CN115246907A - Preparation method of water-oil universal hydroxy acrylic acid dispersion - Google Patents
Preparation method of water-oil universal hydroxy acrylic acid dispersion Download PDFInfo
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- CN115246907A CN115246907A CN202210080234.6A CN202210080234A CN115246907A CN 115246907 A CN115246907 A CN 115246907A CN 202210080234 A CN202210080234 A CN 202210080234A CN 115246907 A CN115246907 A CN 115246907A
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- C—CHEMISTRY; METALLURGY
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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Abstract
The scheme relates to a preparation method of a water-oil universal hydroxy acrylic acid dispersion, which comprises the steps of heating a solvent, a reactive emulsifier and a reactive diluent to 138-143 ℃; dripping a mixed solution of 80% of vinyl monomer, 80% of functional monomer and 80% of initiator; then, dropwise adding an organic acid reaction type monomer, and mixing the organic acid reaction type monomer with the mixed solution of the remaining 20% of vinyl monomers and 20% of initiator; adding an initiator, and continuously preserving the heat for 1.5 hours; cooling, adding a neutralizer, slowly dropwise adding deionized water, stirring and dispersing, and then discharging; wherein the reactive emulsifier is selected from one of allyl sulfate, vinyl sulfate and polyoxyethylene ether sulfate. The hydroxyl acrylic acid dispersoid prepared by the invention has good compatibility with an oily curing agent and no oil shrinkage; the emulsion has better emulsification effect and is more stable; the emulsion has more transparent appearance and finer particle size; the paint film is transparent and has excellent performance; low hydroxyl content and high performance can be realized; the universal type is strong, and the stirring can be directly performed by hand, so that better performance can be obtained.
Description
Technical Field
The invention relates to the technical field of preparation of hydroxyl acrylic acid dispersoids, in particular to a preparation method of a water-oil universal hydroxyl acrylic acid dispersoid.
Background
The waterborne bi-component polyurethane coating is mainly formed by crosslinking a waterborne hydroxyl acrylic acid dispersion with a waterborne isocyanate curing agent, and has excellent performances such as good flexibility, light and color retention, so that the waterborne hydroxyl acrylic acid dispersion is rapidly popularized in the market, most waterborne hydroxyl acrylic acid dispersions in the market are matched with a waterborne isocyanate curing agent for use at present, and the waterborne bi-component polyurethane coating has the advantages of good compatibility, high paint film gloss and the like.
At present, the price of raw materials in the chemical industry is soaring, wherein the price of isocyanate is higher than that of a water-swelling ship, the price of a water-based isocyanate curing agent is increased all the way, and a state of supply and demand shortage also appears.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a water-oil universal hydroxy acrylic acid dispersion; the prepared dispersion has good compatibility with both a water-based curing agent and an oily curing agent, so that the production cost is reduced, and the problems of gloss loss, oil shrinkage and the like of the oily curing agent adopted by the common hydroxyl acrylic dispersion are solved.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a water-oil universal type hydroxy acrylic acid dispersion comprises the following steps:
1) Adding a quantitative weighed solvent, a reaction type emulsifier and a reactive diluent into a four-neck flask with condensation, and heating to 138-143 ℃;
2) Weighing 80% of vinyl monomer, 80% of functional monomer and 80% of initiator quantitatively, mixing to obtain a solution A, and slowly dripping the solution A into the four-neck flask obtained in the step 1) within 5-6 hours;
3) Weighing organic acid reaction type monomers quantitatively, mixing the organic acid reaction type monomers with the rest 20% of vinyl type monomers and 20% of initiator to obtain a solution B, continuously dripping the solution B into the four-neck flask within 1.5-2h after the dripping in the step 2) is finished,
4) After the dropwise addition is finished, adding an initiator, and continuously preserving the heat for 1.5h at the temperature of 138-143 ℃;
5) Cooling, adding a neutralizing agent, slowly dropwise adding deionized water, stirring and dispersing, and then discharging;
wherein, the reactive emulsifier is selected from one or any combination of allyl sulfate, vinyl sulfate and polyoxyethylene ether sulfate.
Preferably, the solvent, the reactive emulsifier, the reactive diluent, the vinyl monomer, the functional monomer, the organic acid reactive monomer, the initiator and the neutralizer respectively account for 5-6%, 1-3%, 1-2%, 26-31%, 7-10%, 1.2-1.4%, 1.4-1.6%, 1.4-2.4% of the total feeding mass ratio, and the balance is deionized water, and the total mass ratio is 100%.
Preferably, the solvent is selected from one or more of ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, propylene glycol methyl ether acetate, and ethylene glycol methyl ether acetate.
Preferably, the reactive diluent is selected from one or any combination of polyester polyol, polycaprolactone polyol and polycarbonate polyol.
Preferably, the vinyl monomer is selected from one or a combination of methyl (meth) acrylate, benzyl (meth) acrylate, styrene, isooctyl (meth) acrylate and lauryl (meth) acrylate.
Preferably, the functional monomer is selected from one or any combination of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and diacrylate polyethylene glycol 200.
Preferably, the organic acid reactive monomer is selected from one or any combination of carboxylic acid, sulfonic acid and phosphoric acid reactive monomers.
Preferably, the initiator is selected from one or a mixture of any more of tert-butyl peroxymaleate, tert-amyl peroxybenzoate and tert-butyl peroxyacetate; the neutralizing agent is selected from one or any combination of several of dimethylethanolamine, triethylamine, triethanolamine, AMP-95, morpholine and polyether amine.
The beneficial effects of the invention are: (1) The hydroxyl acrylic acid dispersoid prepared by the invention has good compatibility with an oily curing agent and no oil shrinkage; (2) the emulsion has better emulsification effect and is more stable; (3) the emulsion has more transparent appearance and finer particle size; (4) the paint film is transparent and has excellent performance; (5) low hydroxyl high performance can be achieved; (6) The universal type is strong, and the stirring can be directly performed by hand, so that better performance can be obtained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows a hydroxyacrylic acid dispersion obtained in example 4 of the present application.
FIG. 2 is a commercial hydroxyacrylic dispersion.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Furthermore, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The specific examples were obtained according to the following preparation processes.
Weighing the following components according to the mixture ratio of the raw materials: the solvent, the reactive emulsifier, the reactive diluent, the vinyl monomer, the functional monomer, the organic acid reactive monomer, the initiator and the neutralizer respectively account for 5-6%, 1-3%, 1-2%, 26-31%, 7-10%, 1.2-1.4%, 1.4-1.6%, 1.4-2.4% of the total feeding mass ratio, and the balance is deionized water, and the total amount is 100%.
1) Adding a quantitative weighed solvent, a reaction type emulsifier and a reactive diluent into a four-neck flask with condensation, and heating to 138-143 ℃;
2) Weighing 80% of vinyl monomer, 80% of functional monomer and 80% of initiator quantitatively, mixing to obtain a solution A, and slowly dripping the solution A into the four-neck flask obtained in the step 1) within 5-6 hours;
3) Weighing organic acid reaction type monomers quantitatively, mixing the organic acid reaction type monomers with the rest 20% of vinyl monomers and 20% of initiator to obtain a solution B, continuously dripping the solution B into the four-neck flask within 1.5-2h after the dripping in the step 2) is finished,
4) After the dropwise addition is finished, adding an initiator, and continuously preserving the heat for 1.5h at the temperature of 138-143 ℃;
6) Cooling, adding a neutralizer, slowly dropwise adding deionized water, stirring and dispersing, and then discharging;
wherein, the reactive emulsifier is selected from one or a combination of any of allyl sulfate, vinyl sulfate and polyoxyethylene ether sulfate. The reactive emulsifier is creatively added in the preparation process, has a reactive group and a hydrophilic group, and can improve the HLB value of the whole dispersion when being connected to an acrylic monomer main chain, so that the emulsibility of the whole dispersion is enhanced, and the oily curing agent has better compatibility.
The solvent is selected from one or more of ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, propylene glycol methyl ether acetate and ethylene glycol methyl ether acetate; the reactive diluent is selected from one or the combination of any more of polyester polyol, polycaprolactone polyol and polycarbonate polyol. The introduction of the small molecular reactive diluent into the solvent can be beneficial to reducing the dosage of a solvent system, reducing the solvent volatilization and improving the solid content; on the other hand, the introduction of the small-molecule reactive diluent can greatly improve the performance of the integral dispersion paint film.
The vinyl monomer is a conventional acrylic monomer, and is preferably one or a combination of methyl (meth) acrylate, benzyl (meth) acrylate, styrene, isooctyl (meth) acrylate and lauryl (meth) acrylate.
The initiator is selected from one or a mixture of any more of tert-butyl peroxymaleate, tert-amyl peroxybenzoate and tert-butyl peroxyacetate; the neutralizing agent is selected from one or any combination of several of dimethylethanolamine, triethylamine, triethanolamine, AMP-95, morpholine and polyether amine.
The functional monomer is selected from one or a combination of more of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and diacrylate polyethylene glycol 200; the organic acid reactive monomer is selected from one or a combination of any of carboxylic acid, sulfonic acid and phosphoric acid reactive monomers. The functional monomer contains better polar groups, which not only can provide strength during crosslinking, but also can improve the adhesive force to a base material; and the organic acid reactive monomer is used for introducing an acidic group, so that on one hand, the emulsifier is endowed with better polarity and adhesion to a base material, and on the other hand, the acidic group of the emulsifier is neutralized by a neutralizing agent, so that the dispersion performance is endowed. Therefore, the water-oil universal hydroxy acrylic acid dispersoid can be obtained only by reasonably matching the reactive emulsifier, the functional monomer, the organic acid reactive monomer and the other auxiliary agents. The specific embodiments and effects are as follows.
Example 1: 6g of ethylene glycol butyl ether, 2g of sodium vinyl sulfate, 1g of polycaprolactone polyol, 13.3g of methyl methacrylate, 10g of isooctyl acrylate, 7g of hydroxyethyl methacrylate, 5g of benzyl methacrylate, 2.5g of lauryl methacrylate, 1.2g of acrylic acid, 1.3g of tert-butyl peroxymaleate, 1.3g of dimethylethanolamine and the balance of deionized water, wherein the total amount is 100g.
Example 2: 6g of propylene glycol butyl ether, 1.5g of sodium allyl sulfate, 1.5g of polyester polyol, 13.3g of methyl methacrylate, 10g of isooctyl acrylate, 7g of hydroxyethyl methacrylate, 5g of benzyl methacrylate, 2.5g of lauryl methacrylate, 1.2g of acrylic acid, 1.3g of tert-amyl peroxybenzoate, 2.3g of triethanolamine and the balance of deionized water, wherein the total amount is 100g.
Example 3: 7g of propylene glycol methyl ether, 1g of sodium polyoxyethylene ether sulfate, 1.5g of polyester polyol, 12.8g of methyl methacrylate, 10g of isooctyl acrylate, 7.5g of hydroxyethyl methacrylate, 4.5g of benzyl methacrylate, 2.5g of lauryl methacrylate, 1.2g of methacrylic acid, 1.4g of tert-butyl peroxyacetate, 1.5g of AMP-95, and the balance of deionized water, and the total amount is 100g.
Example 4: 7g of dipropylene glycol methyl ether, 1.5g of sodium polyoxyethylene ether sulfate, 1g of polycarbonate polyol, 12.8g of methyl methacrylate, 10g of isooctyl acrylate, 7.5g of hydroxyethyl methacrylate, 4.5g of benzyl methacrylate, 2.5g of lauryl methacrylate, 1.2g of acrylic acid, 1.4g of tert-butyl peroxyacetate, 1.5g of triethylamine and the balance of deionized water, wherein the total amount is 100g.
Example 5: 7g of propylene glycol methyl ether acetate, 1g of polyoxyethylene ether sodium sulfate, 1.5g of polyester polyol, 10.8g of methyl methacrylate, 11g of isooctyl acrylate, 8.5g of hydroxyethyl methacrylate, 4.5g of benzyl methacrylate, 2.5g of lauryl methacrylate, 1.2g of acrylic acid, 1.4g of tert-butyl peroxyacetate, 1.45g of polyetheramine and the balance of deionized water, and the total is 100g.
Comparative example:
the preparation process of the examples is distinguished by the fact that the reactive emulsifier in examples 1 to 5 is removed without addition of reactive emulsifier, corresponding comparative examples 1 to 5 are obtained and the dispersions obtained are examined with respect to their relevant properties and are reported in Table 1.
TABLE 1
As can be seen from Table 1, the water-oil universal hydroxy acrylic acid dispersion can be successfully prepared by adopting the method of the invention, the prepared dispersion has better compatibility (mixing with an oily curing agent) and emulsion stability, and compared with a plurality of experimental data, the dispersions prepared in examples 1 to 5 have better advantages in all properties, wherein the gloss is the highest in example 4. Fig. 1 is a hydroxyacrylic acid dispersion prepared in example 4 of the present invention, and fig. 2 is a state of the hydroxyacrylic acid dispersion, and it is apparent from the figure that the self-made hydroxypropylated emulsion has a smaller particle size and is translucent, and the emulsion performance is more stable. In addition, by comparing the properties with those of comparative examples 1 to 5, the dispersions of examples 1 to 5 have greater advantages in all respects than the dispersions of comparative examples, wherein the better compatibility indicates that the reactive emulsifier plays an important role in producing a dispersion with good compatibility.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (8)
1. The preparation method of the water-oil universal hydroxyl acrylic acid dispersion is characterized by comprising the following steps:
1) Adding a quantitative weighed solvent, a reaction type emulsifier and a reactive diluent into a four-neck flask with condensation, and heating to 138-143 ℃;
2) Weighing 80% of vinyl monomer, 80% of functional monomer and 80% of initiator quantitatively, mixing to obtain a solution A, and slowly dripping the solution A into the four-neck flask obtained in the step 1) within 5-6 hours;
3) Weighing organic acid reaction type monomers quantitatively, mixing the organic acid reaction type monomers with the rest 20% of vinyl monomers and 20% of initiator to obtain a solution B, continuously dripping the solution B into the four-neck flask within 1.5-2h after the dripping in the step 2) is finished,
4) After the dropwise addition is finished, adding an initiator, and continuously preserving the heat for 1.5h at the temperature of 138-143 ℃;
5) Cooling, adding a neutralizing agent, slowly dropwise adding deionized water, stirring and dispersing, and then discharging;
wherein, the reactive emulsifier is selected from one or any combination of allyl sulfate, vinyl sulfate and polyoxyethylene ether sulfate.
2. The method for preparing the water-oil universal hydroxyacrylic acid dispersion according to claim 1, wherein the solvent, the reactive emulsifier, the reactive diluent, the vinyl monomer, the functional monomer, the organic acid reactive monomer, the initiator and the neutralizer respectively account for 5-6%, 1-3%, 1-2%, 26-31%, 7-10%, 1.2-1.4%, 1.4-1.6%, 1.4-2.4% and the balance deionized water of the total feeding mass ratio, and the total amount is 100%.
3. The method for preparing a water-oil universal type hydroxyacrylic acid dispersion according to claim 1, wherein the solvent is one or more selected from the group consisting of ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, propylene glycol methyl ether acetate, and ethylene glycol methyl ether acetate.
4. The method for preparing the water-oil general hydroxyl acrylic dispersion as claimed in claim 1, wherein the reactive diluent is selected from one or a combination of any of polyester polyol, polycaprolactone polyol and polycarbonate polyol.
5. The method for preparing the water-oil universal hydroxyacrylic acid dispersion according to claim 1, wherein the vinyl monomer is selected from one or a combination of methyl (meth) acrylate, benzyl (meth) acrylate, styrene, isooctyl (meth) acrylate, lauryl (meth) acrylate.
6. The method for preparing the water-oil universal type hydroxy acrylic acid dispersion according to claim 1, wherein the functional monomer is one or a combination of any of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and diacrylate polyethylene glycol 200.
7. The method for preparing the water-oil universal type hydroxy acrylic acid dispersion according to claim 1, wherein the organic acid type reactive monomer is one or a combination of any two of carboxylic acid type, sulfonic acid type and phosphoric acid type reactive monomers.
8. The method for preparing the water-oil universal type hydroxy acrylic acid dispersoid as claimed in claim 1, wherein the initiator is one or a mixture of any more of tert-butyl peroxymaleate, tert-amyl peroxybenzoate and tert-butyl peroxyacetate; the neutralizing agent is selected from one or any combination of several of dimethylethanolamine, triethylamine, triethanolamine, AMP-95, morpholine and polyether amine.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530578A (en) * | 2018-04-20 | 2018-09-14 | 同光（江苏）新材料科技有限公司 | A kind of aqueous hydroxy acryl acid resin secondary breakup body and its synthetic method |
| CN108586670A (en) * | 2018-04-04 | 2018-09-28 | 广东衡光新材料科技有限公司 | A kind of hydroxyl acrylic aqueous dispersion and its synthetic method |
| CN110577614A (en) * | 2019-10-18 | 2019-12-17 | 江苏富琪森新材料有限公司 | Preparation of high-solid-content hydroxy acrylic acid dispersion |
| CN113651903A (en) * | 2021-08-10 | 2021-11-16 | 上海中化科技有限公司 | Method for preparing large-particle-size polybutadiene latex based on polymer agglomeration technology |
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- 2022-01-24 CN CN202210080234.6A patent/CN115246907A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586670A (en) * | 2018-04-04 | 2018-09-28 | 广东衡光新材料科技有限公司 | A kind of hydroxyl acrylic aqueous dispersion and its synthetic method |
| CN108530578A (en) * | 2018-04-20 | 2018-09-14 | 同光（江苏）新材料科技有限公司 | A kind of aqueous hydroxy acryl acid resin secondary breakup body and its synthetic method |
| CN110577614A (en) * | 2019-10-18 | 2019-12-17 | 江苏富琪森新材料有限公司 | Preparation of high-solid-content hydroxy acrylic acid dispersion |
| CN113651903A (en) * | 2021-08-10 | 2021-11-16 | 上海中化科技有限公司 | Method for preparing large-particle-size polybutadiene latex based on polymer agglomeration technology |
Non-Patent Citations (1)
| Title |
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| 刘国杰主编: "《现代涂料工艺新技术》", 中国轻工业出版社, pages: 436 * |
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