CN1130436C - Organosilicon-acrylic resin emulsion - Google Patents
Organosilicon-acrylic resin emulsion Download PDFInfo
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- CN1130436C CN1130436C CN 01105008 CN01105008A CN1130436C CN 1130436 C CN1130436 C CN 1130436C CN 01105008 CN01105008 CN 01105008 CN 01105008 A CN01105008 A CN 01105008A CN 1130436 C CN1130436 C CN 1130436C
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- acrylic resin
- unsaturated
- organosilicon
- resin emulsion
- emulsion
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Abstract
The present invention relates to organosilicon acrylic resin emulsion. The present invention mainly solves the problems of paint made of the existing emulsion of poor water resistance performance, poor wash resistance performance, poor stain resistance performance and poor ageing resistance performance. The present invention has the technical scheme that the organosilicon acrylic resin emulsion is prepared from 1 to 20 wt% of organosilicon monomers with unsaturated polyester double bonds, 1 to 20 wt% of unsaturated acid, 40 to 96 wt% of unsaturated monomers, 1 to 20 wt% of hydroxy silicone and 1 to 10 wt% of emulsifying agents, wherein the emulsifying agents are prepared from at least one kinds of materials in succinic acid alkyl allyloxy hydroxypropyl diester sulfonate, succinic acid allyl alkyl diester sulfonate, propenyl phenol polyethenoxy ether or nonylphenyl beta-allyloxy methylene substituted polyethenoxy ether carboxylate. The present invention solves the problems in the prior art, and the organosilicon acrylic resin emulsion can be used in the industrial production of high performance paint.
Description
The present invention relates to organosilicon-acrylic resin emulsion.
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 one 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, utilizing the Si-O covalent bond energy is 108 kcal/mol, than common C-C bond energy big (83 kcal/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 introduce in the document US 3468836 and use acrylate copolymer and the polysiloxane reaction that contains hydroxyl; Document JP 58-154766 introduces among the JP59-20360 and uses the siloxanes that obtains containing 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.Document JP 03-255273, JP06-122734, JP51-146525, JP54-3512 has 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 separate, coacervation, not high by its water tolerance of coating, abrasion resistance, contamination resistance and the ageing-resistant performance that above-mentioned document makes in addition, be still waiting to improve.
The organosilicon-modified acrylic emulsion that makes with traditional emulsifying agent, its coating increases at ultraviolet resistance and oxygen, aspect of performance water-fast and all kinds of SOLVENTS, as Canadian Patent CA 842947 and U.S. Pat 3,766,697, but the emulsion water tolerance that these patented technologies make also is not very good, uses traditional emulsifying agent when its reason is emulsion preparation.They only are adsorbed on emulsified particle surface when letex polymerization, rather than participate in acrylic acid copolyreaction.In the European patent EP 401,496, contain sulfonic reactive emulsifier though use, styrene content was too high during emulsion was formed, and its coating weathering resistance is poor.UV-irradiation is easily decoloured.U.S. Pat 5,214, though used reactive emulsifier in 095, the gained stability of emulsion is bad.
The objective of the invention is to have the imperfect shortcoming of water tolerance, abrasion resistance, contamination resistance and ageing-resistant performance after in the past organosilicon-acrylic resin emulsion is made coating, a kind of new organosilicon-acrylic resin emulsion is provided in order to overcome.This emulsion has water tolerance, pollution resistance, abrasion resistance and ageing resistance preferably after making coating.
The objective of the invention is to realize by following technical scheme: a kind of organosilicon-acrylic resin emulsion by weight percentage, comprising:
(a) contain the organosilane monomer 1～20% of unsaturated double-bond, organosilane monomer is selected from least a in vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane or the gamma-methyl allyl acyloxypropyl trimethoxysilane;
(b) unsaturated acid 1～20%, and unsaturated acid is selected from acrylic or methacrylic acid and composition thereof;
(c) unsaturated monomer 40～96%, and unsaturated monomer is selected from least two kinds in methyl methacrylate, methyl acrylate, butyl acrylate, butyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, dimethylaminoethyl acrylate methyl ammonia ethyl ester or the glycidyl methacrylate;
(d) the hydroxyl polysiloxane 1～20%, by the dimethyldiethoxysilane hydrolysis, takes off ethanol again and makes;
(e) emulsifying agent 1～10%, and wherein emulsifying agent contains succsinic acid alkyl allyloxy hydroxypropyl two sulfonated esters, succsinic acid allyl group alkyl diester sulfonate, propenyl phenol Soxylat A 25-7 or nonyl phenol β-allyloxy methylene radical and replaces at least a in the polyethenoxy ether carboxylate;
Carry out emulsion copolymerization earlier by the composition (a) and (b) with (c) in the presence of (e), multipolymer makes with composition (d) reaction more then.
In the technique scheme by weight percentage the amount preferable range of unsaturated acid be 2～8%, the amount preferable range of hydroxyl polysiloxane is 1～10%, emulsification dosage preferable range is 3～6%.
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, strongly acidic styrene's Zeo-karb (732
#The type Zeo-karb), is warming up to 60 ℃, begins to reflux, drip the water of metering subsequently, finished in 0.5～1 hour, be warming up to 70～80 ℃, kept 2～3 hours.Leach 732
#The type resin boils off ethanol again, obtains the hydroxyl polysiloxane of about 10 centipoises of viscosity.
The reactive emulsifier that uses among the present invention is to contain the unsaturated double-bond that radical polymerization can take place in molecule, and they can be anionic or non-ionic type.As:
(or K, NH
4Deng) A or
(or K, NH
4Deng) B or CH
3-CH=CH-(C
6H
4)-O-(CH
2-CH
2-O)
n-H C or
(or K, NH
4Deng) D wherein R be the alkyl or the alkalimetal ion of H, 1～4 carbon.Emulsifying agent A: succsinic acid alkyl allyloxy hydroxypropyl two sulfonated ester emulsifying agent B: succsinic acid allyl group alkyl diester sulfonate emulsifying agent C: propenyl phenol Soxylat A 25-7 emulsifying agent D: nonyl phenol β-allyloxy methylene radical replaces polyethenoxy ether carboxylate
The mentioned emulsifier principal feature is to have the emulsification function group in the molecule, as: sulphonate-base, carboxylate group or ether etc., play the emulsifying agent effect in letex polymerization; Also have two keys in the molecule simultaneously, it participates in copolymerization as monomer in letex polymerization become a part in the multipolymer macromolecular chain, polymerization finishes it and also exhausts substantially, the result no longer contains small-molecular emulsifier at the emulsion product, thereby has fundamentally eliminated the fatal shortcoming that causes the emulsion coatings poor water resistance owing to conventional emulsifier.
The preparation of organosilicon-acrylic resin emulsion of the present invention is to carry out emulsion copolymerization earlier by organosilane monomer, unsaturated acid and the unsaturated monomer that contains unsaturated double-bond in the presence of emulsifying agent, obtains with the reaction of hydroxyl polysiloxane again.The letex polymerization temperature is 70～90 ℃, its technology is: with deionized water, emulsifying agent and water-based initiator add in the reactor, be warming up to 70～90 ℃, drip the mixed solution of the organosilane monomer, unsaturated acid and the unsaturated monomer that contain unsaturated double-bond 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 emulsifying agent is composited by anion surfactant and nonionic surface active agent, anion surfactant such as category-A, category-B, D class, and consumption is 0.5～3% by weight percentage; Nonionic surface active agent such as polyoxyethylene phenolic ether in the ninth of the ten Heavenly Stems, Voranol EP 2001, C class etc., consumption is 1～8% by weight percentage.
The water-based initiator adopts persulphate, and as Potassium Persulphate or ammonium persulphate, consumption is 0.2～3% by weight percentage.Silicon alcohol condensation catalyst such as dibutyl tin dilaurate, dibutyl tin acetate or tetrabutyl titanate etc., consumption is 0.05～5% by weight percentage.
In the present invention, introduce the unsaturated acid molecule, make and introduced numerous strong hydrophilicity groups in the emulsion that makes, increased the stability that emulsion is made coating.Introduce the hard monomer as methyl methacrylate, the coating that emulsion is made has had good hardness of film, photostabilization, has improved the minimum film-forming temperature of emulsion.Introduce soft monomer, increased the snappiness of coating as butyl acrylate, sticking power, water tolerance has reduced the film-forming temperature of emulsion.Introduce unsaturated acid and contain the organosilane monomer of unsaturated double-bond,, thereby make the coating can be at the back crosslinking curing that is heated for above-mentioned unsaturated monomer provides cross-linking set.Because during emulsion film forming, polysiloxane generally is enriched in the multipolymer surface, therefore introduces the hydroxyl polysiloxane and improved the water resistance that emulsion is made coating greatly.
In the coating that emulsion of the present invention is made, component owing to the organosilane monomer that contains unsaturated double-bond, unsaturated acid, unsaturated monomer, hydroxyl polysiloxane, thereby the coating that this emulsion is made is compared with the coating that the conventional art emulsion is made, in the coating property of emulsion of the present invention, its water resistance has improved nearly 5 times than in the past, it is nearly 50% that wash-resistant property has improved, and contamination resistance improves greatly, ageing resistance is the highest to have risen closely 70%, has obtained effect preferably.The coating made of this emulsion 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 salt 1 gram of emulsifying agent D, emulsifying agent C2 gram, 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 43 grams added in 2 hours, kept reaction 2 hours in 75 ℃.Add dibutyl tin dilaurate 0.3 gram then, drip hydroxyl polysiloxane 5 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.[embodiment 2]
Just change the component and sodium salt that consumption is emulsifying agent A 4 grams of organosilane monomer, unsaturated acid, unsaturated monomer and the emulsifying agent of unsaturated double-bond, vinyl three TMOSs 3 grams, methacrylic acid 4 grams, methyl acrylate 43 grams, butyl methacrylate 40 grams, hydroxyl polysiloxane 10 grams, other prescription and technology are identical with embodiment 1.Get the organosilicon-modified acrylic copolymer emulsion.[embodiment 3]
Just change the component and sodium salt that consumption is emulsifying agent B 3 grams of organosilane monomer, unsaturated acid, unsaturated monomer and the emulsifying agent of unsaturated double-bond, emulsifying agent C3 gram, gamma-methyl allyl acyloxypropyl trimethoxysilane 10 grams, vinylformic acid 3 grams, methyl methacrylate 43 grams, butyl methacrylate 43 grams, hydroxyl polysiloxane 1 gram, other prescription and technology are identical with embodiment 1.Get the organosilicon-modified acrylic copolymer emulsion.[comparative example 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.[comparative example 2]
The component and the consumption that just change organosilane monomer, unsaturated acid and the unsaturated monomer of unsaturated double-bond are vinyltriethoxysilane 5 grams, vinylformic acid 3 grams, methyl methacrylate 44 grams, the mixture of butyl acrylate 48 grams, other prescription and technology and comparative example 1 get the organosilicon-modified acrylic copolymer emulsion.
To become coating by following formulated by the emulsion of the foregoing description and comparative example gained, and test coating property then, the result is as shown in table 1.
Formulation for coating material: emulsion 40%
Titanium dioxide 20%
Lime carbonate 20%
Sodium polyacrylate 1%
Deionized water 19%
Table 1 coating property test result
Above performance test standard: GB/T9755-1995 exterior wall coating material of synthetic resin emulsion (acceptable end product)
| Water tolerance | Abrasion resistance | Contamination resistance % | Ageing resistance hour | Time of drying hour | Contrast ratio | |
| Embodiment 1 | 576 hours no abnormal | 1500 | 27 | 380 | 1 | 0.94 |
| Embodiment 2 | 576 hours no abnormal | 1530 | 26 | 352 | 1 | 0.90 |
| Embodiment 3 | 576 hours no abnormal | 1490 | 24 | 360 | 1 | 0.91 |
| Comparative example 1 | 96 hours micro bubbles | 1000 | 33 | 200 | 1 | 0.83 |
| Comparative example 2 | 96 hours micro bubbles | 1100 | 31 | 220 | 1 | 0.86 |
Claims (4)
1, a kind of organosilicon-acrylic resin emulsion comprises by weight percentage:
(a) contain the organosilane monomer 1～20% of unsaturated double-bond, organosilane monomer is selected from least a in vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane or the gamma-methyl allyl acyloxypropyl trimethoxysilane;
(b) unsaturated acid 1～20%, and unsaturated acid is selected from acrylic or methacrylic acid and composition thereof;
(c) unsaturated monomer 40～96%, and unsaturated monomer is selected from least two kinds in methyl methacrylate, methyl acrylate, butyl acrylate, butyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, dimethylaminoethyl acrylate methyl ammonia ethyl ester or the glycidyl methacrylate;
(d) the hydroxyl polysiloxane 1～20%, and by the dimethyldiethoxysilane hydrolysis, condensation is taken off ethanol and made again;
(e) emulsifying agent 1～10%, and wherein emulsifying agent contains succsinic acid alkyl allyloxy hydroxypropyl two sulfonated esters, succsinic acid allyl group alkyl diester sulfonate, propenyl phenol Soxylat A 25-7 or nonyl phenol β-allyloxy methylene radical and replaces at least a in the polyethenoxy ether carboxylate;
Carry out emulsion copolymerization earlier by the composition (a) and (b) with (c) in the presence of (e), multipolymer makes with composition (d) reaction more then.
2,, it is characterized in that unsaturated acid is 2～8% by weight percentage according to the described organosilicon-acrylic resin emulsion of claim 1.
3,, it is characterized in that the hydroxyl polysiloxane is 1～10% by weight percentage according to the described organosilicon-acrylic resin emulsion of claim 1.
According to the described organosilicon-acrylic resin emulsion of claim 1, it is characterized in that by weight percentage that 4, emulsification dosage is 3～6%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01105008 CN1130436C (en) | 2001-01-03 | 2001-01-03 | Organosilicon-acrylic resin emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01105008 CN1130436C (en) | 2001-01-03 | 2001-01-03 | Organosilicon-acrylic resin emulsion |
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| CN1130436C true CN1130436C (en) | 2003-12-10 |
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| CN1796428B (en) * | 2004-12-27 | 2010-05-05 | 深圳市海川实业股份有限公司 | Method for preparing Silicone acrylic emulsion |
| CN100345874C (en) * | 2005-02-28 | 2007-10-31 | 仪征多科特水性化学品有限责任公司 | Organosilicon modified acrylate emulsion for ambient temperature crosslinked aqueous paint and method for preparing same |
| CN101581045B (en) * | 2009-06-12 | 2011-06-08 | 辽宁恒星精细化工（集团）有限公司 | Elastic colorized printing paste and production method thereof |
| CN108842440B (en) * | 2018-06-26 | 2021-03-30 | 杭州新生印染有限公司 | Production process of flame-retardant blended fabric |
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