CN1063770C - Organosilicon modified propenoic acid emulsion paint - Google Patents
Organosilicon modified propenoic acid emulsion paint Download PDFInfo
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- CN1063770C CN1063770C CN97106714A CN97106714A CN1063770C CN 1063770 C CN1063770 C CN 1063770C CN 97106714 A CN97106714 A CN 97106714A CN 97106714 A CN97106714 A CN 97106714A CN 1063770 C CN1063770 C CN 1063770C
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Abstract
The present invention relates to organosilicon modified acrylic acid emulsion paint which is prepared from 1 to 20 wt% of organosilicon monomers with unsaturated polyester double bonds, 1 to 20 wt% of unsaturated acid, 40 to 97 wt% of unsaturated monomers and 1 to 20 wt% of hydroxy silicone. The organosilicon modified acrylic acid emulsion paint has the characteristics of good water resistance performance, good dirt resistance performance, good water prevention performance and good ageing resistance performance, is superior to pure acrylic acid series paint, and can be used in paint production.
Description
The present invention relates to organosilicon modified propenoic acid emulsion paint.
With the multipolymer of (methyl) vinylformic acid and ester thereof is that the coating of main film forming substance is referred to as acrylic coating.Acrylic acid series coating look shallow, and film is plentiful, and physical strength is good, become the important coating variety of a class.But its pollution resistance, water-repellancy is not good enough, and weathering resistance is also good inadequately, and polysiloxane just in time can remedy this defective.The surface daub on a wall of metal building sheet material, the hard supercoat of frostings such as synthetic glass, polycarbonate not only requires coating gloss, and color and luster is good, and the physical strength height also requires it to have good antifouling, dustproof, ageing resistance.People have proposed vinylformic acid-organosilicon coating for this reason, this coating is the length of collection acrylic coating and organosilicon coating, by a certain amount of organosilicon of introducing functional group on acrylic resin macromolecular main chain and side chain, utilize the Si-O covalent bond energy to be 108kcal/mol, than common C-C bond energy big (83kcal/mol), to heat, stable to light, be not subject to action of ultraviolet light and the characteristic of deterioration, improved the weathering resistance of acrylic coating greatly, and it is good also to have coating adhesion, the water tolerance excellence, the over-all properties that paint film is full.For obtaining this acid-organosilicon crylic acid coating, early stage, people's mixed and modified method commonly used is mixed with acrylic resin and silicone resin, reaches the modification purpose.But silicone resin and other resin compatible are not good enough, and this modified effect can not be lasting, and after long-time the use, silicone ingredients can slowly disappear from the film surface.Often adopt chemical modification to make the organosilicon modified crylic acid resin coating of excellent performance in recent years.For example US3468836 reacts with acrylate copolymer that contains hydroxyl and polysiloxane; JP58-154766, JP59-20360 obtain containing the siloxanes of acrylic acid groups earlier, and the method with the unsaturated monomer copolymerization prepares again.Aforesaid method obtains solvent type resin all by solution polymerization, owing to leave solvent in the product, can cause environmental pollution, and consumes energy, so limited its application.JP51-146525, JP54-3512 have narrated with the polysiloxane that contains unsaturated group and other vinyl monomer method of emulsion polymerization in water, but the polymer-modified stability of emulsion that obtains is not good enough, easily separates, coacervation.
For overcoming the defective that above-mentioned document exists, the purpose of this invention is to provide a kind of new organosilicon modified propenoic acid emulsion paint, this latex coating has water tolerance, pollution resistance, the characteristics that water-repellancy, resistance to deterioration are all good.The objective of the invention is to realize by following technical scheme: a kind of organosilicon modified propenoic acid emulsion paint comprises by weight percentage:
(a) contain the organosilane monomer 1～20% of unsaturated double-bond, organosilane monomer is selected from least a or its mixture in vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane, the gamma-methyl allyl acyloxypropyl trimethoxysilane;
(b) unsaturated acid 1～20%, and unsaturated acid is selected from vinylformic acid, methacrylic acid or its mixture;
(c) unsaturated monomer 40～97%, and unsaturated monomer is selected from least two kinds or its mixture in methyl methacrylate, methyl acrylate, butyl acrylate, butyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, vinylbenzene, vinyl acetate between to for plastic, vinyl cyanide, acrylamide, dimethylaminoethyl acrylate methyl ammonia ethyl ester, the glycidyl methacrylate; (d) the hydroxyl polysiloxane 1～20%;
Be to carry out letex polymerization under 70～90 ℃ earlier by the composition (a) and (b) and (c), gained multipolymer and composition (d) reacted down at 70～90 ℃ obtain in temperature.
In the technique scheme by weight percentage the preferable range of unsaturated acid be 2～8%, the preferable range of hydroxyl polysiloxane is 1～10%.
Above-mentioned hydroxyl polysiloxane is taken off ethanol again and is made by the dimethyldiethoxysilane hydrolysis.Concrete steps: having prolong, in the four-necked bottle of Dropping feeder, adding dimethyldiethoxysilane, 732
#The type Zeo-karb is warming up to 60 ℃, begins to reflux, and drips the water of metering subsequently, finishes in 0.5～1 hour, is warming up to 70～80 ℃, keeps 2～3 hours.Leach 732
#Resin boils off ethanol again, obtains the hydroxyl polysiloxane of the about 10cp of viscosity.
The preparation of organosilicon modified propenoic acid emulsion paint of the present invention is the emulsion copolymerization by vinyl monomer, obtains with the reaction of hydroxyl polysiloxane again.The letex polymerization temperature is 70～90 ℃, and its technology is: with deionized water, compound emulsifying agent adds in the reactor, be warming up to 70～90 ℃, add partial monosomy and water-based initiator, drip remaining monomer and water-based initiator subsequently, added in 2～3 hours, equality of temperature is kept reaction 2 hours again.Add silicon alcohol condensation catalyst and hydroxyl polysiloxane then, keep reaction 2 hours, be cooled to below 50 ℃, regulate pH value to 8～9 with ammoniacal liquor.After 200 order net filtrations must be with the blue light emulsion.Hydroxyl polysiloxane and silicon alcohol condensation catalyst also can just add before emulsion copolymerization begins.
Above-mentioned compound emulsifying agent is composited by anion surfactant and nonionic surface active agent, anion surfactant such as sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, consumption 0.5～3%: nonionic surface active agent such as polyoxyethylene phenolic ether in the ninth of the ten Heavenly Stems, Voranol EP 2001, polyoxyethylene sorbitol acid anhydride oleic acid ester, polyoxyethylene sorbitol acid anhydride stearate etc., consumption 1～8%.
The water-based initiator adopts persulphate, as Potassium Persulphate, and ammonium persulphate, consumption 0.2～3%.Silicon alcohol condensation catalyst such as dibutyl tin dilaurate, dibutyl tin acetate, tetrabutyl titanate etc., consumption 0.05～5%.
In the present invention, introduce the unsaturated acid molecule, make and introduced numerous strong hydrophilicity groups in the latex coating that makes, increased the stability of latex coating.Introduce hard monomer, make latex coating that good hardness of film, photostabilization arranged, improved the minimum film-forming temperature of latex as methyl methacrylate.Introduce soft monomer, increased the snappiness of coating as butyl acrylate, sticking power, water tolerance has reduced the film-forming temperature of latex.Introduce unsaturated acid and the organosilane monomer that contains unsaturated double-bond, for above-mentioned unsaturated monomer provides cross-linking set, thus crosslinking curing after coating can be heated.Because during the latex film forming, siloxanes generally is enriched in the multipolymer surface, therefore introduce the water resistance that the hydroxyl polysiloxane has improved latex coating greatly.
In the latex coating of the present invention, owing to contain the component of the organosilane monomer that is equivalent to unsaturated double-bond, unsaturated acid, unsaturated monomer, hydroxyl polysiloxane, therefore water tolerance, pollution resistance, the water-repellancy performance of this latex coating obviously are better than pure acrylic acid coating, have obtained effect preferably.This latex coating has satisfactory stability simultaneously, and can reach more than 1 year storage period.
The invention will be further elaborated below by embodiment.[embodiment 1]
Have prolong, Dropping feeder, in the four-hole boiling flask of stirring, thermometer, adding entry 154 grams, sodium lauryl sulphate 1 gram, Voranol EP 2001 3 grams, Potassium Persulphate 0.4 gram is heated to 75 ℃.Drip vinyltrimethoxy silane 5 grams, vinylformic acid 3 grams, methyl methacrylate 44 grams, the mixture of butyl acrylate 48 grams added in 2 hours, kept reaction 2 hours in 75 ℃.Add dibutyl tin dilaurate 0.3 gram then, drip hydroxyl polysiloxane 3 grams,, be cooled to below 50 ℃, regulate pH value to 8～9,, must be with blue light organosilicon-modified acrylic copolymer emulsion through 200 order net filtrations with ammoniacal liquor in 75 ℃ of reactions 2 hours.Yield 98.1%, solid content 40%.[embodiment 2]
Vinyltriethoxysilane 15 grams, methyl methacrylate 38 grams, butyl methacrylate 43 grams, other prescription and technology are identical with embodiment 1.Get the organosilicon-modified acrylic copolymer emulsion, its yield 98.6%, solid content 40.1%.[embodiment 3]
Mix monomer is by vinyltrimethoxy silane 3 grams, and methacrylic acid 5 restrains, methyl methacrylate 44 grams, and butyl acrylate 48 grams, glycidyl methacrylate 6 grams mix, and other prescription and technology are identical with embodiment 1.Get the organosilicon-modified acrylic copolymer emulsion, its yield 99.2%, solid content 40.2%.[embodiment 4]
Glycidyl methacrylate is used Jia Jibingxisuanβ-Qiang Yizhi instead in the mix monomer, and other prescription and technology are identical with embodiment 3.Get the organosilicon-modified acrylic copolymer emulsion, its yield 99.3%, solid content 40.5%.[embodiment 5]
In four-hole boiling flask, add deionized water 154 grams, sodium lauryl sulphate 1 gram, Voranol EP 2001 3 grams, hydroxyl polysiloxane 10 grams, dibutyl tin dilaurate 0.3 gram, Potassium Persulphate 0.4 gram is warming up to 75 ℃.Drip vinyltrimethoxy silane 5 grams, vinylformic acid 3 grams, methyl methacrylate 44 grams, the mixture of butyl acrylate 48 grams added in 2 hours, kept reaction 2 hours in 75 ℃ again.Be cooled to below 50 ℃, regulate pH value to 8～9 with ammoniacal liquor.Get the organosilicon-modified acrylic copolymer emulsion, its yield 99.2%, solid content 40.7%.[comparative example 1]
In four-hole boiling flask, add deionized water 154 grams, sodium lauryl sulphate 1 gram, Voranol EP 2001 3 grams, Potassium Persulphate 0.4 gram, be warming up to 75 ℃, dropwise addition of acrylic acid 3 restrains then, methyl methacrylate 44 grams, the mixture of butyl acrylate 48 grams, added in 2 hours, and kept reaction 2 hours in 75 ℃ again.Get the acrylic copolymer emulsion.[comparative example 2]
Mix monomer is vinyltrimethoxy silane 5 grams, vinylformic acid 3 grams, and methyl methacrylate 44 grams, the mixture of butyl acrylate 48 grams, other prescription and technology are identical with comparative example 1.
Get the tinplate of 50 * 120 * 0.2mm, polish repeatedly with No. 0 sand paper earlier, remove tin coating, use alcohol, acetone scrub again.The emulsion that obtains in the foregoing description and the comparative example evenly is applied on the tinplate, in 150 ℃ of dryings 10 minutes, smooth, bright filming.Film performance is as shown in table 1.
Table 1 film performance
| Latex | Sticking power (level) | Pencil hardness | Shock strength (Kg/cm) | Gloss (45 °) | Water tolerance | Water-repellancy |
| Embodiment 1 | ?1 | ?2H | ?50 | ?107 | Slight loss of gloss | High (contact angle＞90 °) |
| Embodiment 2 | ?1 | ?3H | ?50 | ?83 | No abnormal | High (contact angle＞90 °) |
| Embodiment 3 | ?1 | ?2H | ?50 | ?100 | Slight loss of gloss | High (contact angle＞90 °) |
| Embodiment 4 | ?1 | ?2H | ?50 | ?98 | No abnormal | High (contact angle＞90 °) |
| Embodiment 5 | ?1 | ?2H | ?50 | ?109 | No abnormal | High (contact angle＞90 °) |
| Comparative example 1 | ?1 | ?2H | ?50 | ?/ | Bubble is arranged, get rusty | Low (contact angle＜＜90 °) |
| Comparative example 2 | ?1 | ?2H | ?50 | ?/ | Bubble is arranged, get rusty | Low (contact angle＜＜90 °) |
With the latex coating that the foregoing description 1～5 makes, at room temperature left standstill no change 1 year.
The film performance testing method:
Sticking power: GB1720-79
Pencil hardness: GB6739-86
Shock strength: GB1732-79
Gloss: GB1743-79
Water tolerance: test plate (panel) in distilled water immersion 7 days, is observed coating and is changed under room temperature.
Water-repellancy: film to go up to drip and go up deionized water, estimate its contact angle size.The big expression water-repellancy of contact angle height.
Claims (3)
1, a kind of organosilicon modified propenoic acid emulsion paint comprises by weight percentage:
(a) contain the organosilane monomer 1～20% of unsaturated double-bond, organosilane monomer is selected from least a or its mixture in vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane, the gamma-methyl allyl acyloxypropyl trimethoxysilane;
(b) unsaturated acid 1～20%, and unsaturated acid is selected from vinylformic acid, methacrylic acid or its mixture;
(c) unsaturated monomer 40～97%, and unsaturated monomer is selected from least two kinds or its mixture in methyl methacrylate, methyl acrylate, butyl acrylate, butyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, vinylbenzene, vinyl acetate between to for plastic, vinyl cyanide, acrylamide, dimethylaminoethyl acrylate methyl ammonia ethyl ester, the glycidyl methacrylate; (d) the hydroxyl polysiloxane 1～20%;
Be to carry out letex polymerization under 70～90 ℃ earlier by the composition (a) and (b) and (c), gained multipolymer and composition (d) reacted down at 70～90 ℃ obtain in temperature.
2, organosilicon modified propenoic acid emulsion paint according to claim 1 is characterized in that unsaturated acid is 2～8% by weight percentage.
3, organosilicon modified propenoic acid emulsion paint according to claim 1 is characterized in that hydroxyl polysiloxane by weight percentage 1～10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106714A CN1063770C (en) | 1997-11-13 | 1997-11-13 | Organosilicon modified propenoic acid emulsion paint |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106714A CN1063770C (en) | 1997-11-13 | 1997-11-13 | Organosilicon modified propenoic acid emulsion paint |
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| CN1217361A CN1217361A (en) | 1999-05-26 |
| CN1063770C true CN1063770C (en) | 2001-03-28 |
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| CN97106714A Expired - Fee Related CN1063770C (en) | 1997-11-13 | 1997-11-13 | Organosilicon modified propenoic acid emulsion paint |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100362048C (en) * | 2003-07-30 | 2008-01-16 | 宜通工程有限公司 | Polymeric colloidal sol compositon, aqueous colloidal sol composition, and its preparing method and use |
| CN101457112B (en) * | 2008-10-17 | 2011-03-30 | 芜湖力特尔涂料制造有限公司 | Automobile reflecting layer coating |
| CN101457111B (en) * | 2008-10-17 | 2011-06-15 | 芜湖力特尔涂料制造有限公司 | Reflecting layer coating |
| CN101457113B (en) * | 2008-10-17 | 2011-06-22 | 芜湖力特尔涂料制造有限公司 | Automobile reflecting layer coating |
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| CN1103341C (en) * | 1999-11-09 | 2003-03-19 | 复旦大学 | Organosilicon modified acrylate latex with core-shell structure and its preparing process |
| CN1313550C (en) * | 2004-06-11 | 2007-05-02 | 中国石油天然气集团公司 | Acrylic resin paint for reflecting light and its production process |
| CN1305988C (en) * | 2005-09-23 | 2007-03-21 | 浙江大学 | Prepn of organosilicon modified pressure-sensitive acrylate adhesive |
| CN100410286C (en) * | 2006-06-07 | 2008-08-13 | 刘晓国 | Silicone modified polyacrylate and its prepn and application |
| DE102006037270A1 (en) | 2006-08-09 | 2008-02-14 | Wacker Chemie Ag | Self-dispersible silicone copolymers and process for their preparation and their use |
| CN101348611B (en) * | 2008-09-05 | 2010-12-29 | 中国海洋石油总公司 | Acroleic acid modified polysiloxane resin and coating thereof |
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| JPH09208643A (en) * | 1996-02-07 | 1997-08-12 | Toshiba Silicone Co Ltd | Modified polyorganosiloxane emulsion |
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Patent Citations (4)
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| JPS51146525A (en) * | 1975-06-10 | 1976-12-16 | Shinetsu Chemical Co | Water hardening cement mixture |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100362048C (en) * | 2003-07-30 | 2008-01-16 | 宜通工程有限公司 | Polymeric colloidal sol compositon, aqueous colloidal sol composition, and its preparing method and use |
| CN101457112B (en) * | 2008-10-17 | 2011-03-30 | 芜湖力特尔涂料制造有限公司 | Automobile reflecting layer coating |
| CN101457111B (en) * | 2008-10-17 | 2011-06-15 | 芜湖力特尔涂料制造有限公司 | Reflecting layer coating |
| CN101457113B (en) * | 2008-10-17 | 2011-06-22 | 芜湖力特尔涂料制造有限公司 | Automobile reflecting layer coating |
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| CN1217361A (en) | 1999-05-26 |
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