CN1155634C - Organosilicon grafted and modified acrylic resin emulsion - Google Patents
Organosilicon grafted and modified acrylic resin emulsion Download PDFInfo
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- CN1155634C CN1155634C CNB01105011XA CN01105011A CN1155634C CN 1155634 C CN1155634 C CN 1155634C CN B01105011X A CNB01105011X A CN B01105011XA CN 01105011 A CN01105011 A CN 01105011A CN 1155634 C CN1155634 C CN 1155634C
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- organosilicon
- acrylic resin
- modified acrylic
- resin emulsion
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Abstract
The present invention relates to organosilicon grafted and modified acrylic resin emulsion. The present invention mainly solves the problems of paint prepared from 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 grafted and modified acrylic resin emulsion is prepared from 1 to 30 wt% of active organosilicon macromolecules with unsaturated polyester double bonds, 1 to 20 wt% of unsaturated acid, 40 to 97 wt% of unsaturated monomers and 1 to 10% of emulsifying agents, wherein the emulsifying agents comprise 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 organosilicon grafted and modified acrylic resin emulsion can be used in the industrial production of high performance paint.
Description
The present invention relates to organosilicon grafted and modified 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-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 separates, coacervation, the coating that makes by above-mentioned document in addition, its water tolerance, abrasion resistance, contamination resistance, ageing-resistant performance are not high, are 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 water tolerance, abrasion resistance, contamination resistance, the imperfect shortcoming of ageing-resistant performance, a kind of new organosilicon grafted and modified acrylic resin emulsion is provided for after overcoming in the past organosilicon-acrylic resin emulsion and making coating.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 grafted and modified acrylic resin emulsion by weight percentage, comprising:
(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 10～50% of active organosilicon macromolecule by weight percentage, the hydroxyl polysiloxane is by the dimethyldiethoxysilane hydrolysis, and condensation is taken off ethanol and made again;
(b) unsaturated acid 1～20%, and unsaturated acid is selected from acrylic or methacrylic acid and composition thereof;
(c) unsaturated monomer 40～97%, 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;
(d) 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.
In the technique scheme by weight percentage the preferable range of unsaturated acid be 2～8%, the macromolecular amount preferable range of active organosilicon that contains unsaturated double-bond is 1～20%, more preferably scope 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 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, adding above-mentioned hydroxyl polysiloxane and silicone macromolecule monomer, 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 contains unsaturated double-bond of about 15 centipoises of viscosity.
The emulsifying agent 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 is the alkyl or the alkalimetal ion of H, 1～4 carbon.
Emulsifying agent A: succsinic acid alkyl allyloxy hydroxypropyl two sulfonated esters
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 grafted and modified acrylic resin emulsion of the present invention, be by unsaturated monomer and unsaturated acid and the active organosilicon macromole that contains unsaturated double-bond in the presence of emulsifying agent, emulsion copolymerization makes under 70～90 ℃ of conditions of temperature.Its technology is: with deionized water, emulsifying agent and water-based initiator add in the reactor, are warming up to 70～90 ℃, drip unsaturated monomer, unsaturated acid subsequently and contain the active organosilicon macromole of unsaturated double-bond, added 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 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.
In the present invention, introduce the unsaturated acid molecule, make and introduced numerous strong hydrophilicity groups in the emulsion that makes, increased the stability of the coating that emulsion makes.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 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 water resistance that the hydroxyl polysiloxane has improved latex coating greatly.And before emulsion copolymerization, just finish graft reaction owing to contain the active organosilicon monomer and the hydroxyl polysiloxane of unsaturated double-bond, gel content that this has just improved percentage of grafting greatly and has reduced letex polymerization has further improved the water tolerance of the coating that emulsion makes.
In the coating that emulsion of the present invention is made, because the component of the active organosilicon macromole that contains unsaturated double-bond, unsaturated acid, unsaturated monomer is arranged, 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 25% than in the past, wash-resistant property has improved nearly 50%, contamination resistance improves greatly, from 33% dropped to 13% in the past, it is nearly 80% that ageing resistance has improved than in the past, 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 2 grams of emulsifying agent B, emulsifying agent C 2 grams, Potassium Persulphate 0.4 gram is heated to 75 ℃.The active organosilicon macromole that dropping contains unsaturated double-bond (contains vinyltrimethoxy silane 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 organosilicon-modified acrylic copolymer emulsion through 200 order net filtrations with ammoniacal liquor.
[embodiment 2]
Just change the component of the active organosilicon macromole, unsaturated acid, unsaturated monomer and the emulsifying agent that contain unsaturated double-bond and sodium salt 5 grams that consumption is emulsifying agent A, active organosilicon macromole 10 grams that contain unsaturated double-bond (contain vinyltriethoxysilane 70% by weight percentage, the hydroxyl polysiloxane is (by the dimethyldiethoxysilane hydrolysis, condensation is taken off ethanol and is made again) 30%), vinylformic acid 4 grams, methyl methacrylate 39 grams, ethyl propenoate 47 grams, other prescription and technology are identical with embodiment 1.Get the organosilicon-modified acrylic copolymer emulsion.
[embodiment 3]
Change the active organosilicon macromole that contains unsaturated double-bond, unsaturated acid, the component of unsaturated monomer and emulsifying agent and consumption are sodium salt 2 grams of emulsifying agent D, emulsifying agent C 1 gram, 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%) 20 grams, methacrylic acid 5 grams, methyl acrylate 35 grams, butyl acrylate 34 grams, glycidyl methacrylate 6 grams, 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 change silicone macromolecule, unsaturated acid and 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 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
| Water resistance | Abrasion resistance | Contamination resistance % | Ageing resistance hour | Time of drying hour | Contrast ratio | |
| Embodiment 1 | 120 hours no abnormal | 1500 | 13 | 390 | 1 | 0.92 |
| Embodiment 2 | 120 hours no abnormal | 1530 | 14 | 386 | 1 | 0.93 |
| Embodiment 3 | 120 hours no abnormal | 1490 | 13 | 385 | 1 | 0.90 |
| 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 |
Above performance test standard: GB/T9755-1995 exterior wall coating material of synthetic resin emulsion (acceptable end product)
Claims (5)
1, a kind of organosilicon grafted and modified acrylic resin 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 10～50% of active organosilicon macromolecule by weight percentage, the hydroxyl polysiloxane is by the dimethyldiethoxysilane hydrolysis, and condensation is taken off ethanol and made again;
(b) unsaturated acid 1～20%, and unsaturated acid is selected from acrylic or methacrylic acid and composition thereof;
(c) unsaturated monomer 40～97%, 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;
(d) 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;
By composition (b), (c) and (a) in the presence of (d) emulsion copolymerization make.
2, organosilicon grafted and modified acrylic resin emulsion according to claim 1 is characterized in that unsaturated acid is 2～8% by weight percentage.
3, organosilicon grafted and modified acrylic resin emulsion according to claim 1, the active organosilicon macromole that it is characterized in that containing unsaturated double-bond is 1～20% by weight percentage.
4, organosilicon grafted and modified acrylic resin emulsion according to claim 3, the active organosilicon macromole that it is characterized in that containing unsaturated double-bond is 1～10% by weight percentage.
5, organosilicon grafted and modified acrylic resin emulsion according to claim 1 is characterized in that by weight percentage, and emulsification dosage is 3～6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01105011XA CN1155634C (en) | 2001-01-03 | 2001-01-03 | Organosilicon grafted and modified acrylic resin emulsion |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01105011XA CN1155634C (en) | 2001-01-03 | 2001-01-03 | Organosilicon grafted and modified acrylic resin emulsion |
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| Publication Number | Publication Date |
|---|---|
| CN1362431A CN1362431A (en) | 2002-08-07 |
| CN1155634C true CN1155634C (en) | 2004-06-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB01105011XA Expired - Fee Related CN1155634C (en) | 2001-01-03 | 2001-01-03 | Organosilicon grafted and modified acrylic resin emulsion |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108383937A (en) * | 2018-02-28 | 2018-08-10 | 中山市巴德富化工科技有限公司 | A kind of water-fast acrylic acid ester emulsion of hydrophobic high rigidity and preparation method thereof |
| CN110581247B (en) * | 2018-06-08 | 2022-07-22 | 上海恩捷新材料科技有限公司 | Ceramic composite diaphragm and preparation method thereof |
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Granted publication date: 20040630 Termination date: 20120103 |