CN101914185A - Hydroxy acrylic resin aqueous dispersion and water-based coating prepared therefrom - Google Patents
Hydroxy acrylic resin aqueous dispersion and water-based coating prepared therefrom Download PDFInfo
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- CN101914185A CN101914185A CN 201010275369 CN201010275369A CN101914185A CN 101914185 A CN101914185 A CN 101914185A CN 201010275369 CN201010275369 CN 201010275369 CN 201010275369 A CN201010275369 A CN 201010275369A CN 101914185 A CN101914185 A CN 101914185A
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Abstract
The invention discloses a method for preparing a hydroxy acrylic resin aqueous dispersion and the hydroxy acrylic resin aqueous dispersion prepared by the same and water-based coating using the hydroxy acrylic resin aqueous dispersion as a film forming matter. The hydroxy acrylic resin aqueous dispersion is prepared by a step free radical solution polymerization process and obtains a nucleus-shell structure by using an initiator of a specific type and a chain transfer agent and by a high-temperature polymerization reaction. The nucleus has weak hydrophilicity and no carboxyl, and the shell has a strong hydrophilicity and is rich in carboxyl, so stable storage can be realized. The obtained hydroxy acrylic resin aqueous dispersion has the characteristics of low solution content, high solid content and low viscosity. The coating prepared from the hydroxy acrylic resin aqueous dispersion and a water-based amino resin or a water-based polyurethane cross-linking agent has the characteristics of high brightness, good water resistance and excellent weather resistance. The hydroxy acrylic resin aqueous dispersion can be used for preparing an excellent base material of high-performance environment-friendly industrial protective coatings and widely applied to topcoats and primer-topcoat coatings in various fields.
Description
Technical field
The present invention relates to a kind of Hydroxylated acrylic resin water dispersion in the chemical industry water-borne coatings field and with the water-borne coatings of its preparation.
Background technology
Solvent based coating is owing to cause serious environment and health problem, and use is restricted, and eco-friendly water-borne coatings is the trend of current coating industry development, and all kinds of aqueous dispersion type resins all can be seen on market.The water-based hydroxyl acrylic resin is because its gloss height, good weatherability, guarantor's look gloss retention is widely used in water-based amino-stoving varnish finish paint and two component polyurethane coats with lacquer from dried noodle, but domestic water-based hydroxyl acrylic resin mostly is emulsion-type or the very big resin aqueous dispersions of viscosity.The former gloss is low, because the existence of emulsifying agent is arranged, the bad problem of water-fast protection against corrosion is arranged also; The latter constructs and contains lowly admittedly, and gloss is also not high enough, also is difficult to promote the use of.
The general aqueous dispersion type Hydroxylated acrylic resin of producing all is to introduce a certain amount of carboxylic monomer in polymerization single polymerization monomer, free radical solution polymerization prepares resin then, all or part of solvent is removed in distillation, makes that carboxylic ionsization can be dispersed in the water resin on the resin thereby add amine substance again.In order to pursue the storage stability of resin water dispersion, generally need to introduce more carboxyl, need make the acid number of solid resin reach 30-50 mg KOH/g resin at least, but this descends water-fast, the alkali resistance of Hydroxylated acrylic resin.And the general viscosity of Hydroxylated acrylic resin of preparation is bigger in this way, reduces to 30% (weight fraction) back resin dispersion and just has certain flowability admittedly contain.It is low that this just makes the made coating application of this resin contain admittedly, uses inconvenient; Even if use reluctantly, gloss is also not high enough.
As mentioned above, possess storage-stable, high-solid lower-viscosity and gloss of film height, the good Hydroxylated acrylic resin water dispersion of protection against corrosion and water resistance is still undiscovered.
Summary of the invention
The problem that invention will solve
The present invention be intended to overcome above-mentioned water-based hydroxyl acrylic resin shortcoming, a kind of storage-stable is provided, high-solid lower-viscosity, the protection against corrosion water resistance is good, and the high weather-proof good hydroxy resin water dispersion of gloss, and provide the method for preparing water-borne coatings with this resin combination.
The means of dealing with problems
The inventor finds:
(1) the resin aqueous dispersions viscosity of the production of the initiator a little less than the hydrogen-taking capacity is less than the resin aqueous dispersions of the strong initiator production of hydrogen-taking capacity.This polymer molecule that should be the weak initiator of hydrogen-taking capacity makes mostly is linear structure, and the strong initiator of hydrogen-taking capacity makes the polymkeric substance that makes mostly be Grafting Structure, so the former viscosity is lower than the latter owing to capture hydrogen on the polymer macromolecule.
(2) suitably improve the temperature polyreaction, make half-lives of initiators in several minutes, gained resin aqueous dispersions viscosity can reduce.It is big and cause due to polymericular weight reduces that this should be that initiator decomposes fast when making polyreaction number of free radical.And the initiator that makes higher concentration is dissolved in the monomer and take to drip monomeric polymerization technique, though then decomposition of initiator comparatively fast also can make monomer conversion reach more than 99%.
(3) step-by-step polymerization, most of monomer uses the weak initiator initiated polymerization of hydrogen-taking capacity during the first step polymerization, second step during polymerization small part monomer use the strong initiator initiated polymerization of hydrogen-taking capacity, the resin aqueous dispersions viscosity that the initiator of the viscosity of resulting polymers aqueous dispersions a little less than near hydrogen-taking capacity produced, and if in the first step polymerization, there is not carboxylic monomer, and carboxylic monomer is enriched in the second step polymerization, then gained resin water dispersion viscosity is less unexpectedly.This may be that the strong initiator of hydrogen-taking capacity is rich in the macromole of carboxyl except making second step polymeric monomer being synthetic in the second step polymerization, also makes to be rich in the carboxyl macromole and to graft on the linear polymer that produces in the first step polymerization.When the graftomer after the neutralization is scattered in water, the second step polymerized product becomes the shell polymkeric substance owing to be rich in the strong surface that is distributed in the water dispersed resin particulate of carboxylated hydrophilic, and the inside that the first step polymerisate is positioned at the water dispersed resin particulate by force owing to hydrophobicity becomes the nuclear of water dispersed resin particulate.Owing to formed this nucleocapsid structure, the polymer macromolecule number that is in extended configuration in the resin water dispersion significantly reduced, thereby greatly reduce the viscosity of resin water dispersion.Owing to formed this structure, also make to keep the required carboxyl number of resin water dispersion storage-stable significantly to reduce, thereby improved the water tolerance alkali resistance and the non-corrosibility of resin.
(4) solution polymerization viscosity helps polyreaction for a short time carries out smoothly, but too much the existence of solution also can make the resin water dispersion viscosity of gained increase and the storage stability variation except causing environmental pollution.Take pyroreaction to reduce in the polyreaction requirement to solvent.Resin liquid viscosity was low when temperature was high, and the little resin liquid viscosity that also can make of the high resulting polymers molecular weight of product of temperature of reaction reduces.So pyroreaction is used helpful to reducing solvent.
(5) introduce chain-transfer agent in the radical polymerization polymericular weight is dwindled, also help preparing the Hydroxylated acrylic resin water dispersion of high-solid lower-viscosity.
Therefore, on the basis that the inventor finds, the Hydroxylated acrylic resin water dispersion that the invention provides a kind of manufacture method of Hydroxylated acrylic resin water dispersion and make in this way.It is characterized in that polymerization is carried out in two steps, the first step is a free radical solution polymerization preparation nuclear, and the monomer of preparation nuclear does not have carboxylic monomer, adopts the weak initiator of hydrogen-taking capacity; Second step prepared shell for free radical solution polymerization under the situation of nuclear existence, and the monomer of preparation shell is rich in carboxylic monomer, adopts the strong initiator of hydrogen-taking capacity; Control reaction temperature is higher during polymerization, and adds a certain amount of chain-transfer agent.Add a certain amount of neutralizing agent and water after resins is finished, promptly contained the low Hydroxylated acrylic resin water dispersion of high viscosity admittedly with nucleocapsid structure and be uniformly dispersed.
The water-borne coatings that it is film forming matter that the present invention also provides with above-mentioned Hydroxylated acrylic resin water dispersion is characterized in that, its composition is: Hydroxylated acrylic resin water dispersion provided by the invention, auxiliary agent, color stuffing.
The present invention adopts free radical solution polymerization method synthesis of hydroxy acrylic resin in two steps: the nuclear part of the first step polymerization synthetic resin, this step polymerization spends monomer total amount 80%～96% (weight percent, monomer later on together), use the weak initiator initiated polymerization of hydrogen-taking capacity, second step during polymerization with 4%～20% small part monomer that accounts for the monomer total amount, use the strong initiator initiated polymerization of hydrogen-taking capacity, the resin aqueous dispersions viscosity that the initiator of the viscosity of resulting polymers aqueous dispersions a little less than near hydrogen-taking capacity produced.Do not have carboxylic monomer in the first step polymerization, and carboxylic monomer is enriched in the second step polymerization, then gained resin water dispersion viscosity is less unexpectedly.This may be that the strong initiator of hydrogen-taking capacity is rich in the macromole of carboxyl except making second step polymeric monomer being synthetic in the second step polymerization, also makes to be rich in the carboxyl macromole and to graft on the linear polymer that produces in the first step polymerization.When the graftomer after the neutralization is scattered in water, the second step polymerized product becomes the shell polymkeric substance owing to be rich in the strong surface that is distributed in the water dispersed resin particulate of carboxylated hydrophilic, and the inside that the first step polymerisate is positioned at the water dispersed resin particulate by force owing to hydrophobicity becomes the nuclear of water dispersed resin particulate.Owing to formed this nucleocapsid structure, the polymer macromolecule number that is in extended configuration in the resin water dispersion significantly reduced, thereby greatly reduce the viscosity of resin water dispersion.Add high polymeric reaction temperature of water and low organic solvent content again, thereby prepare the Hydroxylated acrylic resin water dispersion of high-solid lower-viscosity.Owing to formed this nucleocapsid structure, also make to keep the required carboxyl number of resin water dispersion storage-stable significantly to reduce, reduce hydrophilic monomer quantity, thereby improved the water tolerance alkali resistance and the non-corrosibility of resin.
The present invention specifically prepares by following steps:
(1) the first step polymerization: a certain amount of solvent is added reaction vessel, stirring is warming up to 70～170 ℃, be added dropwise to reaction vessel after will participating in the first step polymeric monomer, chain-transfer agent and initiator mixed dissolution, 3～5 hours dropping time, drip and kept temperature of reaction 1 hour, obtain the first step polymerisate, this part product is the nuclear part of water dispersed resin particulate in future.
The solvent that uses in this step is one or more the mixture in N-BUTYL ACETATE, tetracol phenixin, No. 100 solvent oils, No. 200 solvent oils, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone, ethanol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, ethylene glycol, propylene glycol, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol monobutyl ether, 1-Methoxy-2-propyl acetate, the diethylene glycol monobutyl ether.Come selective solvent or solvent mixture according to solvent boiling point a little more than the principle of temperature of reaction.The consumption of solvent is 80～92% for making the first step polymerization gained resin solution solids content.
Participating in this step polymeric monomer is vinyl acetate between to for plastic, vinylchlorid, dichloro-ethene, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) dodecylacrylate, (methyl) vinylformic acid cocinin, (methyl) vinylformic acid stearyl, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, vinylbenzene, vinyl cyanide, (methyl) acrylamide, (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid lignocaine ethyl ester, (methyl) vinylformic acid dimethylamino propyl ester, N-(1,1-dimethyl-3-oxo butyl) (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-n-butoxy (methyl) acrylamide, N-isobutoxy (methyl) acrylamide, (methyl) glycidyl acrylate, Vinylstyrene, ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the mixture of one or more in trimethylolpropane tris (methyl) acrylate wherein must contain carboxylic monomer.This nuclear part resin hydroxy radical content is 1～5% (solid weight ratio), and the best is 3～4%.
The chain-transfer agent that adopts in the polymerization of this step is 2 mercapto ethanol or n-dodecyl mercaptan, and its consumption is 0.5～3% of a monomer weight, and optimum is 1～2%.
The weak initiator of hydrogen-taking capacity is adopted in the polymerization of this step, for: one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), two t-amyl peroxy things, ditertiary butyl peroxide, the tertbutyl peroxide or several common use.Initiator amount is 1～5% of a monomer weight, and optimum quantity is 2～4%.
The temperature of reaction that this step polymerization is adopted is that the temperature when being 1～10 minute according to used half-lives of initiators is decided, and optimal reaction temperature is the temperature of half-lives of initiators when being 3～6 minutes.
(2) second step polymerizations: the resin liquid that the first step polymerization obtains maintains the temperature at 70～170 ℃, be added dropwise to reaction vessel after will participating in the second step polymeric monomer, chain-transfer agent and initiator mixed dissolution, 0.5～1 hour dropping time, drip and add an amount of initiator maintenance temperature of reaction 2～4 hours, obtain grafting Hydroxylated acrylic resin solution, the polymkeric substance that the polymer graft that the second step polymerization forms forms in the first step polymerization.
Participating in this step polymeric monomer is vinyl acetate between to for plastic, vinylchlorid, dichloro-ethene, methylene-succinic acid, maleic anhydride, (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) dodecylacrylate, (methyl) vinylformic acid cocinin, (methyl) vinylformic acid stearyl, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, vinylbenzene, vinyl cyanide, (methyl) acrylamide, (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid lignocaine ethyl ester, (methyl) vinylformic acid dimethylamino propyl ester, N-(1,1-dimethyl-3-oxo butyl) (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-n-butoxy (methyl) acrylamide, N-isobutoxy (methyl) acrylamide, (methyl) glycidyl acrylate, Vinylstyrene, ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the mixture of two or more in trimethylolpropane tris (methyl) acrylate, it must contain carboxylic monomer and carboxylic monomer.Hydroxy radical content 1～5% (solid weight ratio), the best is 3～4%; Carboxyl-content is that to make the whole acid number of gained Hydroxylated acrylic resin be 10～40mg KOH/g solid resin, and the best is 15～25mg KOH/g solid resin.
The chain-transfer agent that adopts in the polymerization of this step is 2 mercapto ethanol or n-dodecyl mercaptan, and its consumption is 0.5～3% of a monomer weight, and optimum is 1～2%.
The strong initiator of hydrogen-taking capacity is adopted in the polymerization of this step, for: the new certain herbaceous plants with big flowers tert-butyl acrylate of peroxidation, the peroxidation trimethylacetic acid tert-butyl ester, dilauroyl peroxide, dibenzoyl peroxide, peroxidized t-butyl perbenzoate, tert-butyl peroxy acetate, dicumyl peroxide, isopropyl benzene hydroperoxide, the special pentyl ester of peroxidation-2 ethyl hexanoic acid, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidation-3,5, one or more in the 5-tri-methyl hexanoic acid tert-butyl ester.Initiator amount is 1～5% of a monomer weight, and optimum quantity is 2～4%.
The temperature of reaction that this step polymerization is adopted is that the temperature when being 1～10 minute according to used half-lives of initiators is decided, and optimal reaction temperature is the temperature of half-lives of initiators when being 3～6 minutes.
(3) gained Hydroxylated acrylic resin solution is reduced to suitable temp, add alkaline neutraliser,, both obtained the Hydroxylated acrylic resin water dispersion of storage-stable adding the quick dispersed with stirring of entry to evenly.The consolidating to contain of resin water dispersion can reach 42～55%.
Neutralizing agent of the present invention is N, and N-dimethylethanolamine, triethylamine and composition thereof, degree of neutralization are 50-100%, and optimum is 75-85%.
The present invention also provides a kind of water-borne coatings, and it prepares with common preparation method for coating, and this water-borne coatings contains the present invention prepared Hydroxylated acrylic resin water dispersion, auxiliary agent, color stuffing.Gained coating is green environmental friendly coatings.It cooperates with water-compatible amino resin or aqueous polyurethane linking agent, can be made into water-based amino-stoving varnish or air-dry water-based bicomponent polyurethane paint.Paint film can reach pencil hardness B～HB in 24 hours, 60 ° of gloss reach 80～90.This coating weatherability is protected the look gloss retention, water-fast solvent resistance, the excellent property of struggling against the corrosive influence.
Embodiment
Below by example the present invention is done further to specify, but the present invention is not limited to these examples.
Example 1
This example is intended to show the preparation method of Hydroxylated acrylic resin water dispersion, and is as follows:
(1) 100g propylene glycol butyl ether adding reaction vessel and stirring are warming up to 150～160 ℃; With 100g vinylbenzene, 150g methyl methacrylate, 30g butyl acrylate, 90g Hydroxyethyl acrylate, 30g dodecylacrylate, 4g n-dodecyl mercaptan, 12g ditertiary butyl peroxide mixed dissolution are made the monomer dropping material, and the question response vessel temp rises to 150～160 ℃ with monomer dropping gob adding reactor.Keep 150～160 ℃ of temperature of reaction, 4 hours monomer dropping time.Intact 150～160 ℃ of insulations of monomer dropping 1 hour.Gained resin solution weight contains 80% admittedly, does not contain carboxyl, resin number-average molecular weight 4000～5000.
(2) the first step polymerisate maintains the temperature at 140～150 ℃, with 45g methyl methacrylate, 20g butyl acrylate, 23g Hydroxyethyl acrylate, 12g vinylformic acid, 1g n-dodecyl mercaptan, 3g peroxidized t-butyl perbenzoate mixed dissolution, in 0.5～1 hour, be added dropwise in the first step polymerisate, the intact 1g of adding of monomer dropping peroxidized t-butyl perbenzoate is incubated 1 hour, add the 1g peroxidized t-butyl perbenzoate again, be incubated 1 hour.Cooling then.
(3) products therefrom is cooled to 80 ℃, adds triethylamine 12g, water 550g, and quick then dispersed with stirring obtains the emulsion form resin water dispersion that the appearance white exquisiteness has blue light.
It is 43.2% that the weight of this Hydroxylated acrylic resin water dispersion contains admittedly, and VOC content is 8.7ml/100g, viscosity 300 centipoises, and 50 ℃ of storages were stablized solid resin acid number 18.7mg KOH/g, solid resin hydroxy radical content 3.3% in 30 days.The water-based isocyanate crosslinking agent B ayhydur VPLS 2319 of itself and German Bayer AG, VPLS 2336 grades cooperate the gained resin coating film, and 12 hours pencil hardnesss of normal temperature self-drying are HB, and doing 72 hours pencil hardnesss certainly is 2H.And cooperate the amino-stoving varnish that obtains to form hardness after toasting with the water-compatible amino resin Cymel of Norway Cytec company 303 is filming of 3H.These two kinds of paint film common ground are that coating film gloss, levelling are splendid, weather-proof, protect look gloss retention energy, the water resistance of anti-the solvent is superior, is suitable as top-coat resin or paint for priming paint and top lacquer resin.
Example 2
This example is showed the Hydroxylated acrylic resin water dispersion that uses different initiator preparations, and is as follows:
(1) 100g butyl glycol ether adding reaction vessel and stirring are warming up to 155～165 ℃; With 100g vinylbenzene, 200g methyl methacrylate, 216g butyl acrylate, 224g Rocryl 410,60g vinylformic acid cocinin, 8g n-dodecyl mercaptan, 24g two t-amyl peroxy thing mixed dissolutions are made the monomer dropping material, and the question response vessel temp rises to 155～165 ℃ with monomer dropping gob adding reactor.Keep 155～165 ℃ of temperature of reaction, 4 hours monomer dropping time.Intact 155～165 ℃ of insulations of monomer dropping 1 hour.Gained resin solution weight contains 89% admittedly.Do not contain carboxyl, resin number-average molecular weight 3500～4500.
(2) the first step polymerisate maintains the temperature at 150～160 ℃, with 33g methyl methacrylate, 15g butyl acrylate, 28g Rocryl 410,24g vinylformic acid, 1g n-dodecyl mercaptan, 3g dicumyl peroxide mixed dissolution, in 0.5～1 hour, be added dropwise in the first step polymerisate, the intact 1g of adding of monomer dropping dicumyl peroxide is incubated 1 hour, add the 1g dicumyl peroxide again, be incubated 1 hour.Cooling then.
(3) products therefrom is cooled to 120 ℃, adds N, N-dimethylethanolamine 24g, and water 1000g, quick then dispersed with stirring obtains the emulsion form resin water dispersion that the appearance white exquisiteness has blue light.
It is 45.1% that the weight of this hydroxyl acrylic acid water dispersoid contains admittedly, and VOC content is 4.5ml/100g, viscosity 260 centipoises, and 50 ℃ of storages were stablized solid resin acid number 20.8mg KOH/g, solid resin hydroxy radical content 3.3% in 30 days.Itself and to cooperate the amino-stoving varnish that obtains to form hardness after toasting with the water-compatible amino resin Cymel of Norway Cytec company 303 be filming of 3H.The paint film characteristics are as amino-stoving varnish, its hardness and pliable and tough all good, and coating film gloss, levelling be splendid, weather-proof, protect look gloss retention energy, the water resistance of anti-the solvent is superior, is suitable as finish paint or paint for priming paint and top lacquer resin.
Example 3
This example is intended to show the Hydroxylated acrylic resin water dispersion for preparing different hydroxy radical contents
(1) 140g propylene glycol butyl ether adding reaction vessel and stirring are warming up to 155～165 ℃; With 200g vinylbenzene, 300g methyl methacrylate, 100g butyl acrylate, 140g hydroxyethyl methylacrylate, 60g dodecylacrylate, 8g n-dodecyl mercaptan, 24g two t-amyl peroxy thing mixed dissolutions are made the monomer dropping material, and the question response vessel temp rises to 155～165 ℃ with monomer dropping gob adding reactor.Keep 155～165 ℃ of temperature of reaction, 4 hours monomer dropping time.Intact 155～165 ℃ of insulations of monomer dropping 1 hour.Gained resin solution weight contains 85% admittedly.
(2) the first step polymerisate maintains the temperature at 155～165 ℃, with 30g methyl methacrylate, 15g butyl acrylate, 15g hydroxyethyl methylacrylate, 20g vinylformic acid, 1g n-dodecyl mercaptan, 3g isopropyl benzene hydroperoxide mixed dissolution, in 0.5～1 hour, be added dropwise in the first step polymerisate, the intact 1g of adding of monomer dropping isopropyl benzene hydroperoxide is incubated 2 hours, add the 1g isopropyl benzene hydroperoxide again, be incubated 2 hours.Cooling then.
(3) products therefrom is cooled to 120 ℃, adds N, N-dimethylethanolamine 20g, and water 700g, quick then dispersed with stirring obtains the emulsion form resin water dispersion that the appearance white exquisiteness has blue light.
It is 50.5% that the weight of this hydroxyl acrylic acid water dispersoid contains admittedly, and VOC content is 7.2ml/100g, viscosity 500 centipoises, and 50 ℃ of storages were stablized solid resin acid number 17.7mg KOH/g, solid resin hydroxy radical content 2.3% in 30 days.The water-based isocyanate crosslinking agent B ayhydur VPLS 2319 of itself and German Bayer AG, VPLS 2336 grades cooperate the gained resin coating film, and 12 hours pencil hardnesss of normal temperature self-drying are HB, and doing 72 hours pencil hardnesss certainly is 2H.And cooperate the amino-stoving varnish that obtains to form hardness after toasting with the water-compatible amino resin Cymel of Norway Cytec company 303 is filming of 3H.These two kinds of paint film common ground are that coating film gloss, levelling are splendid, weather-proof, protect look gloss retention energy, water resistance is superior, the wiping properties of anti-the butanone is poor slightly.Be suitable as top-coat resin or paint for priming paint and top lacquer resin.Its hydroxy radical content is low, and required supporting linking agent is few during paint, and the cost of lacquer is low.
Example 4
This example is intended to show that previous example 1 Hydroxylated acrylic resin water dispersion prepares the high light white paint of aqueous two-component polyurethane, and is as follows:
(1) adds Hydroxylated acrylic resin water dispersion 200g of the present invention and dispersion agent 760W (Tianjin Tego company) 0.8g in the high speed dispersor earlier, start stirring, add titanium white 930 (Mitsubishi Chemical) 73g, add proper quantity of defoaming agent, water again, start stirring, disperse fast.
(2) quick dispersed with stirring is to the fineness≤20 μ m of lacquer.Add an amount of thickening material and regulate the viscosity of lacquer, filter and promptly get the Hydroxylated acrylic resin lacquer.It is Part A as a component of the high light white paint of two component polyurethane.
(3) after itself and Bayhydur VPLS 2319 were used, the gained film performance was as follows:
| Surface drying, minute | 60? |
| Do solid work, minute | 240? |
| Film thickness, μ m | 40～50? |
| 72 hours postadhesion power of room temperature, cross-hatching | ≤ 1 grade |
| Room temperature is hardness after 72 hours | 2H? |
| Impact the weight method | ≥50cm? |
| Pliable and tough | 1mm? |
| Gloss of film, 60 ° | 84? |
[0057]?
| The butanone wiping is calculated once back and forth | 100 slightly deliquescing of paint film, no loss of gloss breakage |
| Paint film is from doing immersion after three days | 24 hours out of question |
| Paint film is towards southern solar exposure | 1000 hours, no loss of gloss did not have variable color and does not have efflorescence |
Example 5
This example is intended to show that previous example 2 Hydroxylated acrylic resin water dispersions prepare single-component amino-stoving varnish varnish, and is as follows:
(1) add Hydroxylated acrylic resin water dispersion 300g of the present invention in the high speed dispersor earlier, add proper quantity of defoaming agent, water again, start stirring.
(2) add the water-compatible amino resin Cymel of an amount of Norway Cytec company 303, an acidic catalyst stirs, and adds an amount of auxiliary rheological agents again and is adjusted to appropriate viscosity.
(3) 140 ℃ of bakings of paint film are after 30 minutes, and the gained film performance is as follows:
| Film thickness, μ m | 30～40? |
| 72 hours postadhesion power of room temperature, cross-hatching | ≤ 1 grade |
| Room temperature is hardness after 72 hours | 3H? |
| Impact the weight method | ≥50cm? |
| Pliable and tough | 1mm? |
| Gloss of film, 60 ° | 92? |
| The butanone wiping is calculated once back and forth | 100 times, the breakage of no deliquescing loss of gloss |
| Immersion | 21 days out of question |
Advantage according to the Hydroxylated acrylic resin water dispersion of the present invention preparation is conspicuous, it contains height admittedly, viscosity is low, solvent is few, cooperates with aminoresin or aqueous polyurethane linking agent, and be filming of film forming matter with it, the gloss height, weathering resistance is protected the look gloss retention, excellent propertys such as protection against corrosion water tolerance.It is the outstanding base-material of preparation high-performance environment-friendly industry anti-corrosion paint, can be widely used in finish paint and paint for priming paint and top lacquer that each field comprises the anti-corrosion of metal field.
Claims (12)
1. the preparation method of a Hydroxylated acrylic resin water dispersion, it is characterized in that: step-by-step polymerization obtains resin, and this resin of water-dispersion obtains the resin water dispersion with nucleocapsid structure of storage-stable, and polymerization is carried out in two steps:
The first step is that free radical solution polymerization prepares resin core, and the monomer of preparation nuclear does not have carboxylic monomer, adopts the weak initiator of hydrogen-taking capacity;
Second step prepared resin shell for free radical solution polymerization under the situation of nuclear existence, and the monomer of preparation shell has carboxylic monomer, adopts the strong initiator of hydrogen-taking capacity; Control reaction temperature is higher during polymerization, and adds a certain amount of chain-transfer agent, and cooling added a certain amount of neutralizing agent and water after resins was finished, and was uniformly dispersed and promptly got the Hydroxylated acrylic resin water dispersion with nucleocapsid structure.
2. the preparation method of a kind of Hydroxylated acrylic resin water dispersion as claimed in claim 1, it is characterized in that: the monomer for preparing described nuclear is a vinyl acetate between to for plastic, vinylchlorid, dichloro-ethene, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) dodecylacrylate, (methyl) vinylformic acid cocinin, (methyl) vinylformic acid stearyl, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, vinylbenzene, vinyl cyanide, (methyl) acrylamide, (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid lignocaine ethyl ester, (methyl) vinylformic acid dimethylamino propyl ester, N-(1,1-dimethyl-3-oxo butyl) (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-n-butoxy (methyl) acrylamide, N-isobutoxy (methyl) acrylamide, (methyl) glycidyl acrylate, Vinylstyrene, ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, in trimethylolpropane tris (methyl) acrylate one or more, wherein contain carboxylic monomer, nuclear resin hydroxyl solid weight ratio content is 1～5%.
3. the preparation method of a kind of Hydroxylated acrylic resin water dispersion as claimed in claim 2, the solid weight ratio of nuclear resin hydroxy radical content is 3～4%.
4. the preparation method of a kind of Hydroxylated acrylic resin water dispersion as claimed in claim 1, it is characterized in that: the monomer for preparing described shell is a vinyl acetate between to for plastic, vinylchlorid, dichloro-ethene, methylene-succinic acid, maleic anhydride, (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid cocinin, (methyl) vinylformic acid stearyl, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, vinylbenzene, vinyl cyanide, (methyl) acrylamide, (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid lignocaine ethyl ester, (methyl) vinylformic acid dimethylamino propyl ester, N-(1,1-dimethyl-3-oxo butyl) (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-n-butoxy (methyl) acrylamide, N-isobutoxy (methyl) acrylamide, (methyl) glycidyl acrylate, Vinylstyrene, ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, in trimethylolpropane tris (methyl) acrylate two or more, it contains carboxylic monomer and carboxylic monomer, the content of hydroxyl solid weight ratio is 1～5%, is preferably 3～4%; It is 10～40mgKOH/ gram solid resin that carboxyl-content makes the whole acid number of water-dispersion Hydroxylated acrylic resin, is preferably 15～25mg KOH/g solid resin.
5. the preparation method of a kind of Hydroxylated acrylic resin water dispersion as claimed in claim 1 is characterized in that: the described solvent that uses in its preparation is: the mixture of one or more in N-BUTYL ACETATE, tetracol phenixin, No. 100 solvent oils, No. 200 solvent oils, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone, ethanol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, ethylene glycol, propylene glycol, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol monobutyl ether, 1-Methoxy-2-propyl acetate, the diethylene glycol monobutyl ether
6. the preparation method of a kind of Hydroxylated acrylic resin water dispersion as claimed in claim 1, it is characterized in that: the required weak initiator of hydrogen-taking capacity is one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), two t-amyl peroxy things, ditertiary butyl peroxide, the tertbutyl peroxide in its preparation process, initiator amount is 1～5% of a monomer weight, is preferably 2～4%; The initiator that required hydrogen-taking capacity is strong is the new certain herbaceous plants with big flowers tert-butyl acrylate of peroxidation, the peroxidation trimethylacetic acid tert-butyl ester, dilauroyl peroxide, dibenzoyl peroxide, peroxidized t-butyl perbenzoate, tert-butyl peroxy acetate, dicumyl peroxide, isopropyl benzene hydroperoxide, the special pentyl ester of peroxidation-2 ethyl hexanoic acid, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidation-3,5, in the 5-tri-methyl hexanoic acid tert-butyl ester one or more, initiator amount is 1～5% of a monomer weight, is preferably 2～4%.
7. the preparation method of Hydroxylated acrylic resin water dispersion as claimed in claim 1, it is characterized in that: the temperature the when polymeric reaction temperature of preparation is 1～10 minute according to used half-lives of initiators is decided, and the best is the temperature of half-lives of initiators when being 3～6 minutes.
8. the preparation method of Hydroxylated acrylic resin water dispersion as claimed in claim 1 is characterized in that, the chain-transfer agent that adopts in the preparation is 2 mercapto ethanol or n-dodecyl mercaptan, and its consumption is 0.5～3% of a monomer weight, is preferably 1～2%.
9. the preparation method of Hydroxylated acrylic resin water dispersion as claimed in claim 1 is characterized in that, the neutralizing agent that adopts in the preparation is triethylamine or N, the N-dimethylethanolamine, and degree of neutralization is 50-100%, is preferably 75-80%.
10. as the preparation method of the described Hydroxylated acrylic resin water dispersion of arbitrary claim among the claim 1-9 and the Hydroxylated acrylic resin water dispersion that obtains, it is characterized in that: its composition (weight part) is:
11. Hydroxylated acrylic resin water dispersion as claimed in claim 10 is characterized in that: its water dispersed resin particulate has nucleocapsid structure, admittedly contain height and viscosity is low.
12. a water-borne coatings is characterized in that, this water-borne coatings composition is: Hydroxylated acrylic resin water dispersion as claimed in claim 10 and auxiliary agent and color stuffing.
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| CN2010102753695A CN101914185B (en) | 2010-09-08 | 2010-09-08 | Hydroxy acrylic resin aqueous dispersion and water-based coating prepared therefrom |
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| CN2010102753695A CN101914185B (en) | 2010-09-08 | 2010-09-08 | Hydroxy acrylic resin aqueous dispersion and water-based coating prepared therefrom |
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| CN117402544B (en) * | 2023-11-17 | 2024-04-12 | 东莞市瑞盟涂料有限公司 | Low-VOC (volatile organic compound) water-based paint and preparation method thereof |
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| CN101914185B (en) | 2011-12-07 |
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