CN103012714A - High-flexibility aqueous acrylic acid polyurethane elastic resin and coating thereof - Google Patents
High-flexibility aqueous acrylic acid polyurethane elastic resin and coating thereof Download PDFInfo
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- CN103012714A CN103012714A CN2012105802052A CN201210580205A CN103012714A CN 103012714 A CN103012714 A CN 103012714A CN 2012105802052 A CN2012105802052 A CN 2012105802052A CN 201210580205 A CN201210580205 A CN 201210580205A CN 103012714 A CN103012714 A CN 103012714A
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Abstract
The invention provides high-flexibility aqueous acrylic acid polyurethane elastic resin, which is prepared by the following steps of: modifying an organic silicon monomer, an acrylic acid long-chain monomer and a hydroxyl monomer through specially designing a vitrification temperature of an acrylic acid monomer; synthesizing hydroxyl acrylic resin with the very low vitrification temperature; and compounding the acrylic resin and a multi-isocyanate curing agent to obtain the high-flexibility aqueous acrylic acid polyurethane elastic resin. According to the high-flexibility aqueous acrylic acid polyurethane elastic resin, the organic silicon monomer, the long-chain monomer and the hydroxyl monomer are adopted; hydroxyl type aqueous acrylic resin with the high flexibility is synthesized by specially designing the vitrification temperature; and the resin is matched with the multi-isocyanate curing agent to be used as a film forming material to prepare a self-drying type aqueous elastic coating which can be applied to the surface of a flexible plastic product.
Description
Technical field
The present invention relates to a kind of high-flexibility water-borne acrylic resin, relate in particular to a kind of high-flexibility water soluble acrylic acid elastic polyurethane resin, and the coating take it as main film forming matter.
Background technology
Acrylic coating have look shallow, protect look, protect light, the advantage such as weather-proof, corrosion-resistant and anti-pollution.Water-borne acrylic type coating have price low, use safety, saving resource and the advantages such as the energy, environmental contamination reduction and public hazards, become one of main research and development direction of current coatings industry.In the plastelast field, need coating to have high snappiness and bend largely toughness to satisfy it, but need simultaneously to guarantee certain intensity, because there is the defective such as become fragile under the relatively poor and low temperature of anti-solvent ability in the water-borne acrylic resin of single-component, therefore the application in this respect of single-component water-based acrylic resin has been subject to many restrictions.For solving these defectives, water-borne acrylic resin is carried out the attention that modification more and more obtains people.
At present the modification technology of acrylic resin mainly contains: 1) physical method, i.e. and blending method, by mixing, the hybrid resin of gained can show both over-all propertieies with the resin of acrylic resin and another component.But this method is not owing to carry out chemical graft, and resin modified degree is limited.2) chemical process, this method can be divided into again hybrid system and hydridization method.The hydridization method is in the resin building-up process two components to be carried out chemical graft, this method complicated operation but the grafting degree is high, and the resin property that obtains is outstanding, also is widely used in the multiple coating field.Hybrid system is with acrylic resin and another kind of mixed with resin with reactive group with reactive group, by two kinds of active group reactive grafting, has improved the over-all properties of resin.This method technique is simple, and purposes is wide and the chemical graft rate is higher.
Chinese invention patent application 201110210844.5 discloses a kind of preparation method of interpenetrating network polyurethane acrylate emulsion, with Acrylic Acid Monomer as solvent, urethane, tolylene diisocyanate TDI, polyethers and catalyzer be dissolved in the Acrylic Acid Monomer fully react, add again emulsifying agent, neutralizing agent and deionized water and further react, thereby form interpenetrating network polyurethane acrylate emulsion.This technology can improve the consistency of polyacrylic ester (PA) emulsion and urethane (PU) emulsion, thereby make these two kinds of polymkeric substance intermolecular each self-crosslinking, interpenetrate, improve physical and chemical performance and decorate properties behind the prepared acroleic acid polyurethane emulsion film forming.But this method operation more complicated, real industrialization is produced difficult.
Summary of the invention
One object of the present invention is to provide a kind of high-flexibility water soluble acrylic acid elastic polyurethane resin, and this resin has high snappiness by molecular designing and modification, is equipped with suitable solidifying agent again and can realizes at low temperatures solidifying.
Another object of the present invention is to provide a kind of coating for the plastelast surface, take high-flexibility water soluble acrylic acid elastic polyurethane resin as main film forming matter, improves snappiness and the erosion resistance of coating.
The second-order transition temperature of acrylic monomer (Tg) is to affect the flexible key index of resin, is the key factor that can resin freely stretch, and second-order transition temperature is lower, and resin flexible toughness is better; The acrylate long-chain monomer is because side chain has longer carbochain, so that the flexible ability of the winding of resin is stronger, also can further improve the snappiness of whole resin.
Because the bond energy of covalent bond between Siliciumatom and the carbon atom is high, and high erosion resistance and weathering resistance are arranged, and silicone resin can form the space reticulated structure, improved the intensity of resin integral body.
The present invention carries out particular design by the Tg to acrylic monomer, first obtain the extremely low high-flexibility water-borne acrylic resin of Tg with vinylformic acid short chain monomer, acrylate long-chain monomer and carboxylic monomer and organosilane monomer with radical polymerization technique, and then with the composite crosslinked high-flexibility water soluble acrylic acid elastic polyurethane resin that obtains of polyisocyanate curing agent.
The Tg scope of various high-flexibility water soluble acrylic acid polyurethane elastomer resins provided by the invention is-40 ℃--20 ℃, belong to the extremely low resin of the alleged Tg of the present invention.
The radical polymerization technique of producing high-flexibility water-borne acrylic resin of the present invention belongs to the general operation technical ability that those of ordinary skills should possess, also can be according to " coating process (third edition) " (coating process editorial committee volume, Chemical Industry Press, 1997) guidance of a book prepares.Initiator is used for realizing Raolical polymerizable, those skilled in the art just can realize the initiator type and the consumption that are fit to reaction are selected according to the guidance of textbook or laboratory manual, as: but be not limited only to Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide (BPO), dilauroyl peroxide, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidation-2 ethyl hexanoic acid tert-pentyl ester, tert-butyl peroxy acetate, peroxidized t-butyl perbenzoate (TBPB), peroxidation-3,5, the 5-tri-methyl hexanoic acid tert-butyl ester, tertbutyl peroxide (TBHP), isopropyl benzene hydroperoxide, ditertiary butyl peroxide (DTBP), one or more of percarbonic acid two cyclohexyls and percarbonic acid two (2-ethylhexyl).
Among the present invention, one group of acrylic monomer that various vinylformic acid short chain monomers are interpreted as vinylformic acid and become the ester composition with C1-C6 unit alcohol institute as: but be not limited only to methyl methacrylate (MMA), butyl methacrylate (BMA), butyl acrylate (BA), methacrylic acid and vinylformic acid (AA).Its mode with two or more is applied to the present invention, and total amount is 40wt%-54wt%.
Among the present invention, various acrylate long-chain monomers, be the acrylate that forms of vinylformic acid and C10-C20 unit alcohol as: but be not limited only to vinylformic acid lauryl alcohol ester (LMA), vinylformic acid hexadecanol ester and vinylformic acid stearyl alcohol ester etc., the consumption of these acrylate long-chain monomers is 5wt%-10wt%, is applied to the present invention with the form of independent or several combinations.
Among the present invention, carboxylic monomer is vinylformic acid short chain monomer that hydrogen atom is replaced by hydroxyl on its carbochain, as: hydroxyethyl methylacrylate (HEMA), Hydroxyethyl acrylate (HEA), Rocryl 410 (HPMA) and Propylene glycol monoacrylate (HPA).The carboxylic monomer consumption is 15wt%-25wt%, and forms independent or several combinations are applied to the present invention.
Among the present invention, organosilane monomer is a kind of or its combination of vinyltrimethoxy silane and methacryloxypropyl triethoxyl silane.Consumption is the 2%-3% of Acrylic Acid Monomer weight.
When producing the various high-flexibility water-borne acrylic resin of the present invention, need to add the solubility promoter of 16wt%-20wt%, with the dissolving that helps each monomer with mix.These applicable solubility promoters as: but be not limited only to ethanol, propyl alcohol, butanols and N-BUTYL ACETATE, its form with independent or several combinations is applied to the present invention.
When producing the various high-flexibility water-borne acrylic resin of the present invention, need to reaction last add an amount of neutralizing agent as: but be not limited only to ammoniacal liquor, triethylamine and N, N-dimethylethanolamine etc., its form with independent or several combinations is applied to the present invention.
The used solidifying agent of the present invention is polyisocyanates, and it is the general name of the various ester classes that become with isocyanic acid, and has more than three-the NCO group, as: but be not limited only to the N3390 of Beyer Co., Ltd, N75 and 3175 etc.Its form with independent or several combinations is applied to the present invention.
A kind of high-flexibility water soluble acrylic acid elastic polyurethane resin provided by the invention, by the following method preparation:
Step 1: add the 16wt%-20wt% solubility promoter in the reaction vessel, use the nitrogen replacement air, temperature rises to 80 ℃-90 ℃, add 40wt%-54wt% vinylformic acid short chain monomer, 15wt%-25wt% carboxylic monomer, 5wt%-10wt% acrylate long-chain monomer and 2wt%-3wt% organosilane monomer, after carrying out radical polymerization 2-4 hour under the effect of 0.9wt%-1.2wt% initiator, be cooled to 60 ℃, add the 3wt%-4wt% neutralizing agent, be watered dilution and namely get the high-flexibility water-borne acrylic resin.
Step 2: step 1 gained high-flexibility water-borne acrylic resin and polyisocyanate curing agent is composite, obtain high-flexibility water soluble acrylic acid elastic polyurethane resin.
Another kind of high-flexibility water soluble acrylic acid elastic polyurethane resin provided by the invention, by the following method preparation:
Step 1: add the 16wt%-20wt% solubility promoter in the reaction vessel, use the nitrogen replacement air, temperature rises to 80 ℃-90 ℃, the mixture that is comprised of 0wt%-10wt%MMA, 10wt%-20wt%BMA, 15wt%-21wt%BA, 2.5wt%-3wt%AA, 15wt%-20wt%HEA, 5wt%-10wt%LMA, 2wt%-3wt% organosilane monomer and 0.8wt%-1wt% initiator is added dropwise to container, keep reaction 1 hour in 80 ℃-90 ℃ of temperature after dropwising, add the 0.1wt%-0.2wt% initiator, continue insulation 2 hours; Be cooled to 60 ℃, add the 3wt%-4wt% neutralizing agent, be watered dilution and namely get the high-flexibility water-borne acrylic resin.
Step 2: step 1 gained high-flexibility water-borne acrylic resin and polyisocyanate curing agent is composite, obtain high-flexibility water soluble acrylic acid elastic polyurethane resin.
The Tg that the present invention makes various high-flexibility water-borne acrylic resins is extremely low, at-40 ℃--and between 20 ℃.
According to the actual needs, the high-flexibility water-borne acrylic resin thin up various of the present invention that makes after deviating from partial solvent and filtering, can get the resin that solid content is generally 45%-50%.
The various high-flexibility water soluble acrylic acid elastic polyurethane resins that make take the present invention are as main film forming matter, be equipped with again color stuffing and multiple auxiliary agent (as: wetting dispersing agent, flow agent and defoamer etc.), snappiness and the erosion resistance of the coating that makes significantly improve, and can be applicable to the coating on plastelast surface.
Those of ordinary skills in conjunction with the actual needs of the characteristic and application of plastelast, optionally are equipped with an amount of pigment, filler, film coalescence aid, wetting dispersing agent, flow agent and defoamer etc. and form the water-borne coatings that is used for glass.The component kind such as pigment, filler, film coalescence aid, wetting dispersing agent, flow agent and defoamer and concrete consumption must not limit the present invention.
The beneficial effect that technical solution of the present invention realizes:
High-flexibility water soluble acrylic acid elastic polyurethane resin provided by the invention, from hydroxyl aqueous acrylic resin is synthetic, be equipped with again suitable isocyanate curing agent crosslinking curing, the resin percentage of grafting of gained is high, effectively utilize the advantage of two kinds of resins, improved the over-all properties of resin, as: low temperature (40 ℃) snappiness is good, fastness to rubbing (wiping alcohol fade grading) is good, and is water-fast and weathering resistance is good.
It is main film forming matter that the present invention adopts high-flexibility water soluble acrylic acid elastic polyurethane resin, applicable to the plastelast surface daub on a wall, improves snappiness and the erosion resistance of coating.
Embodiment
Below describe technical scheme of the present invention in detail.The embodiment of the invention is only unrestricted in order to technical scheme of the present invention to be described, although with reference to preferred embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement the technical scheme of invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the claim scope of the present invention.
If the used reagent of the present invention does not clearly indicate, then all available from Sigma-aldrich (Sigma-Aldrich).
Below the high-flexibility water soluble acrylic acid elastic polyurethane resin of the present invention that provides of each embodiment, all make as follows:
Step 1: add ethanol and N-BUTYL ACETATE in the reaction vessel, mix, use the nitrogen replacement air, temperature rises to 80 ℃-90 ℃, the mixture that acrylic ester monomer, hydroxyl substituted acrylate class monomer, organosilane monomer and Diisopropyl azodicarboxylate are formed is added dropwise to container, keep reaction 1 hour in 80 ℃-90 ℃ of temperature after dropwising, add Diisopropyl azodicarboxylate, continue insulation 2 hours; Be cooled to 60 ℃, add N, the neutralization of N-Mono Methyl Ethanol Amine is watered dilution and namely gets solid content 45%-50% high-flexibility water-borne acrylic resin (each component and by weight consumption referring to table 1).
Step 2: high-flexibility water-borne acrylic resin and polyisocyanate curing agent that step 1 makes is composite, make high-flexibility water soluble acrylic acid polyurethane elastomer resin (wherein each component and by weight consumption referring to table 2).
Table 1
* the numeric representation total amount of Diisopropyl azodicarboxylate.
Table 2
The various resins that above-described embodiment 1-embodiment 4 is made are made into varnish, and prescription is such as table 3.
Table 3 lacquer formulation
After the cryodrying film forming, gained paint film properties detects, and the results are shown in Table 4 to gained coating.
Table 4 paint film property index
According to the technology of the present invention effect, the percentage of grafting of prepared high-flexibility water soluble acrylic acid elastic polyurethane resin is high, effectively utilized the advantage of two kinds of resins, not only thermostability, chemical-resistant and weathering resistance all are improved, and the over-all properties of resin also obtains to significantly improve.
Claims (11)
1. high-flexibility water soluble acrylic acid elastic polyurethane resin is made by following steps:
Step 1: by 40wt%-54wt% vinylformic acid short chain monomer, 15wt%-25wt% carboxylic monomer, 5wt%-10wt% acrylate long-chain monomer and 2wt%-3wt% organosilane monomer, after carrying out radical polymerization 2-4 hour under the participation of 16wt%-20wt% solubility promoter and the effect of 0.9wt%-1.2wt% initiator, make the high-flexibility water-borne acrylic resin;
Step 2: water-borne acrylic resin and polyisocyanate curing agent that step 1 makes is composite, make high-flexibility water soluble acrylic acid polyurethane elastomer resin;
Described vinylformic acid short chain monomer is vinylformic acid and the one group of acrylic monomer that becomes the ester composition with C1-C6 unit alcohol institute thereof;
Described acrylate long-chain monomer is the acrylate that vinylformic acid and C10-C20 unit alcohol form;
Described carboxylic monomer is vinylformic acid short chain monomer that hydrogen atom is replaced by hydroxyl on its carbochain.
2. high-flexibility water soluble acrylic acid elastic polyurethane resin according to claim 1 is characterized in that described high-flexibility water soluble acrylic acid polyurethane elastomer resin Tg is-40 ℃--20 ℃.
3. high-flexibility water soluble acrylic acid elastic polyurethane resin according to claim 1 is characterized in that described vinylformic acid short chain monomer is selected from two or more combination of methyl methacrylate, butyl methacrylate, butyl acrylate, methacrylic acid and vinylformic acid.
4. high-flexibility water soluble acrylic acid elastic polyurethane resin according to claim 1 is characterized in that described acrylate long-chain monomer is selected from one or more of vinylformic acid lauryl alcohol ester, vinylformic acid hexadecanol ester and vinylformic acid stearyl alcohol ester.
5. high-flexibility water soluble acrylic acid elastic polyurethane resin according to claim 1 is characterized in that described hydroxy kind monomer is selected from one or more of hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Rocryl 410 and Propylene glycol monoacrylate.
6. high-flexibility water soluble acrylic acid elastic polyurethane resin according to claim 1 is characterized in that described organosilane monomer is selected from one or more of vinyltrimethoxy silane and methacryloxypropyl triethoxyl silane.
7. high-flexibility water soluble acrylic acid elastic polyurethane resin according to claim 1 is characterized in that described neutralizing agent is selected from ammoniacal liquor, triethylamine and N, one or more of N-dimethylethanolamine.
8. high-flexibility water soluble acrylic acid elastic polyurethane resin according to claim 1 is characterized in that described polyisocyanate curing agent is selected from one or more of N3390, N75 and 3175.
9. high-flexibility water soluble acrylic acid elastic polyurethane resin is made by following steps:
Step 1: add the 16wt%-20wt% solubility promoter in the reaction vessel, use the nitrogen replacement air, temperature rises to 80 ℃-90 ℃, the mixture that is comprised of 0wt%-10wt%MMA, 10wt%-20wt%BMA, 15wt%-21wt%BA, 2.5wt%-3wt%AA, 15wt%-20wt%HEA, 5wt%-10wt%LMA, 2wt%-3wt% organosilane monomer and 0.8wt%-1wt% initiator is added dropwise to container, keep reaction 1 hour in 80 ℃-90 ℃ of temperature after dropwising, add the 0.1wt%-0.2wt% initiator, continue insulation 2 hours; Be cooled to 60 ℃, add the 3wt%-4wt% neutralizing agent, be watered dilution and namely get the high-flexibility water-borne acrylic resin;
Step 2: step 1 gained high-flexibility water-borne acrylic resin and polyisocyanate curing agent is composite, obtain high-flexibility water soluble acrylic acid elastic polyurethane resin.
10. coating is take the described high-flexibility water soluble acrylic acid of one of claim 1-9 elastic polyurethane resin as main film forming matter.
11. coating according to claim 10 is characterized in that described coating also comprises one or more of pigment, filler, wetting dispersing agent, flow agent and defoamer.
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| CN106833223A (en) * | 2017-01-14 | 2017-06-13 | 中山市博海精细化工有限公司 | A kind of high-flexibility water varnish of suitable UV offset printings and preparation method thereof |
| CN108178957A (en) * | 2017-11-30 | 2018-06-19 | 漳州三德利油漆涂料有限公司 | Unburned enamel-like paint and its preparation method and application |
| CN108653997A (en) * | 2018-06-21 | 2018-10-16 | 江苏杰威体育设施有限公司 | High-comfort massaging and body-building wab board and its coating |
| CN110845921A (en) * | 2019-11-21 | 2020-02-28 | 深圳市高域化学材料有限公司 | Water-based high-performance coating for plastic |
| CN111057210A (en) * | 2019-12-31 | 2020-04-24 | 阜阳欣奕华材料科技有限公司 | Waterborne polyurethane coating agent and preparation method and application thereof |
| CN111875769A (en) * | 2020-08-21 | 2020-11-03 | 山西省应用化学研究所(有限公司) | High-solid-content aqueous polyurethane composite emulsion and preparation method thereof |
| CN112111220A (en) * | 2020-09-21 | 2020-12-22 | Ppg涂料(天津)有限公司 | Single-layer anti-fingerprint coating composition |
| CN112500773A (en) * | 2020-11-23 | 2021-03-16 | 宁波瑞凌新能源科技有限公司 | Water-based two-component coating and application thereof |
| CN113583187A (en) * | 2021-08-19 | 2021-11-02 | 广州市斯洛柯高分子聚合物有限公司 | Polyurethane modified acrylic emulsion for glass paint and preparation method thereof |
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| CN106833223A (en) * | 2017-01-14 | 2017-06-13 | 中山市博海精细化工有限公司 | A kind of high-flexibility water varnish of suitable UV offset printings and preparation method thereof |
| CN106833223B (en) * | 2017-01-14 | 2019-10-25 | 广东博海化工科技有限公司 | A kind of high-flexibility water varnish and preparation method thereof of suitable UV offset printing |
| CN108178957A (en) * | 2017-11-30 | 2018-06-19 | 漳州三德利油漆涂料有限公司 | Unburned enamel-like paint and its preparation method and application |
| CN108653997A (en) * | 2018-06-21 | 2018-10-16 | 江苏杰威体育设施有限公司 | High-comfort massaging and body-building wab board and its coating |
| CN110845921A (en) * | 2019-11-21 | 2020-02-28 | 深圳市高域化学材料有限公司 | Water-based high-performance coating for plastic |
| CN111057210A (en) * | 2019-12-31 | 2020-04-24 | 阜阳欣奕华材料科技有限公司 | Waterborne polyurethane coating agent and preparation method and application thereof |
| CN111875769A (en) * | 2020-08-21 | 2020-11-03 | 山西省应用化学研究所(有限公司) | High-solid-content aqueous polyurethane composite emulsion and preparation method thereof |
| CN111875769B (en) * | 2020-08-21 | 2022-03-22 | 山西省应用化学研究所(有限公司) | High-solid-content aqueous polyurethane composite emulsion and preparation method thereof |
| CN112111220A (en) * | 2020-09-21 | 2020-12-22 | Ppg涂料(天津)有限公司 | Single-layer anti-fingerprint coating composition |
| CN112111220B (en) * | 2020-09-21 | 2022-07-08 | Ppg涂料(天津)有限公司 | Single-layer anti-fingerprint coating composition |
| CN112500773A (en) * | 2020-11-23 | 2021-03-16 | 宁波瑞凌新能源科技有限公司 | Water-based two-component coating and application thereof |
| CN113583187A (en) * | 2021-08-19 | 2021-11-02 | 广州市斯洛柯高分子聚合物有限公司 | Polyurethane modified acrylic emulsion for glass paint and preparation method thereof |
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