hour, 80 ± 2 ℃ of temperature dropwised 2-3 hour postcooling of back insulation.
After system is cooled to room temperature, the system pH value is adjusted to 7, adds 2 parts of adipic dihydrazides, a small amount of defoamer, mould inhibitor with 2-methyl 2-aminopropanol.Filter discharging with 200 mesh filter screens, promptly get fluorine-silicon modified self-crosslinking acrylic ester emulsion with self-crosslinking structure.
Above-mentioned embodiment has just exemplified exemplary embodiments of the present invention; can only think explanation of the present invention rather than restriction the present invention; those skilled in the art can do corresponding changes and improvements under the prompting of specification sheets, but should think in claims protection domain of the present invention.
Claims (5)
1. the preparation method of a fluorine-silicon modified self-crosslinking acrylic ester emulsion is characterized in that, this method comprises following two steps:
The first step: the preparation of nuclear emulsion
Part deionized water, partial emulsifier, initiator, PH buffer reagent is rebasing, (methyl) acrylic monomer carries out pre-emulsification by remaining another part deionized water and another part emulsifying agent, dripped 2-4 hour at 70-90 ℃, make the nuclear emulsion, wherein each component concentration is as follows:
Deionized water 100-180 part
Emulsifying agent 1-4 part
Initiator 0.2-1.0 part
PH buffer reagent 0.2-1.0 part
(methyl) acrylic monomer 80-120 part;
Second step: the preparation of core-shell emulsion
Deionized water, emulsifying agent, initiator and organosilane monomer, fluorine-containing class monomer, (methyl) acrylic monomer and self-cross linking monomer are carried out pre-emulsification, make the shell pre-emulsion; Under 70-90 ℃, described shell pre-emulsion is splashed in the above-mentioned nuclear emulsion, carry out letex polymerization, 2-4 hour dropping time, after reacting completely, add solidifying agent and PH conditioning agent, make the fluorine-silicon modified self-crosslinking acrylic ester emulsion with nucleocapsid structure, wherein each component concentration is as follows:
Deionized water 30-60 part
Emulsifying agent 0.5-3 part
Initiator 0.1-0.5 part
Organosilane monomer 1-10 part
(methyl) acrylic monomer 60-100 part
Fluorine-containing class monomer 2-20 part
Self-cross linking monomer 1-10 part
Solidifying agent 0.3-5 part
PH conditioning agent 0.2-2 part;
Wherein, organosilane monomer is one or more the mixture in vinyltrimethoxy silane, vinyltriethoxysilane, (methyl) acryloxy propyl trimethoxy silicane;
Fluorine-containing class monomer is one or more the mixture in (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid hexafluoro butyl ester, the vinylformic acid perfluor alkyl ethide ester;
(methyl) acrylic monomer is one or more the mixture in vinylformic acid, methacrylic acid, methyl methacrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, glycol diacrylate, the 1,4 butanediol diacrylate;
Self-cross linking monomer is one or both the mixture in diacetone-acryloamide(DAA), the vinylformic acid acetoacetyl oxygen ethyl ester;
Solidifying agent is a kind of in carbonic acid hydrazides, succinic acid hydrazide ii, the adipic dihydrazide.
2. the preparation method of fluorine-silicon modified self-crosslinking acrylic ester emulsion according to claim 1, it is characterized in that described emulsifying agent is one or more the mixture in alkylphenol polyoxyethylene ammonium sulfate, alkylphenol polyoxyethylene, allyl group alkylphenol polyoxyethylene, allyl group alkylphenol polyoxyethylene ammonium sulfate, the fluorine-containing emulsifier.
3. the preparation method of fluorine-silicon modified self-crosslinking acrylic ester emulsion according to claim 1 is characterized in that, described initiator is a kind of in ammonium persulphate, the Potassium Persulphate.
4. the preparation method of fluorine-silicon modified self-crosslinking acrylic ester emulsion according to claim 1 is characterized in that, described PH buffer reagent is a kind of in SODIUM PHOSPHATE, MONOBASIC, the sodium bicarbonate.
5. the preparation method of fluorine-silicon modified self-crosslinking acrylic ester emulsion according to claim 1 is characterized in that, described PH conditioning agent is a kind of in sodium hydroxide, potassium hydroxide, ammoniacal liquor, the 2-methyl 2-aminopropanol.
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| CN111087546B (en) * | 2019-12-24 | 2022-08-19 | 佛山市顺德区巴德富实业有限公司 | Industrial water-based high-gloss light-weight anticorrosive acrylic emulsion and preparation method thereof |
| CN114525059A (en) * | 2022-01-10 | 2022-05-24 | 上海三棵树防水技术有限公司 | Waterproof coating with interface reinforcing effect and preparation method thereof |
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2008
- 2008-07-28 CN CN2008101172531A patent/CN101348595B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801769A (en) * | 2016-05-05 | 2016-07-27 | 常熟林润氟硅材料有限公司 | Method for preparing fluorine-silicon modified aqueous crylic acid anti-doodling emulsion |
| CN105801769B (en) * | 2016-05-05 | 2018-01-02 | 常熟林润氟硅材料有限公司 | A kind of preparation method of the anti-graffiti emulsion of fluorinated silicone modified water soluble acrylic acid |
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| CN101348595A (en) | 2009-01-21 |
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