CN108192046B - Novel hydroxyl acrylic acid dispersion and application thereof - Google Patents
Novel hydroxyl acrylic acid dispersion and application thereof Download PDFInfo
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- CN108192046B CN108192046B CN201810004702.5A CN201810004702A CN108192046B CN 108192046 B CN108192046 B CN 108192046B CN 201810004702 A CN201810004702 A CN 201810004702A CN 108192046 B CN108192046 B CN 108192046B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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Abstract
The invention relates to a novel hydroxyl acrylic acid dispersoid and application thereof, wherein the novel hydroxyl acrylic acid dispersoid is polyether polyol-unsaturated polyester modified hydroxyl acrylic acid dispersoid, the solid content of the dispersoid is 54 +/-1.0%, the viscosity of the dispersoid is 2100 +/-50 mpa.s, the hydroxyl value of the dispersoid is 5.2 +/-0.1, and the VOC content of the dispersoid is 26 +/-4.0 mu g/g. The hydroxyl acrylic acid dispersoid has the characteristics of high solid content, high hydroxyl value, low viscosity, good paint making fullness, luster, water resistance and the like, is expected to be applied to the field of paint making and widely replaces the traditional hydroxyl acrylic acid dispersoid.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a novel hydroxyl acrylic acid dispersion and application thereof.
Background
The waterborne two-component polyurethane is mainly prepared by curing and crosslinking a hydroxyl functional group in a waterborne hydroxyl acrylic acid dispersoid and a waterborne polyisocyanate curing agent. The waterborne two-component polyurethane has the advantages of high gloss, good color retention and weather resistance and the like, along with the development of economy and society, the diversification of the market and the stricter environmental requirements, the dosage of the solvent-type resin is controlled day by day, and the waterborne resin is favored by consumers and markets because of the obvious advantages of low VOC content and the like. In addition, the traditional water-based hydroxyl acrylic acid dispersoid has defects of certain degree in luster and fullness due to the fact that the solid content is relatively low. Therefore, a material which can effectively improve the water resistance of a two-component polyurethane system paint film, reduce the viscosity of resin and improve the solid content of dispersion is urgently needed to replace the traditional polyurethane material. In order to overcome the limitations, the invention develops a novel hydroxyl acrylic acid dispersion, which has the solid content of 54 +/-1.0 percent, the viscosity of 2100 +/-50 mpa.s, the hydroxyl value of 5.2 +/-0.1 and the VOC content of 26 +/-4.0 mu g/g.
Disclosure of Invention
The invention provides a polyether polyol-unsaturated polyester modified hydroxyl acrylic acid dispersoid which is characterized by comprising the following steps:
(1) mixing organic epoxide, compound containing active hydrogen group, solvent, catalyst and unsaturated polyester, heating to 140-145 ℃, and stirring for reaction for 0.5-1h to obtain a reaction mixture;
(2) adding an initiator and an acrylate monomer into the reaction mixture obtained in the step (1) in two steps, keeping the temperature for 1-2h after dropwise adding, cooling to 75-80 ℃, adding a neutralizing agent, adding deionized water, stirring and dispersing for 1-2h to obtain the polyether polyol-unsaturated polyester modified hydroxyl acrylic acid dispersoid.
The organic epoxide in the step (1) is selected from one or more of ethylene oxide, propylene oxide, epichlorohydrin, butylene oxide, furan and tetrahydrofuran; the compound containing active hydrogen groups is selected from any one of propylene glycol, glycerol, trimethylolpropane, ethylenediamine pentaerythritol, xylitol, triethylene diamine, sorbitol, sucrose, bisphenol A, bisphenol S, tris (2-hydroxyethyl) isocyanate, toluene diamine, ethylene glycol, m-xylylenediamine, ethylene diamine, isocyanate, butanediol, triethanolamine, n-butanol, and isopropanol; the solvent is a conventional solvent for resin preparation, preferably one of propylene glycol methyl ether acetate, propylene glycol diacetate and propylene glycol ethyl ether; the catalyst is a conventional catalyst for preparing polyether polyols, preferably alkali metal hydroxides (e.g. NaOH, KOH, CsOH).
The initiator in the step (2) is selected from one of tert-butyl peroxybenzoate, tert-butyl peroxide, dibenzoyl peroxide, ammonium persulfate, azobisisobutyronitrile, tert-butyl peroxybenzoate, cumene hydroperoxide or dicumyl peroxide; the neutralizer is: triethylamine, N-dimethylethanolamine, ammonia water or tripropylamine, and acrylate monomer selected from one or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and hydroxyethyl methacrylate.
The weight parts of the raw materials of the components in the steps (1) and (2) are as follows:
2-3 parts of organic epoxide, 2-5 parts of compound containing active hydrogen group, 2-3 parts of solvent, 0.01-0.03 part of catalyst, 2-3 parts of unsaturated polyester, 1-2 parts of initiator, 30-40 parts of acrylate monomer, 4-6 parts of neutralizer and the balance of deionized water, wherein the total is 100 parts.
The polyether polyol-unsaturated polyester modified hydroxyl acrylic acid dispersoid has the solid content of 54 +/-1.0 percent, the viscosity of 2100 +/-50 mpa.s, the hydroxyl value of 5.2 +/-0.1 and the VOC content of 26 +/-4.0 mu g/g.
Another embodiment of the invention provides the use of the polyether polyol-unsaturated polyester-modified hydroxyacrylic dispersions for the preparation of lacquers and coatings.
The initiator and the acrylic monomer are added in two steps, preferably, half of the mass of the initiator and the acrylic monomer are added in the first step; the second step adds the remaining half mass of initiator and acrylic monomer.
The unsaturated polyester of the invention contains unsaturated double bonds, has an acid value of 10-25 mg KOH/g solid content of 70-78%, and further preferably contains acrylic acid copolymer. The purpose of containing unsaturated double bonds is mainly to realize effective grafting through copolymerization of the unsaturated double bonds in the polyester and acrylate monomers. The purpose of containing acrylic acid is mainly to neutralize and salify with amine neutralizer in the later period, effectively realize water-based emulsification and achieve the effect of self-emulsification.
Compared with the prior art, the invention has the advantages that: (1) the method adopts the organic epoxide, the active hydrogen compound, the catalyst and a small amount of conventional solvent to synthesize the polyether polyol, and simultaneously uses the organic epoxide, the active hydrogen compound, the catalyst and the unsaturated polyester (as a priming solvent) as reaction media for synthesizing the hydroxyl acrylic acid dispersoid, so that the dosage of the cosolvent can be effectively reduced, and the emission of the total amount of VOC (the unsaturated polyester is used as the reaction media, the solid content of the system is improved, the dosage of the solvent is reduced, and the content of VOC is reduced) is reduced from the source; (2) the unsaturated polyester has the advantages of high fullness, good flexibility and the like, and the unsaturated double bond in the unsaturated polyester and the acrylate monomer are copolymerized through free radicals so as to be grafted together, so that the gloss and the fullness of the hydroxyl acrylic acid dispersoid can be effectively improved; (3) the polyether polyol is generated by the organic epoxide and the active hydrogen compound under the action of the catalyst, has stronger hydrophobicity, and can effectively improve the water resistance of a paint film of a bi-component polyurethane system, reduce the viscosity of resin and improve the solid content of the dispersion by introducing the polyether polyol into the hydroxyl acrylic acid dispersion; (4) the hydroxyl acrylic acid dispersoid prepared by the invention has the following characteristics: the solvent content is lower, and the environment is friendly; high hydroxyl content, relatively high solid content and low viscosity; third, the fullness, the luster and the water resistance are excellent; narrow particle size distribution range and blue light intensity; relatively low cost, simple preparation process, easy control and high economic value.
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IR diagram of product A in FIG. 1
FIG. 2 particle size distribution diagram of product A
Detailed Description
In order to facilitate a further understanding of the invention, the following examples are provided to illustrate it in more detail. However, these examples are only for better understanding of the present invention and are not intended to limit the scope or the principle of the present invention, and the embodiments of the present invention are not limited to the following.
The unsaturated polyester used in the examples of the present invention was purchased from Changzhou Kexiang high molecular materials Co., Ltd, and the unsaturated polyester contained an acrylic copolymer, having an unsaturated double bond, an acid value of 10 to 25 mg KOH/g solid, and a solid content of 70 to 78%.
Example 1
(1) Mixing 2g of epoxy propane, 3.0g of butanediol, 2g of propylene glycol methyl ether acetate, 0.02g of potassium hydroxide and 2.0g of unsaturated polyester, heating to 145 ℃ for 140 ℃, and stirring for reaction for 0.5-1h to obtain a reaction mixture;
(2) and (2) dropwise adding 0.5g of di-tert-butyl peroxide, 5g of methyl acrylate, 6g of methyl methacrylate and 4g of butyl acrylate into the reaction mixture obtained in the step (1), keeping the temperature for 1h after dropwise adding, continuously dropwise adding 0.5g of the rest di-tert-butyl peroxide, 5g of methyl acrylate, 6g of methyl methacrylate and 4g of butyl acrylate, keeping the temperature for 1-2h after dropwise adding, cooling to 75-80 ℃, adding 4g of N, N-dimethylethanolamine for neutralization, adding a proper amount of deionized water, stirring and dispersing for 1-2h, and discharging to obtain the polyether polyol-unsaturated polyester modified hydroxyacrylic acid dispersoid (hereinafter referred to as product A).
Example 2
(1) Mixing 3g of epoxy chloropropane, 5.0g of propylene glycol, 3g of propylene glycol methyl ether acetate, 0.03g of potassium hydroxide and 3.0g of unsaturated polyester, heating to 145 ℃ for 140 ℃, and stirring for reaction for 0.5-1h to obtain a reaction mixture;
(2) adding 1.0g of dibenzoyl peroxide, 8g of methyl acrylate, 2g of methyl methacrylate, 5g of hydroxyethyl methacrylate and 5g of ethyl acrylate into the reaction mixture obtained in the step (1), keeping the temperature for 1h after the addition, continuously adding the rest 1.0g of dibenzoyl peroxide, 8g of methyl acrylate, 2g of methyl methacrylate, 5g of hydroxyethyl methacrylate and 5g of ethyl acrylate, keeping the temperature for 1-2h after the addition, cooling to 75-80 ℃, adding 6g of triethylamine for neutralization, adding a proper amount of deionized water, stirring and dispersing for 1-2h, and discharging to obtain the polyether polyol-unsaturated polyester modified hydroxyacrylic acid dispersion (hereinafter referred to as a product B).
Example 3
(1) Mixing 2.37g of propylene oxide, 3.66g of butanediol, 3g of propylene glycol methyl ether acetate, 0.02g of potassium hydroxide and 2.21g of unsaturated polyester, heating to 145 ℃ and stirring for reaction for 0.5-1h to obtain a reaction mixture;
(2) and (2) dropwise adding 0.56g of di-tert-butyl peroxide and 18.0g of acrylate monomers (the mass ratio of methyl acrylate to methyl methacrylate to butyl acrylate is 1:1:1), keeping the temperature for 1h after dropwise adding, continuously dropwise adding 0.56g of the rest di-tert-butyl peroxide and 18.0g of the acrylate monomers (the mass ratio of methyl acrylate to methyl methacrylate to butyl acrylate is 1:1:1), keeping the temperature for 1-2h after dropwise adding, cooling to 75-80 ℃, adding 5.4g of N, N-dimethylethanolamine for neutralization, adding a proper amount of deionized water, stirring and dispersing for 1-2h, and discharging to obtain the polyether polyol-unsaturated polyester modified hydroxyacrylic acid dispersion (hereinafter referred to as product C).
Example 4
(1) Mixing 3.0g of tetrahydrofuran, 3.0g of butanediol, 2.5g of propylene glycol methyl ether acetate, 0.01g of potassium hydroxide and 2.0g of unsaturated polyester, heating to 145 ℃ for 140 ℃, and stirring for reaction for 0.5-1h to obtain a reaction mixture;
(2) and (2) dropwise adding 0.5g of di-tert-butyl peroxide, 5g of methyl acrylate, 6g of methyl methacrylate and 4g of butyl acrylate into the reaction mixture obtained in the step (1), keeping the temperature for 1h after dropwise adding, continuously dropwise adding 0.5g of the rest di-tert-butyl peroxide, 5g of methyl acrylate, 6g of methyl methacrylate and 4g of butyl acrylate, keeping the temperature for 1-2h after dropwise adding, cooling to 75-80 ℃, adding 4g of N, N-dimethylethanolamine for neutralization, adding a proper amount of deionized water, stirring and dispersing for 1-2h, and discharging to obtain the polyether polyol-unsaturated polyester modified hydroxyacrylic acid dispersoid (hereinafter referred to as product D).
Example 5
(1) Mixing 2g of epoxy propane, 3.0g of butanediol, 2g of propylene glycol methyl ether acetate, 0.02g of potassium hydroxide and 2.0g of styrene, heating to 145 ℃ and stirring for reaction for 0.5-1h to obtain a reaction mixture;
(2) and (2) dropwise adding 0.5g of di-tert-butyl peroxide, 5g of methyl acrylate, 6g of methyl methacrylate and 4g of butyl acrylate into the reaction mixture obtained in the step (1), keeping the temperature for 1h after dropwise adding, continuously dropwise adding 0.5g of the rest di-tert-butyl peroxide, 5g of methyl acrylate, 6g of methyl methacrylate and 4g of butyl acrylate, keeping the temperature for 1-2h after dropwise adding, cooling to 75-80 ℃, adding 4g of N, N-dimethylethanolamine for neutralization, adding a proper amount of deionized water, stirring and dispersing for 1-2h, and discharging to obtain a product E.
Example 6
(1) Mixing 2g of propylene glycol methyl ether acetate and 2.0g of unsaturated polyester, heating to 140-145 ℃, and stirring for reaction for 0.5-1h to obtain a reaction mixture;
(2) and (2) dropwise adding 0.5g of di-tert-butyl peroxide, 5g of methyl acrylate, 6g of methyl methacrylate and 4g of butyl acrylate into the reaction mixture obtained in the step (1), keeping the temperature for 1h after dropwise adding, continuously dropwise adding 0.5g of the rest di-tert-butyl peroxide, 5g of methyl acrylate, 6g of methyl methacrylate and 4g of butyl acrylate, keeping the temperature for 1-2h after dropwise adding, cooling to 75-80 ℃, adding 4g of N, N-dimethylethanolamine for neutralization, adding a proper amount of deionized water, stirring and dispersing for 1-2h, and discharging to obtain a product F.
Example 7
The viscosity of the dispersions of the examples was measured using a rotational viscometer and the solids content of the dispersions was measured using a 160 ℃ bake for 1 h. The specific data are shown in Table 1.
TABLE 1
"-" indicates not measured.
Example 8
The hydroxyl acrylic acid dispersoid of the product A, the product of the market model 1121 and the product of the Chinese invention patent (application number: 201611200208.3) in the example 1 (the patent product for short) and the polyisocyanate curing agent are crosslinked to prepare paint, and the specific data are shown in the table 2 in a comparison experiment.
TABLE 2
As can be seen from the test results of examples 7-8, the polyether polyol-unsaturated polyester modified hydroxy acrylic acid dispersion prepared by the invention has higher solid content and hydroxyl value, low VOC content, excellent water resistance in paint preparation, and no foaming, no falling and no color change after 2 days.
Claims (2)
1. A polyether polyol-unsaturated polyester modified hydroxy acrylic acid dispersion is characterized in that the preparation method comprises the following steps:
(1) mixing 3g of epoxy chloropropane, 5.0g of propylene glycol, 3g of propylene glycol methyl ether acetate, 0.03g of potassium hydroxide and 3.0g of unsaturated polyester, heating to 145 ℃ for 140 ℃, and stirring for reaction for 0.5-1h to obtain a reaction mixture;
(2) adding 1.0g of dibenzoyl peroxide, 8g of methyl acrylate, 2g of methyl methacrylate, 5g of hydroxyethyl methacrylate and 5g of ethyl acrylate into the reaction mixture obtained in the step (1), keeping the temperature for 1h after the addition, continuously adding the rest 1.0g of dibenzoyl peroxide, 8g of methyl acrylate, 2g of methyl methacrylate, 5g of hydroxyethyl methacrylate and 5g of ethyl acrylate, keeping the temperature for 1-2h after the addition, cooling to 75-80 ℃, adding 6g of triethylamine for neutralization, adding a proper amount of deionized water, stirring and dispersing for 1-2h, and discharging to obtain the polyether polyol-unsaturated polyester modified hydroxyacrylic acid dispersion.
2. Use of the polyether polyol-unsaturated polyester modified hydroxyacrylic dispersion according to claim 1 for the preparation of paints and coatings.
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| CN112300306B (en) * | 2020-11-09 | 2022-03-29 | 广东石油化工学院 | Biodegradable radiation-curable (methyl) acrylate and preparation method thereof |
| CN114058028B (en) * | 2021-11-04 | 2023-06-16 | 万华化学集团股份有限公司 | Hydroxy acrylic acid dispersoid and preparation method and application thereof |
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| CN105622857B (en) * | 2016-04-01 | 2017-09-29 | 武汉大学 | A kind of preparation method of inierpeneirating network structure aqueous polyurethane nano composite |
| WO2017191653A1 (en) * | 2016-05-02 | 2017-11-09 | Asian Paints Ltd. | Water borne castor oil modified acrylic copolymer dispersions for surface coatings |
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