CN104231147A - Preparation method of acrylate-fluorinated acrylate and silica sol hybrid latex - Google Patents
Preparation method of acrylate-fluorinated acrylate and silica sol hybrid latex Download PDFInfo
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- CN104231147A CN104231147A CN201410498884.8A CN201410498884A CN104231147A CN 104231147 A CN104231147 A CN 104231147A CN 201410498884 A CN201410498884 A CN 201410498884A CN 104231147 A CN104231147 A CN 104231147A
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Abstract
The invention discloses a preparation method of acrylate-fluorinated acrylate and silica sol hybrid latex. In the preparation method, silica sol is used as a seed, and acrylate latex of which the surface is rich in fluorinated acrylate with strong polarity is synthesized by using a hybridizing technology. The latex adopts a core-shell structure with the silica sol as a core; a latex coating is enabled to have high hardness and the shell is rich in the fluorinated acrylate, so that the latex coating has better water resistance, chemical resistance, stain resistance and weather resistance, and further the latex can be widely applied to water-based wood paint; if a glass plate is coated with the latex, the coating thickness is 50 microns, the hardness of the latex reaches 2H, the water resistance reaches 96h, the whitening is avoided, the 60-degree gloss reaches 85, and no significant change occurs after artificial aging for 250 hours.
Description
Technical field
The present invention relates to a kind of preparation method of aqueous industrial paint latex, the concrete preparation method proposing a kind of acrylate-fluorinated acrylate and silicon sol hydridization latex.
Background technology
Acrylic emulsion is as the universal macromolecular material of one, there are outstanding water tolerance, weathering resistance and gloss retention, have a wide range of applications in building coating and water-based industrial paint, but due to the shortcoming that its heat is glutinous cold short, be difficult to reach desirable effect during application in a lot of fields, be very restricted in water-based industrial paint application especially.
Silicon sol is utilized to carry out modification to Acrylic emulsion at present, use Mixed Pinyin processing method, these Mixed Pinyin techniques also can solve a part difficult problem certainly, but are difficult to the problem of the comprehensive aspect such as hardness, fullness ratio, high temperature resistant, water tolerance, water-whitening resistance, chemical resistant properties, anti-stain characteristic solving paint film in water-based industrial paint.
CN102924664A discloses a kind of nucleocapsid fluorochemical urethane-Acrylic emulsion preparation method, aqueous polyurethane and fluorinated acrylate is mainly utilized to carry out heterozygosis modification to acrylate, because fluorocarbon resin has thermotolerance and the chemical resistant properties of ultralow surface energy, superelevation weathering resistance, anti-stain characteristic and excellence, therefore the ester modified composite emulsion of fluorine-containing is utilized obviously can to improve the water tolerance of latex and weathering resistance and thermotolerance, but it is not high mainly to there is hardness in this kind of latex, glossiness and the bad situation of fullness ratio.
Summary of the invention
The object of the present invention is to overcome the technical deficiency of aqueous industrial paint latex on conventional preparation techniques, the preparation method of a kind of acrylate-fluorinated acrylate and silicon sol hydridization latex is provided, the method perfect technology, working specification, effectively can improve the water-whitening resistance of water-based industrial paint, chemical resistant properties, thermotolerance, hardness of paint film, fullness ratio and anti-stain characteristic benefit, reach ideal effect.
For realizing above-mentioned object, the present invention takes following technical scheme, provides the preparation method of a kind of acrylate-fluorinated acrylate and silicon sol hydridization latex, mainly comprises the following steps:
(1), get the raw materials ready, by weight total amount 1000 parts, wherein
Pre-emulsion material:
Water 80-300 part
Emulsifying agent 1-10 part
Alkyl acrylate monomer 80-300 part of C4-C12
Alkyl methacrylate monomer 150-400 part of C4-C20
Functional monomer 5-30 part;
Backing material:
Water 80-300 part
Emulsifying agent 1-10 part
Silicon sol 5-30 part
Sodium bicarbonate 1-3 part;
All the other small powders:
Initiator 1-3 part
Water 40-150 part
Fluorinated acrylate 5-30 part
Oxygenant 0.5-1 part
Reductive agent 0.5-1 part;
(2), the water of pre-emulsion material in step (1), emulsifying agent, the alkyl acrylate monomer of C4-C12, the alkyl methacrylate monomer of C4-C20, functional monomer be sequentially added into obtaining pre-emulsion with 200-1000r/min rotating speed high speed dispersion in the emulsification container stirred;
(3), the water of backing material in step (1), emulsifying agent, silicon sol and sodium bicarbonate are joined with in the reaction vessel stirred, with 20-120r/min rotating speed stirring at low speed and the half initiator added after being heated to 80-90 DEG C in step (1) in all the other small powders, drip the aqueous solution of pre-emulsion and second half initiator again, control dropping temperature is 80-90 DEG C, time for adding is 2-4 hour, when pre-emulsification drop remains 1/3 to 1/10, fluorinated acrylate is added in pre-emulsion, stirs and continue to drip;
(4), 80-90 DEG C insulation 1-2 hour, be cooled to 65-75 DEG C, the aqueous solution adding Oxidizing and Reducing Agents carries out aftertreatment, is cooled to 40 DEG C, regulates pH value 7-9 discharging with ammoniacal liquor.
Emulsifying agent in above-mentioned steps (1) is one or more in anionic emulsifier, nonionic emulsifying agent and reactive emulsifier, and wherein anionic emulsifier is at least one in succinic acid alkyl polyoxyethylene ether monoesters disodium sulfonate, alkyl phenol polyethenoxy ether sodium sulfate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate; Nonionic emulsifying agent is at least one in isomerous tridecanol polyoxyethylene ether, polyoxyethylene nonylphenol ether, ethoxylated dodecyl alcohol; Reactive emulsifier is at least one in allyloxy hydroxypropyl azochlorosulfonate acid sodium, alkane alkene amido alkyl sodium sulfonate, allyloxy polyoxyethylene nonylphenol ether ammonium sulfate; The alkyl acrylate monomer of the C4-C12 in step (1) is one or more in methyl acrylate, ethyl propenoate, butyl acrylate, ethyl acrylate, decyl acrylate monomer; The alkyl methacrylate monomer of the C4-C20 in step (1) is one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, octadecyl methacrylate monomer; Functional monomer in step (1) by vinylformic acid, acrylamide, n-methylolacrylamide, diacetone-acryloamide(DAA), Viscoat 295, hydroxyethyl methylacrylate monomer at least two kinds form; Silicon sol in step (1) is the water silica sol containing sodium ion or potassium ion; Fluorinated acrylate in step (1) is one or more in trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, vinylformic acid trifluoro ethyl ester monomer; In step (1), oxygenant is tertbutyl peroxide, and reductive agent is sodium bisulfite, and initiator is Sodium Persulfate.
Silicon sol is the dispersion liquid of nano silicon in water, and wherein containing a large amount of hydroxyls, silicon sol is when drying out, and monomeric silicic acid aggregates into high poly-silica gel gradually, and along with the evaporation of moisture, colloid molecules increases, and finally forms-SiO-O-SiO-film, due to Na
2the content of O in silicon sol is low, and silicon sol has the characteristic that a certain amount of film forming is dissolved, and its wear resistance, resistance toheat, hardness are obviously better than organic coating, and film is fine and close and comparatively hard, does not produce electrostatic, and in air, various dust difficulty adheres to.But it is comparatively large to there is volumetric shrinkage in film process in silicon sol, the shortcoming that film is easy to crack.
Fluorinated acrylate has ultralow surface energy, the thermotolerance of the weathering resistance of superelevation, excellent anti-stain characteristic and excellence, therefore fluorine-containing modified polyacrylate latex is utilized, can the water tolerance of more effective raising polyacrylic ester latex, weathering resistance, thermotolerance and contamination resistance.
The present invention utilizes silicon sol for seed, adopts hydridization reaction process, has synthesized a kind of Acrylic emulsion, and be enriched fluorine-containing on latex top layer.The effect of dissolving each other is forced because hydridization technique is distinctive, two or more performance differences material that is very large or that have a difference in functionality can be made to form stable combination by polyreaction, the special molecular structure interface IPN making it be formed, two-phase or heterogeneous continuous structure characteristic, make them in performance or functionally produce special synergy, thus the water-whitening resistance of raising water-based industrial paint, chemical resistant properties, thermotolerance, hardness of paint film, fullness ratio, anti-stain characteristic and glossiness, good combination property, reaches ideal effect.
Preparation method's perfect technology provided by the invention, working specification, ensures quality product, is applicable to batch production.
Embodiment
The technology of the present invention thinking is: take silicon sol as seed, drip pre-emulsion and initiator simultaneously, and by polarity is stronger in the grafting of latex top layer the fluorinated acrylate of phase after the reaction, form silicon sol for supporting, the Acrylic emulsion that surface polarity is stronger, thus obtain one there is high rigidity, excellent water tolerance, weathering resistance, contamination resistance, chemical resistant properties, thermotolerance, high gloss, the aqueous industrial paint latex of high fullness ratio.
Embodiment 1,
(1), by 80g water, 1g allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, 80g butyl acrylate, 400g methyl methacrylate, 2g vinylformic acid, 2g acrylamide, 1g hydroxyethyl methylacrylate, be sequentially added into stir emulsification container in and obtain pre-emulsion with 200r/min rotating speed high speed dispersion.
(2), by 8g succinic acid alkyl polyoxyethylene ether monoesters disodium sulfonate and 2g polyoxyethylene nonylphenol ether, 5g silicon sol, 1g sodium bicarbonate and 300g water, join with in the reaction vessel stirred, be heated to 84 DEG C add 0.5g initiator with 50r/min rotating speed stirring at low speed, drip pre-emulsion and the aqueous solution containing 0.5g Sodium Persulfate initiator simultaneously, control dropping temperature is 83-86 DEG C, and time for adding is 3 hours.When pre-emulsification drop remains 1/3,5g trifluoroethyl methacrylate is added in pre-emulsion, stirs and continue to drip.
(3), 85 DEG C of insulations 1 hour, be cooled to 70 DEG C, add 0.5g tertbutyl peroxide oxygenant and the 0.5g sodium bisulfite reductive agent aqueous solution carries out aftertreatment, be cooled to 40 DEG C, regulate pH value 7-9 discharging with ammoniacal liquor.
The water of dissolving initiator, oxygenant, reductive agent is total up to 111g.
Embodiment 2,
(1), by 200g water, 3g allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, 2g alkane alkene amido alkyl sodium sulfonate, 150g ethyl acrylate, 280g butyl methacrylate, 6g vinylformic acid, 6g acrylamide, 6g Viscoat 295, be sequentially added into stir emulsification container in and obtain pre-emulsion with 800r/min rotating speed high speed dispersion.
(2), by 3g succinic acid alkyl polyoxyethylene ether monoesters disodium sulfonate and 2g isomerous tridecanol polyoxyethylene ether, 20g silicon sol, 2g sodium bicarbonate, 250g water, join with in the reaction vessel stirred, be heated to 84 DEG C add 1g initiator with 50r/min rotating speed stirring at low speed, drip pre-emulsion and the aqueous solution containing 1g initiator simultaneously, control dropping temperature is 84-88 DEG C, and time for adding is 3.5 hours.When pre-emulsification drop remains about 1/5,5g vinylformic acid trifluoro ethyl ester, 5g dodecafluoroheptyl methacrylate are added in pre-emulsion, stir and continue to drip.
(3), 86 DEG C of insulations 1 hour, be cooled to 70 DEG C, the aqueous solution adding 0.8g oxygenant and 0.8g reductive agent carries out aftertreatment, is cooled to 40 DEG C, regulates pH value 8-9 discharging with ammoniacal liquor.
The water of dissolving initiator, oxygenant, reductive agent is total up to 56.4g.
Embodiment 3,
(1), by 300g water, 5g allyloxy hydroxypropyl azochlorosulfonate acid sodium, 5g sodium lauryl sulphate, 300g ethyl propenoate, 150g cyclohexyl methacrylate, 10g vinylformic acid, 10g acrylamide, 10g Viscoat 295 be sequentially added into stir emulsification container in and obtain pre-emulsion with 1000r/min rotating speed high speed dispersion.
(2), by 1g Sodium dodecylbenzene sulfonate, 30g silicon sol, 3g sodium bicarbonate, 100g water, join with in the reaction vessel stirred, be heated to 84 DEG C add 1.5g initiator with 80r/min rotating speed stirring at low speed, drip pre-emulsion and the aqueous solution containing 1.5g initiator simultaneously, control dropping temperature is 83-86 DEG C, and time for adding is 4 hours.When pre-emulsification drop remains about 1/10,15g trifluoroethyl methacrylate, 15g Hexafluorobutyl mathacrylate are added in pre-emulsion, stir and continue to drip.
(3), 86 DEG C of insulations 1 hour, be cooled to 70 DEG C, the aqueous solution adding 1g oxygenant and 1g reductive agent carries out aftertreatment, is cooled to 40 DEG C, regulates pH value 8-9 discharging with ammoniacal liquor.
The water of dissolving initiator, oxygenant, reductive agent is total up to 41g.
Acrylate-the fluorinated acrylate obtained by above-described embodiment and silicon sol hydridization latex, coat on sheet glass, and coating thickness is 50 microns, and its hardness reaches 2H, and water-fast 96h does not whiten, and 60 degree of gloss reach 85, and temper(ing) 250 hours is without considerable change.
Claims (8)
1. a preparation method for acrylate-fluorinated acrylate and silicon sol hydridization latex, is characterized in that this preparation method according to the following steps:
(1), get the raw materials ready, by weight total amount 1000 parts, wherein
Pre-emulsion material:
Water 80-300 part
Emulsifying agent 1-10 part
Alkyl acrylate monomer 80-300 part of C4-C12
Alkyl methacrylate monomer 150-400 part of C4-C20
Functional monomer 5-30 part;
Backing material:
Water 80-300 part
Emulsifying agent 1-10 part
Silicon sol 5-30 part
Sodium bicarbonate 1-3 part;
All the other small powders:
Initiator 1-3 part
Water 40-150 part
Fluorinated acrylate 5-30 part
Oxygenant 0.5-1 part
Reductive agent 0.5-1 part;
(2), the water of pre-emulsion material in step (1), emulsifying agent, the alkyl acrylate monomer of C4-C12, the alkyl methacrylate monomer of C4-C20, functional monomer be sequentially added into obtaining pre-emulsion with 200-1000r/min rotating speed high speed dispersion in the emulsification container stirred;
(3), the water of backing material in step (1), emulsifying agent, silicon sol and sodium bicarbonate are joined with in the reaction vessel stirred, with 20-120r/min rotating speed stirring at low speed and the half initiator added after being heated to 80-90 DEG C in step (1) in all the other small powders, drip the aqueous solution of pre-emulsion and second half initiator again, control dropping temperature is 80-90 DEG C, time for adding is 2-4 hour, when pre-emulsification drop remains 1/3 to 1/10, fluorinated acrylate is added in pre-emulsion, stirs and continue to drip;
(4), 80-90 DEG C insulation 1-2 hour, be cooled to 65-75 DEG C, the aqueous solution adding Oxidizing and Reducing Agents carries out aftertreatment, is cooled to 40 DEG C, regulates pH value 7-9 discharging with ammoniacal liquor.
2. preparation method according to claim 1, the emulsifying agent that it is characterized in that in step (1) is one or more in anionic emulsifier, nonionic emulsifying agent and reactive emulsifier, and wherein anionic emulsifier is at least one in succinic acid alkyl polyoxyethylene ether monoesters disodium sulfonate, alkyl phenol polyethenoxy ether sodium sulfate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate; Nonionic emulsifying agent is at least one in isomerous tridecanol polyoxyethylene ether, polyoxyethylene nonylphenol ether, ethoxylated dodecyl alcohol; Reactive emulsifier is at least one in allyloxy hydroxypropyl azochlorosulfonate acid sodium, alkane alkene amido alkyl sodium sulfonate, allyloxy polyoxyethylene nonylphenol ether ammonium sulfate.
3. preparation method according to claim 1, is characterized in that the alkyl acrylate monomer of the C4-C12 in step (1) is one or more in methyl acrylate, ethyl propenoate, butyl acrylate, ethyl acrylate, decyl acrylate monomer.
4. preparation method according to claim 1, is characterized in that the alkyl methacrylate monomer of the C4-C20 in step (1) is one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, octadecyl methacrylate monomer.
5. preparation method according to claim 1, it is characterized in that functional monomer in step (1) by vinylformic acid, acrylamide, n-methylolacrylamide, diacetone-acryloamide(DAA), Viscoat 295, hydroxyethyl methylacrylate monomer at least two kinds form.
6. preparation method according to claim 1, the silicon sol that it is characterized in that in step (1) is the water silica sol containing sodium ion or potassium ion.
7. preparation method according to claim 1, the fluorinated acrylate that it is characterized in that in step (1) is one or more in trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, vinylformic acid trifluoro ethyl ester monomer.
8. preparation method according to claim 1, it is characterized in that in step (1), oxygenant is tertbutyl peroxide, reductive agent is sodium bisulfite, and initiator is Sodium Persulfate.
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Cited By (3)
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| CN105585272A (en) * | 2015-10-22 | 2016-05-18 | 湖州绿色建材开发有限公司 | Novel concrete reinforcing agent |
| CN108951597A (en) * | 2017-08-24 | 2018-12-07 | 中国科学院寒区旱区环境与工程研究所 | A kind of vegetative sand control method |
| CN114773943A (en) * | 2022-03-30 | 2022-07-22 | 湖南智涂环保科技有限公司 | Coating film forming material resistant to bowl washing machine and preparation method and application thereof |
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| CN102585073A (en) * | 2012-01-16 | 2012-07-18 | 中山大学 | Fluorine silicon-modified acrylic ester emulsion and preparation method thereof |
| CN102675518A (en) * | 2012-06-01 | 2012-09-19 | 江南大学 | Preparation method for organic-inorganic hybrid fluorine-silicon modified nano waterborne resin |
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| CN102585618A (en) * | 2012-01-16 | 2012-07-18 | 嘉宝莉化工集团股份有限公司 | Matte stain-resistant coating and preparation method thereof |
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Cited By (3)
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| CN105585272A (en) * | 2015-10-22 | 2016-05-18 | 湖州绿色建材开发有限公司 | Novel concrete reinforcing agent |
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| CN114773943A (en) * | 2022-03-30 | 2022-07-22 | 湖南智涂环保科技有限公司 | Coating film forming material resistant to bowl washing machine and preparation method and application thereof |
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