CN1155637C - Grafted-organosilicon modified acrylic ester copolymer emulsion - Google Patents
Grafted-organosilicon modified acrylic ester copolymer emulsion Download PDFInfo
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- CN1155637C CN1155637C CNB011050144A CN01105014A CN1155637C CN 1155637 C CN1155637 C CN 1155637C CN B011050144 A CNB011050144 A CN B011050144A CN 01105014 A CN01105014 A CN 01105014A CN 1155637 C CN1155637 C CN 1155637C
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Abstract
The present invention relates to grafted organosilicon and modified acrylic ester copolymerization emulsion which mainly solves the problem of poor stability of emulsion in the past. The present invention adopts the technical scheme that the acrylic ester copolymerization emulsion is composed of components of the following proportion by weight: (a) 1 to 30% of active organosilicon macromolecule containing unsaturated double bond, (b) 1 to 20% of hydrophilicity unsaturated acid monomer, (c) 50 to 97% of hydrophobicity unsaturated monomer, which better solves the defects of technologies existing in the past. Thus, the mechanical stability of the copolymerization emulsion is enhanced by nearly 60% higher than that of the technologies in the past, and thus, the copolymerization emulsion can be used for the industrial production of paint.
Description
The present invention relates to grafted-organosilicon modified acrylic ester copolymer 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, and building external paint 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, 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 physical mechanical, promptly simply two kinds of compound mixing of emulsion of organic and inorganic is reached 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 51-146525 narrated among the JP54-3512 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.
The objective of the invention is provides a kind of new grafted-organosilicon modified acrylic ester copolymer emulsion for overcoming the defective that there is polymer-modified stability of emulsion difference in above-mentioned document.This emulsion has mechanical stability, characteristics that freeze-thaw stability is good.
The objective of the invention is to realize by following technical scheme: a kind of grafted-organosilicon modified acrylic ester copolymer emulsion comprises by weight percentage:
(a) contain the active organosilicon macromole 1～30% of unsaturated double-bond, silicone macromolecule is the grafting reactant of at least a and hydroxyl polysiloxane in vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane or the gamma-methyl allyl acyloxypropyl trimethoxysilane; Wherein, the hydroxyl polysiloxane accounts for whole silicone macromolecule 10～50% by weight percentage, and by the dimethyldiethoxysilane hydrolysis, condensation is taken off ethanol and made again;
(b) the wetting ability unsaturated acid monomer 1～20%, and unsaturated acid is selected from acrylic or methacrylic acid and composition thereof;
(c) the hydrophobicity unsaturated monomer 50～97%, 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.
In the technique scheme by weight percentage the amount preferable range of wetting ability unsaturated acid monomer be 2～8%, the macromolecular amount preferable range of active organosilicon that contains unsaturated double-bond is 5～20%, more preferably scope is 5～10%.
Above-mentioned hydroxyl polysiloxane is by the dimethyldiethoxysilane hydrolysis, and condensation is taken off ethanol and made again.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 above-mentioned active organosilicon macromole that contains unsaturated double-bond is to be made by hydroxyl polysiloxane and organosilane monomer graft reaction.Concrete steps: having prolong, in the four-necked bottle of Dropping feeder, add above-mentioned hydroxyl polysiloxane and at least a organosilane monomer that is selected from vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane or the gamma-methyl allyl acyloxypropyl trimethoxysilane, 732
#The type Zeo-karb is warming up to 65 ℃, begins to reflux, and drips the water of metering subsequently, finishes in 1～1.5 hour, is warming up to 75～85 ℃, keeps 2～3 hours.Leach 732
#The type resin boils off ethanol again, obtains the active organosilicon macromole that about 15 centipoises of viscosity contain unsaturated double-bond.
The preparation of grafted-organosilicon modified acrylic ester copolymer emulsion of the present invention is to make by hydrophobicity unsaturated monomer and wetting ability unsaturated acid monomer and the silicone macromolecule emulsion copolymerization that contains unsaturated double-bond.The letex polymerization temperature is 70～90 ℃, and its technology is: with deionized water, compound emulsifying agent and water-based initiator add in the reactor, be warming up to 70～90 ℃, drip above-mentioned monomer and the silicone macromolecule that contains unsaturated double-bond subsequently, dripped in 3～4 hours, equality of temperature is kept reaction 2 hours again.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.
Above-mentioned compound emulsifying agent is composited by anion surfactant and nonionic surface active agent, anion surfactant such as sodium lauryl sulphate or Sodium dodecylbenzene sulfonate, 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, polyoxyethylene sorbitol acid anhydride oleic acid ester or polyoxyethylene sorbitol acid anhydride stearate 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.
In the present invention, introduce the unsaturated acid monomer molecule, make and introduced numerous strong hydrophilicity groups in the copolymer emulsion that makes, increased the stability of emulsion.Introduce hard monomer, make emulsion that good hardness of film, photostabilization arranged, improved the minimum film-forming temperature of emulsion 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 emulsion.Introduce unsaturated acid and contain the active organosilicon macromole 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 introduce the mechanical stability that the hydroxyl polysiloxane has improved emulsion greatly.And before emulsion copolymerization, just finish graft reaction owing to contain the active organosilicon monomer and the hydroxyl polysiloxane of unsaturated double-bond, the gel content that this has just improved percentage of grafting greatly and has reduced letex polymerization, further can improve the mechanical stability and the freeze-thaw stability of emulsion, it is nearly more than 60% that thereby the mechanical stability that makes copolymer emulsion has improved than conventional art, obtained effect preferably.
In the coating that emulsion of the present invention is made, because the component of the active organosilicon macromole that contains unsaturated double-bond, wetting ability unsaturated acid, hydrophobicity unsaturated monomer is arranged, therefore water tolerance, pollution resistance, the water-repellancy performance of the coating made of this emulsion obviously are better than pure acrylic acid coating, are specially adapted to building external paint.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 156 grams, sodium lauryl sulphate 1 gram, Voranol EP 2001 3 grams, Potassium Persulphate 0.4 gram is heated to 75 ℃.The active organosilicon macromole that dropping contains unsaturated double-bond (contains vinyltriethoxysilane 50% by weight percentage, the hydroxyl polysiloxane is (by the dimethyldiethoxysilane hydrolysis, condensation is taken off ethanol and is made again) 50%) 5 grams, vinylformic acid 3 grams, methyl methacrylate 44 grams, the mixture of butyl acrylate 48 grams added in 4 hours, kept reaction 3 hours in 75 ℃.Be cooled to below 50 ℃, regulate pH value to 8～9,, must be with blue light organic silicon modified propenoic ester copolymer emulsion through 200 order net filtrations with ammoniacal liquor.
[embodiment 2]
The component and the consumption that change the active organosilicon macromole, wetting ability unsaturated acid monomer and the hydrophobicity unsaturated monomer that contain unsaturated double-bond are that the active organosilicon macromole that contains unsaturated double-bond (contains vinyltrimethoxy silane 90% by weight percentage, the hydroxyl polysiloxane is (by the dimethyldiethoxysilane hydrolysis, condensation is taken off ethanol and is made again) 10%) 10 grams, vinylformic acid 3 grams, methyl methacrylate 40 grams, ethyl propenoate 47 grams, other prescription and technology are identical with embodiment 1, get the organic silicon modified propenoic ester copolymer emulsion.
[embodiment 3]
Change the active organosilicon macromole that contains unsaturated double-bond, the component of wetting ability unsaturated acid monomer and hydrophobicity unsaturated monomer and consumption are that the active organosilicon macromole that contains unsaturated double-bond (contains vinyltrimethoxy silane 70% by weight percentage, the hydroxyl polysiloxane is (by the dimethyldiethoxysilane hydrolysis, condensation is taken off ethanol and is made again) 30%) 20 grams, methacrylic acid 5 grams, methyl acrylate 35 grams, butyl acrylate 34 grams, glycidyl methacrylate 6 grams mix, other prescription and technology are identical with embodiment 1, get the organic silicon modified propenoic ester copolymer emulsion.
[comparative example 1]
Have prolong, Dropping feeder, in the four-hole boiling flask of stirring, thermometer, adding entry 156 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 organic silicon modified propenoic ester 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 change silicone macromolecule, wetting ability unsaturated acid monomer and hydrophobicity unsaturated monomer 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 organic silicon modified propenoic ester copolymer emulsion.
Will be by the emulsion test performance of the foregoing description and comparative example gained, the result is as shown in table 1.
Table 1 emulsion property test result
| Residual monomer content | Mechanical stability | Freeze-thaw stability | |
| Embodiment 1 | 0.63％ | 0.80 breakdown of emulsion hour not | No breakdown of emulsion circulates 4 times |
| Embodiment 2 | 0.65％ | 0.78 breakdown of emulsion hour not | No breakdown of emulsion circulates 4 times |
| Embodiment 3 | 0.66％ | 0.81 breakdown of emulsion hour not | No breakdown of emulsion circulates 4 times |
| Comparative example 1 | 1.55％ | 0.5 hour breakdown of emulsion | Breakdown of emulsion circulates 3 times |
| Comparative example 2 | 1.60％ | 0.5 hour breakdown of emulsion | Breakdown of emulsion circulates 3 times |
Above performance test standard: benzene emulsion (JB-01, JB-02, JB-03)
Claims (4)
1, a kind of grafted-organosilicon modified acrylic ester copolymer emulsion, raw material comprises by weight percentage:
(a) contain the active organosilicon macromole 1～30% of unsaturated double-bond, silicone macromolecule is the grafting reactant of at least a and hydroxyl polysiloxane in vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane or the gamma-methyl allyl acyloxypropyl trimethoxysilane, wherein the hydroxyl polysiloxane accounts for active organosilicon macromole 10～50% by weight percentage, by the dimethyldiethoxysilane hydrolysis, condensation is taken off ethanol and is made again;
(b) the wetting ability unsaturated acid monomer 1～20%, and unsaturated acid is selected from acrylic or methacrylic acid and composition thereof;
(c) the hydrophobicity unsaturated monomer 50～97%, 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;
By composition (b), (c) and (a) emulsion copolymerization make.
2, grafted-organosilicon modified acrylic ester copolymer emulsion according to claim 1 is characterized in that the wetting ability unsaturated acid monomer is 2～8% by weight percentage.
3, grafted-organosilicon modified acrylic ester copolymer emulsion according to claim 1, the active organosilicon macromole that it is characterized in that containing unsaturated double-bond is 5～20% by weight percentage.
4, grafted-organosilicon modified acrylic ester copolymer emulsion according to claim 3, the active organosilicon macromole that it is characterized in that containing unsaturated double-bond is 5～10% by weight percentage.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011050144A CN1155637C (en) | 2001-01-03 | 2001-01-03 | Grafted-organosilicon modified acrylic ester copolymer emulsion |
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| CNB011050144A CN1155637C (en) | 2001-01-03 | 2001-01-03 | Grafted-organosilicon modified acrylic ester copolymer emulsion |
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| CN1155637C true CN1155637C (en) | 2004-06-30 |
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| CN103488220A (en) * | 2013-09-28 | 2014-01-01 | 迈普通信技术股份有限公司 | Power supply device and power supply method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101033271B (en) * | 2007-04-23 | 2010-07-28 | 大连交通大学 | Grafted resin with hydrolysis and low surface energy characteristic and anti-fouling paint prepared by the same |
| CN110724430B (en) * | 2019-09-05 | 2021-10-26 | 深圳市安品有机硅材料有限公司 | Water-based composite coating material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103488220A (en) * | 2013-09-28 | 2014-01-01 | 迈普通信技术股份有限公司 | Power supply device and power supply method |
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