CN104277172A - Water-based waterproof acrylate emulsion and preparation method thereof - Google Patents
Water-based waterproof acrylate emulsion and preparation method thereof Download PDFInfo
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- CN104277172A CN104277172A CN201410509042.8A CN201410509042A CN104277172A CN 104277172 A CN104277172 A CN 104277172A CN 201410509042 A CN201410509042 A CN 201410509042A CN 104277172 A CN104277172 A CN 104277172A
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Abstract
The invention discloses a water-based waterproof acrylate emulsion and a preparation method thereof. The water-based waterproof acrylate emulsion is of a core-shell structure, wherein the core is prepared from the following components in percentage by mass: 40%-60% of styrene, 31%-51% of acrylate, 1%-5% of methacrylic acid, 0.1%-2% of methacrylate, and 0.1%-2% of acrylamide; and the shell is prepared from the following components in percentage by mass: 40-60% of styrene, 30%-50% of acrylate, 1%-5% of methacrylic acid, 0.1%-2% of methacrylate, 0.1%-2% of acrylamide and 1%-8% of a waterproof functional monomer. The particle sizes of the waterproof acrylate emulsion are 100-150nm; the glass temperature is 0-40 DEG C; the emulsion molecular weight is 10<5>-10<6>; the water-based waterproof acrylate emulsion is solidified at 20-80 DEG C to form a film; and a film with high waterproofness and chemical resistance is formed after cooling; therefore, the water-based waterproof acrylate emulsion can be widely used as a water-proofing finishing agent for main film-forming substances and fabric of water-based thermosetting coatings such as glass, metal and buildings.
Description
Technical field
The present invention relates to a kind of Waterproof acrylic ester emulsion and preparation method thereof.
Technical background
Very large pollution is had to environment after the solvent evaporates that traditional solvent based coating uses, inflammable and explosive potential safety hazard is there is in construction, storage, transportation, and the dispersion medium used by water-borne coatings is water, so have the features such as green, safety, effect be convenient, and water-borne coatings paint film has the advantages such as stronger sticking power, wear resisting property, time of drying short, good flame retardation effect.Relative to solvent based coating, no matter water-borne coatings is from the feature of environmental protection, economy, security.Efficient and convenient property all has very large advantage.Water-borne Acrylic Coating development is very fast, and acrylate paint is owing to having abundant raw material source, and film forming properties is good, has therefore been widely used in the filmogen of coating.In common acrylic ester emulsion, molecular resin is not due to crosslinked, there is the shortcomings such as compactness difference, water vapour and OTR oxygen transmission rate are high, minimum film-forming temperature is higher in the film forming matter of emulsion, especially when for anticorrosive coating, these shortcomings are doubled amplification especially, are difficult to reach to requirements such as the water tolerance of coating.In order to improve the performance of emulsion, introducing the hydrophobic functional groups such as silica or fluorine carbon in the molecule thereof and making that there are good hydrophobicity, water-repellancy, didirtresistance etc.The water contact angle of the paint film prepared normally is greater than 90 degree, and water can not soak its surface, can only landing.By the modification of organosilicon or organic fluorine hydrophobic monomer, the water tolerance of acrylic polymer emulsion paint film greatly can be improved.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of Waterproof acrylic ester emulsion and preparation method thereof is provided.
The object of the invention is achieved through the following technical solutions:
A kind of Waterproof acrylic ester emulsion, be nucleocapsid structure, described core is made up of the component of following weight percentage: the methacrylic acid of 40-60% vinylbenzene, 31-51% acrylate, 1-5%, 0.1-2% methacrylic ester, 0.1-2% acrylamide; Described shell is made up of the component of following weight percentage: the water-proof function monomer of the methacrylic acid of 40-60% vinylbenzene, 30-50% acrylate, 1-5%, 0.1-2% methacrylic ester, 0.1-2% acrylamide, 1-8%.
In above-mentioned Waterproof acrylic ester emulsion, described water-proof function monomer is preferably
Vinyltrimethoxy silane or vinyl silane triisopropoxide or vinyltriethoxysilane or γ-methacryloxypropyl trimethoxy silane or vinyl silicone oil or perfluorooctylethyl group acrylate or 2-(perfluoro capryl) ethylmethyl acrylate or N-ethylperfluoro octyl group sulfoamido ethyl propylene acid esters.
In above-mentioned Waterproof acrylic ester emulsion, described acrylate is preferably any one or a few the mixture in methyl acrylate, ethyl propenoate, butyl acrylate, 2-methyl methacrylate, ethyl 2-methacrylate.
In above-mentioned Waterproof acrylic ester emulsion, described methacrylic ester is preferably hydroxyethyl methylacrylate, Rocryl 410, methyl methacrylate, butyl methacrylate or Rocryl 410.
In above-mentioned Waterproof acrylic ester emulsion, described acrylamide is preferably N hydroxymethyl acrylamide, N-hydroxyethyl acrylamide or N, N'-methylene-bisacrylamide.
A preparation method for Waterproof acrylic ester emulsion, comprises the steps and processing condition:
(1) pre-mixing of nuclear monomer
The methacrylic acid of 40-60% vinylbenzene, 31-51% acrylate, 1-5%, 0.1-2% methacrylic ester and 0.1-2% acrylamide are dispersed in water under the effect of emulsifying agent, obtain pre-emulsification monomer mixture.
(2) pre-mixing of shell monomer
The water-proof function monomer of the methacrylic acid of 40-60% vinylbenzene, 30-50% acrylate, 1-5%, 0.1-2% methacrylic ester, 0.1-2% acrylamide and 1-8% is dispersed in water under the effect of emulsifying agent, obtains pre-emulsification monomer mixture.
(3) polyreaction
Buffer reagent and emulsifying agent are joined in reaction medium water, fully stir and be warmed up to 80-100 DEG C in reaction vessel, after temperature of reaction to be achieved, premixture and the initiator of nuclear monomer is first dripped with 1-3h, drip premixture and the initiator of shell monomer again with 1-3h after isothermal reaction 0.5-2h, drip rear continuation isothermal reaction 0.5-2h, be incubated rear termination reaction.
Relative to prior art, tool of the present invention has the following advantages and beneficial effect:
Through the acrylic ester emulsion of modification, the functional anti-aqueous monomer added makes to produce crosslinking structure between polymer chain, thus increases hardness, water tolerance and the weathering resistance of latex film.Utilize the functional anti-aqueous monomer added to have surface energy low, be easy to the characteristic to film surface transport, improve the structure properties on film surface, give film coated surface hydrophobic nature and water-repellancy.But also the glossiness, sticking power, solidity to corrosion, thermotolerance, resistance to soiling, mechanical property, ageing-resistant performance etc. that improve film can be played.The particle diameter of gained Waterproof acrylic ester emulsion is 100-150nm, and second-order transition temperature is between 0-40 DEG C, and emulsion molecular weight is 10
5-10
6.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but the scope of protection of present invention is not limited within the scope of embodiment expression.
embodiment 1
A kind of Waterproof acrylic ester emulsion and preparation thereof:
(1) alkylphenol polyoxyethylene of the sodium bicarbonate of 0.5g, 0.5g, the sodium lauryl sulphate of 0.11g are joined in the distilled water of 40g and fully stir and be heated to 80 DEG C, obtain still liquid;
(2) 7g distilled water is got, add the alkylphenol polyoxyethylene of 0.4g, the sodium lauryl sulphate of 0.08g stirs, take nuclear monomer: 11.0g vinylbenzene (55%), 8g butyl acrylate (40%), 0.3g methacrylic acid (1.5%), 0.3g hydroxyethyl methylacrylate (1.5%), 0.4gN-n-methylolacrylamide (2%) fully mixing, slowly be added drop-wise to pre-emulsification in the above-mentioned water containing emulsifying agent, and stir 0.5h and obtain stable pre-emulsion;
(3) initiator potassium persulfate taking 0.2g is dissolved in the distilled water of 10g;
(4) mass content of step (2) and (3) each 20% is joined and be obtained by reacting seed emulsion through 1h in (1);
(5) step (2) and (3) remaining amount are slowly added drop-wise in (4) by 2.5h, are added dropwise to complete rear insulation 1.5h;
(6) 7g distilled water is got, add the alkylphenol polyoxyethylene of 0.04g, the sodium lauryl sulphate of 0.08g stirs, take shell monomer: 9.2g vinylbenzene (46%), 9g butyl acrylate (45%), 0.4g methacrylic acid (2%), 0.1g hydroxyethyl methylacrylate (0.5%), 0.1gN-n-methylolacrylamide (0.5%) and 1.2g vinyl silane triisopropoxide (6%) also fully mix, slowly be added drop-wise to pre-emulsification in the above-mentioned water containing emulsifying agent, and stir 0.5h and obtain stable pre-emulsion;
(7) initiator ammonium persulfate taking 0.2g is dissolved in the distilled water of 10g;
(8) liquid that step (6) and (7) obtain slowly is added drop-wise in (5) by 2.5h, after being added dropwise to complete rear insulation 1.5h, prepares organosilicon-modified acrylate emulsion;
embodiment 2
A kind of Waterproof acrylic ester emulsion and preparation thereof:
(1) alkylphenol polyoxyethylene of the sodium bicarbonate of 0.2g, 0.08g, the sodium lauryl sulphate of 0.11g are joined in the distilled water of 40g and fully stir and be heated to 80 DEG C, obtain still liquid;
(2) 7g distilled water is got, add the alkylphenol polyoxyethylene of 0.04g, the sodium lauryl sulphate of 0.05g stirs, take nuclear monomer: the methacrylic acid (5%) of 10.2g vinylbenzene (51%), 8g ethyl propenoate (40%), 1.0g, 0.4g hydroxyethyl methylacrylate (2%), 0.4gN-hydroxyethyl acrylamide (2%) fully mixing, slowly be added drop-wise to pre-emulsification in the above-mentioned water containing emulsifying agent, and stir 0.5h and obtain stable pre-emulsion;
(3) initiator potassium persulfate taking 0.2g is dissolved in the distilled water of 10g;
(4) mass content of step (2) and (3) each 5% is joined and be obtained by reacting seed emulsion through 1h in (1);
(5) step (2) and (3) remaining amount are slowly added drop-wise in (4) by 2.0h, are added dropwise to complete rear insulation 0.5h;
(6) 7g distilled water is got, add the alkylphenol polyoxyethylene of 0.04g, the sodium lauryl sulphate of 0.08g stirs, take shell monomer: the methacrylic acid (2.5%) of 9.7g vinylbenzene (48.5%), 7.5g butyl acrylate (37.5%), 0.5g, 0.4g hydroxyethyl methylacrylate (2%), 0.4gN-hydroxyethyl acrylamide (2%) and 1.5g vinyl silicone oil (7.5%) also fully mix, slowly be added drop-wise to pre-emulsification in the above-mentioned water containing emulsifying agent, and stir 0.5h and obtain stable pre-emulsion;
(7) initiator ammonium persulfate taking 0.2g is dissolved in the distilled water of 10g;
(8) liquid that step (6) and (7) obtain slowly is added drop-wise in (5) by 2.0h, after being added dropwise to complete rear insulation 0.5h, prepares organosilicon-modified acrylate emulsion;
embodiment 3
A kind of Waterproof acrylic ester emulsion and preparation thereof:
(1) alkylphenol polyoxyethylene of the sodium carbonate of 0.2g, 0.05g, the sodium lauryl sulphate of 0.11g are joined in the distilled water of 40g and fully stir and be heated to 80 DEG C, obtain still liquid;
(2) 7g distilled water is got, add the alkylphenol polyoxyethylene of 0.4g, the sodium lauryl sulphate of 0.8g stirs, take nuclear monomer: the hydroxyethyl methylacrylate (1%) of 11.5g vinylbenzene (57.5%), 7.9g ethyl propenoate (39.5%), 0.25g methacrylic acid (1.25%), 0.2g, 0.15gN-n-methylolacrylamide (0.75%) fully mixing, slowly be added drop-wise to pre-emulsification in the above-mentioned water containing emulsifying agent, and stir 0.5h and obtain stable pre-emulsion;
(3) initiator potassium persulfate taking 0.2g is dissolved in the distilled water of 10g;
(4) mass content of step (2) and (3) each 10% is joined and be obtained by reacting seed emulsion through 0.5h in (1);
(5) step (2) and (3) remaining amount are slowly added drop-wise in (4) by 3.0h, are added dropwise to complete rear insulation 1.0h;
(6) 7g distilled water is got, add the alkylphenol polyoxyethylene of 0.04g, the sodium lauryl sulphate of 0.08g stirs, take shell monomer: the hydroxyethyl methylacrylate (1%) of 11.5g vinylbenzene (57.5%), 7g ethyl propenoate (35%), 0.25g methacrylic acid (1.25%), 0.2g, 0.15gN-n-methylolacrylamide (0.75%) and 0.9g perfluorooctylethyl group acrylate (4.5%) also fully mix, slowly be added drop-wise to pre-emulsification in the above-mentioned water containing emulsifying agent, and stir 0.5h and obtain stable pre-emulsion;
(7) initiator ammonium persulfate taking 0.2g is dissolved in the distilled water of 10g;
(8) liquid that step (6) and (7) obtain slowly is added drop-wise in (5) by 3.0h, after being added dropwise to complete rear insulation 1.0h, prepares organosilicon-modified acrylate emulsion;
embodiment 4
The application of water-proof emulsion on fabric: prepare three kinds of water-proof emulsions by above three embodiments, it is diluted to respectively admittedly containing 25%, impregnated in above emulsion with the cotton fabric of 3cm*3cm respectively, 80 degree of drying in oven are positioned over after being taken out after 1 minute, prepare waterproof fabric, measuring its water resistance again, measuring the contact angle of water on its surface, by impregnated in the water-intake rate in water after 6 hours by contact angle tester.Measure its water-proof acrylic acid ester emulsion property obtained respectively and waterproof fabric performance as table 1:
Table 1 water-proof emulsion performance and waterproof fabric performance
| Index name | Embodiment 1 emulsion | Embodiment 2 emulsion | Embodiment 3 emulsion | Remarks |
| Outward appearance | Milky white colour band blue light | Milky white colour band blue light | Milky white colour band blue light | Range estimation |
| Molecular weight | 1.54×10 6 | 4.48×10 5 | 5.25×10 5 | Gel chromatograph PL-GPC 50 |
| Particle diameter | 112 | 117 | 113 | Malvern ParticleSizer ZS Nano ZS 90, |
| Solid content (%) | 35.01 | 35.05 | 35.04 | Measure by GB/T 1725-1979 |
| PH value | 7.4 | 7.5 | 7.4 | Accurate pH test paper |
| Contact angle | 109.4 | 112.7 | 125.2 | Dynamic Contact angle tester OCA40 Micro |
| Water-intake rate (%) | 105.7 | 81.6 | 60.2 | Measure by GB1738-79 |
Claims (7)
1. a Waterproof acrylic ester emulsion, it is characterized in that nucleocapsid structure, described core is made up of the component of following weight percentage: the methacrylic acid of 40-60% vinylbenzene, 31-51% acrylate, 1-5%, 0.1-2% methacrylic ester, 0.1-2% acrylamide; Described shell is made up of the component of following weight percentage: the water-proof function monomer of the methacrylic acid of 40-60% vinylbenzene, 30-50% acrylate, 1-5%, 0.1-2% methacrylic ester, 0.1-2% acrylamide, 1-8%.
2. Waterproof acrylic ester emulsion according to claim 1, is characterized in that described water-proof function monomer is vinyltrimethoxy silane or vinyl silane triisopropoxide or vinyltriethoxysilane or γ-methacryloxypropyl trimethoxy silane or vinyl silicone oil or perfluorooctylethyl group acrylate or 2-(perfluoro capryl) ethylmethyl acrylate or N-ethylperfluoro octyl group sulfoamido ethyl propylene acid esters.
3. Waterproof acrylic ester emulsion according to claim 1, is characterized in that described acrylate is any one or a few the mixture in methyl acrylate, ethyl propenoate, butyl acrylate, 2-methyl methacrylate, ethyl 2-methacrylate.
4. Waterproof acrylic ester emulsion according to claim 1, is characterized in that described methacrylic ester is hydroxyethyl methylacrylate, Rocryl 410, methyl methacrylate, butyl methacrylate or Rocryl 410.
5. Waterproof acrylic ester emulsion according to claim 1, is characterized in that described acrylamide is N hydroxymethyl acrylamide, N-hydroxyethyl acrylamide or N, N'-methylene-bisacrylamide.
6. the preparation method of Waterproof acrylic ester emulsion described in claim 1, is characterized in that comprising the steps:
(1) pre-mixing of nuclear monomer: the methacrylic acid of 40-60% vinylbenzene, 31-51% acrylate, 1-5%, 0.1-2% methacrylic ester and 0.1-2% acrylamide are dispersed in water under the effect of emulsifying agent, obtain pre-emulsification monomer mixture;
(2) pre-mixing of shell monomer: the water-proof function monomer of the methacrylic acid of 40-60% vinylbenzene, 30-50% acrylate, 1-5%, 0.1-2% methacrylic ester, 0.1-2% acrylamide and 1-8% is dispersed in water under the effect of emulsifying agent, obtains pre-emulsification monomer mixture;
(3) polyreaction: buffer reagent and emulsifying agent are joined in reaction medium water, fully stir and be warmed up to 80-100 DEG C in reaction vessel, after temperature of reaction to be achieved, premixture and the initiator of nuclear monomer is first dripped with 1-3h, drip premixture and the initiator of shell monomer again with 1-3h after isothermal reaction 0.5-2h, drip rear continuation isothermal reaction 0.5-2h, be incubated rear termination reaction.
7. the preparation method of Waterproof acrylic ester emulsion according to claim 6, is characterized in that, described initiator is the mixture of one or more in Potassium Persulphate or Sodium Persulfate or ammonium persulphate.
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| CN105175615A (en) * | 2015-08-28 | 2015-12-23 | 广州市恒珑宇化工科技有限公司 | Water-based environment-friendly film-forming material applied in steel fastener surface, and preparation method and application thereof |
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| JP7171443B2 (en) | 2016-06-03 | 2022-11-15 | ビーエーエスエフ ソシエタス・ヨーロピア | Water-based waterproof coating |
| CN105884966A (en) * | 2016-06-12 | 2016-08-24 | 上海未泉新材料科技有限公司 | High-adhesion acrylic resin |
| CN106436326A (en) * | 2016-08-01 | 2017-02-22 | 宜兴市德泰纺织浆料有限公司 | Acrylate type waterproof woolen sizing agent |
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| GB2620999A (en) * | 2021-12-28 | 2024-01-31 | Univ Qingdao Technology | Styrene-acrylic-siloxane composite core-shell emulsion, preparation method therefor, and use thereof |
| CN115960509A (en) * | 2023-01-06 | 2023-04-14 | 德爱威（中国）有限公司 | Water-based flame-retardant interior wall latex paint and preparation method thereof |
| CN115960509B (en) * | 2023-01-06 | 2024-04-23 | 德爱威（中国）有限公司 | Water-based flame-retardant interior wall emulsion paint and preparation method thereof |
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