CN112341892A - Preparation method and application of resin emulsion for single-component waterborne wood coating - Google Patents
Preparation method and application of resin emulsion for single-component waterborne wood coating Download PDFInfo
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- CN112341892A CN112341892A CN202011324032.9A CN202011324032A CN112341892A CN 112341892 A CN112341892 A CN 112341892A CN 202011324032 A CN202011324032 A CN 202011324032A CN 112341892 A CN112341892 A CN 112341892A
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- wood coating
- waterborne wood
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
Abstract
The invention discloses a preparation method and application of resin emulsion for single-component waterborne wood coating, belonging to the field of coating, wherein deionized water is added into a reaction kettle, stirring is started, and the temperature is raised to 82 ℃; pre-emulsification: sequentially adding an emulsifier, formic acid, butyl ester and methyl ester into a reaction kettle, continuously adding 50-160 parts by weight of water into the reaction kettle, then adding a crosslinking monomer and acyl propyl methacrylate, and then adding formic acid, octyl ester and methyl ester; after the dropwise addition is finished, the temperature is kept for 1 hour, then the temperature is reduced, the elimination is carried out, and then the secondary elimination is carried out after the oxidation reduction; and adding adipic dihydrazide, cooling and filtering to obtain the acrylic polymer woodenware emulsion. The hydroxyl polyacrylic acid polymer core-shell structure is designed, has fine particle size, modifies gelation and core lifting, and can replace wood double-component wood paint. The hydroxy-poly-propionic acid polymer emulsion prepared by the invention provides good early sanding property, blocking resistance and stain resistance.
Description
Technical Field
The invention mainly relates to the field of coatings, in particular to a preparation method and application of a resin emulsion for a single-component waterborne wood coating.
Background
In recent years, the restrictions of VOC by related policy and regulation are more strict, and some local governments have been provided with a series of policies and measures to make the use of solvent-based coatings more strict, so that the demand for the water-based woodware paint is higher and higher. The current commonly used waterborne wood lacquer technology comprises waterborne acrylic acid, polyurethane modified acrylic acid, waterborne polyurethane, waterborne UV, waterborne alkyd and the like. The waterborne acrylic acid and the modified emulsion thereof are paid more attention by people due to the advantages of the waterborne acrylic acid and the modified emulsion thereof in the aspect of cost performance.
However, conventional aqueous acrylic acid solutions often give the impression that: the drying time is long, the paint film hardness build-up is slow, and the solvent system is far from stacking resistance. But wood paints, especially industrial wood paints, generally require excellent hardness and anti-stacking properties to meet the requirements of factory line operations. If the Tg of an acrylic emulsion is simply raised to obtain a harder paint film surface, this will often result in the formulation eventually having to incorporate higher quality coalescents. On one hand, the water-borne wood paint faces increasingly strict limited requirements of Volatile Organic Compounds (VOC); more importantly, in addition to the increase of formulation cost, a large amount of film-forming aid often seriously affects the early resistance hardness and anti-stacking property of the paint film, and the early resistance requirement is particularly important for the waterborne requirement of the waterborne industrial wood paint.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method and application of a resin emulsion for a single-component waterborne wood coating, which has good early sanding property, blocking resistance and stain resistance, and has the advantages of quick hardness establishment, difficult foaming and good construction performance.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
on one hand, the invention provides a preparation method of a single-component waterborne wood coating, which comprises the following steps:
1) adding 200 parts by weight of deionized water and 240 parts by weight of deionized water into a reaction kettle, heating at a set temperature, starting stirring, and heating to 82 ℃;
2) pre-emulsification: 1-6 parts by weight of emulsifier, 1-4 parts by weight of formic acid, 10-50 parts by weight of butyl ester and 50-200 parts by weight of methyl formate are sequentially added into a reaction kettle, and are added in a dropwise adding mode, the time is controlled within 45 minutes, and the next step is carried out after half an hour;
3) adding 50-160 parts by weight of deionized water into a reaction kettle, then adding 15-30 parts by weight of crosslinking monomer and 2-10 parts by weight of propyl methacrylate, and then adding 4-16 parts by weight of formic acid, 50-100 parts by weight of octyl ester and 50-110 parts by weight of methyl formate; adding in a dropping mode, and controlling the time within 45 minutes;
4) after the dropwise addition is finished, the temperature is kept for 1 hour, then the temperature is reduced to 65 ℃, the elimination is carried out, and then the secondary elimination is carried out after the oxidation reduction;
5) and cooling to 45 ℃, blending the pH value to pH7.5 +/-1, adding 0.5-1.5 parts of adipic dihydrazide, cooling and filtering to obtain the hydroxyl polypropionic acid polymer emulsion.
Further, the emulsifier in the step 2) is sodium dodecyl sulfate.
Further, the crosslinking monomer in the step 3) is one or two of diacetone acrylamide and adipic acid dihydrazide.
Further, the elimination process in the step 4) is as follows: adding 3-7 parts by weight of ferrous sulfate, 6-8 parts by weight of tert-butyl hydroperoxide, adding 0.4-1 part by weight of ascorbic acid after 5 minutes, stirring for 10 minutes, and post-eliminating residual monomers.
Further, 0.5-1.5 parts by weight of a bactericide is also added in the step 5).
Further, the coating is milky white liquid, the pH value is 7-9, the viscosity is less than 500CPS, and the solid content is 40-41%.
Further, the performance indexes of the prepared coating are as follows: pH7.5 + -1, viscosity less than 500CPS, and solid content 40.5 + -0.5%.
Further, the resulting emulsion contained 40% by weight of a hydroxy-polypropionic acid polymer.
On the other hand, the single-component waterborne wood coating is prepared by the preparation method and is used as a paint film.
Furthermore, adipic acid dihydrazide is added in the normal-temperature curing process of the paint film for matching and crosslinking with the crosslinking monomer.
After adopting such design, the invention has at least the following advantages:
(1) the hydroxyl polyacrylic acid polymer emulsion prepared by the invention is a high-performance emulsion developed for water-based wood furniture paint coated in factories, provides good early sanding property, blocking resistance and stain resistance, can provide excellent early blocking resistance and transparency, and adopts a greenhouse self-crosslinking technology to ensure that the hardness is quickly established, the foaming is not easy to occur and the construction performance is good. In addition, the production process does not use any surfactant containing APEO, harmful substances and formaldehyde.
(2) The hydroxyl polyacrylic acid polymer core-shell structure is designed, has fine particle size, and can replace wood double-component wood paint.
Detailed Description
The present invention is further illustrated by the following examples, but the present invention is not limited to the following examples, and any products similar or equivalent to the present invention, which are obtained in the light of the present invention, are within the scope of protection (note: the ratio of the raw materials in the examples is in parts by weight).
The invention provides an embodiment of a preparation method of a single-component waterborne wood coating, wherein the single-component waterborne wood coating is a single-component paint coating and comprises a hydroxy-poly-propionic acid polymer emulsion, and the weight percentage of the hydroxy-poly-propionic acid polymer is 40%.
Product index of the coating: appearance: milk white liquid, PH 7-9, viscosity: less than 500CPS (3#/60r/min), solid content: 40% -41%,.
A preferable preparation method of the single-component waterborne wood coating comprises the following steps:
first step (core)
1. Adding 200 portions of deionized water and 240 portions of deionized water into the reaction kettle, raising the temperature at a set temperature, starting stirring and raising the temperature to 82 ℃.
2. Pre-emulsification: deionized water (40-60 parts) and 0.5% of the amount of emulsifier monomer are added. 1-6 parts of emulsifier (K12), 1-4 parts of formic acid, 10-50 parts of butyl ester and 50-200 parts of methyl ester are sequentially added, the time is controlled to be finished within 45 minutes, and the second step is carried out after half an hour.
Second step (shell):
adding 50-60 parts of deionized water, 15-30 parts of crosslinking monomer, 2-10 parts of propyl methacrylate, 4-16 parts of formic acid, 50-100 parts of octyl ester and 50-110 parts of methyl formate into a reaction kettle. The second step time was controlled to be within 45 minutes.
The third step:
1. and after the second step of dripping is finished, preserving heat for 1 hour, cooling to 65 ℃, eliminating, carrying out oxidation reduction, and then carrying out secondary elimination (post elimination of residual monomers) (the secondary elimination is the same as the first elimination process).
The elimination process comprises the following steps: adding 3-7 parts by weight of ferrous sulfate, 6-8 parts by weight of tert-butyl hydroperoxide, adding 0.4-1 part by weight of ascorbic acid after 5 minutes, and stirring for 10 minutes.
2. Cooling to 45 deg.C, regulating pH value to 7.5 + -1, adding 0.5-1.5 weight parts of diethyldithiocarbamate, cooling, filtering and packaging. Bactericides can also be added.
The detection indexes of the product produced by the process are as follows: white in appearance (blue head), PH7.5 ± 1, solid content: 40.5 ± 0.5%, viscosity (mps.a) < 500.
The hydroxyl polyacrylic acid polymer core-shell structure design (the first step of core preparation and the second step of shell preparation) has fine particle size, and the gelation core is modified, so that the hydroxyl polyacrylic acid polymer core-shell structure can replace two-component wood paint for woodenware. The core-shell structure is a chemical synthesis process, and the hardness of the core and the shell can be adjusted according to requirements.
The crosslinking monomer of the invention is a pair of combinations, which is composed of diacetone acrylamide and adipic dihydrazide, the diacetone acrylamide is added during the reaction, the adipic dihydrazide is added during the curing at normal temperature, and when the reaction is finished and added into the emulsion for application (when a paint film is made), the adipic dihydrazide and the emulsion are subjected to crosslinking reaction along with the evaporation of moisture along with the evaporation of air.
The hydroxyl polyacrylic acid polymer emulsion prepared by the invention is a high-performance emulsion developed for water-based wood furniture paint coated in factories, provides good early sanding property, blocking resistance and stain resistance, can provide excellent early blocking resistance and transparency, is shown in table 1, and adopts a greenhouse self-crosslinking technology, so that the hardness is quickly established, the foaming is not easy to occur, and the construction performance is good. In addition, the production process does not use any surfactant containing APEO, harmful substances and formaldehyde.
TABLE 1 Properties of Single-component waterborne Wood coatings made according to the present invention
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention in any way, and it will be apparent to those skilled in the art that the above description of the present invention can be applied to various modifications, equivalent variations or modifications without departing from the spirit and scope of the present invention.
Claims (10)
1. A preparation method of resin emulsion for single-component waterborne wood coating is characterized by comprising the following steps:
1) adding 200 parts by weight of deionized water and 240 parts by weight of deionized water into a reaction kettle, heating at a set temperature, starting stirring, and heating to 82 ℃;
2) pre-emulsification: 1-6 parts by weight of emulsifier, 1-4 parts by weight of formic acid, 10-50 parts by weight of butyl ester and 50-200 parts by weight of methyl formate are sequentially added into a reaction kettle, and are added in a dropwise adding mode, the time is controlled within 45 minutes, and the next step is carried out after half an hour;
3) adding 50-160 parts by weight of deionized water into a reaction kettle, then adding 15-30 parts by weight of crosslinking monomer and 2-10 parts by weight of propyl methacrylate, and then adding 4-16 parts by weight of formic acid, 50-100 parts by weight of octyl ester and 50-110 parts by weight of methyl formate; adding in a dropping mode, and controlling the time within 45 minutes;
4) after the dropwise addition is finished, the temperature is kept for 1 hour, then the temperature is reduced to 65 ℃, the elimination is carried out, and then the secondary elimination is carried out after the oxidation reduction;
5) and cooling to 45 ℃, adjusting the pH value to pH7.5 +/-1, adding 0.5-1.5 parts of adipic acid dihydrazide, cooling and filtering to obtain the acrylic polymer woodware emulsion.
2. The method for preparing a single-component waterborne wood coating according to claim 1, wherein the emulsifier in the step 2) is sodium dodecyl sulfate.
3. The method for preparing a single-component waterborne wood coating according to claim 1 or 2, wherein the crosslinking monomer in the step 3) is diacetone acrylamide, and is used for matching and crosslinking with adipic acid dihydrazide in a normal-temperature curing stage.
4. The method for preparing a single-component waterborne wood coating according to any one of claims 1 to 3, wherein the elimination process in the step 4) is as follows: adding 3-7 parts by weight of ferrous sulfate, 6-8 parts by weight of tert-butyl hydroperoxide, adding 0.4-1 part by weight of ascorbic acid after 5 minutes, stirring for 10 minutes, and post-eliminating residual monomers.
5. The preparation method of the single-component waterborne wood coating according to any one of claims 1 to 4, wherein 0.5 to 1.5 parts by weight of a bactericide is further added in the step 5).
6. The method for preparing the single-component waterborne wood coating according to any one of claims 1 to 5, wherein the coating is a milky white liquid, has a pH value of 7 to 9, a viscosity of less than 500CPS, and a solid content of 40 to 41%.
7. The method for preparing single-component waterborne wood coating according to any one of claims 1 to 6, wherein the performance index of the prepared coating is as follows: pH7.5 + -1, viscosity less than 500CPS, and solid content 40.5 + -0.5%.
8. The method for preparing a single-component waterborne wood coating according to any one of claims 1 to 7, wherein the emulsion contains 40 wt% of hydroxyl polyacrylic acid polymer.
9. The application of the resin emulsion for the single-component waterborne wood coating is characterized in that the single-component waterborne wood coating is prepared by the preparation method of any one of claims 1 to 8 and is used as a paint film.
10. The application of the single-component waterborne wood coating according to claim 9, wherein adipic acid dihydrazide is added in the normal-temperature curing process of the paint film for matching and crosslinking with a crosslinking monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011324032.9A CN112341892A (en) | 2020-11-23 | 2020-11-23 | Preparation method and application of resin emulsion for single-component waterborne wood coating |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011324032.9A CN112341892A (en) | 2020-11-23 | 2020-11-23 | Preparation method and application of resin emulsion for single-component waterborne wood coating |
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| CN112341892A true CN112341892A (en) | 2021-02-09 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319124A (en) * | 2008-07-01 | 2008-12-10 | 窦俊英 | Environment friendly high-density aqueous woodenware emulsion paint and preparation method thereof |
| CN102516465A (en) * | 2011-11-19 | 2012-06-27 | 烟台万华聚氨酯股份有限公司 | High-elasticity waterborne polyurethane-acrylate composite resin, and preparation method and application thereof |
| CN102827322A (en) * | 2012-08-14 | 2012-12-19 | 华南理工大学 | Preparation method and application of internal-external dual cross-linked core-shell structured acrylic acid emulsion |
| CN109439124A (en) * | 2018-10-04 | 2019-03-08 | 湖北嘉德普安涂料股份有限公司 | Woodcare paint aqueous dumb light self-crosslinking acrylic lotion and its synthetic method |
-
2020
- 2020-11-23 CN CN202011324032.9A patent/CN112341892A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319124A (en) * | 2008-07-01 | 2008-12-10 | 窦俊英 | Environment friendly high-density aqueous woodenware emulsion paint and preparation method thereof |
| CN102516465A (en) * | 2011-11-19 | 2012-06-27 | 烟台万华聚氨酯股份有限公司 | High-elasticity waterborne polyurethane-acrylate composite resin, and preparation method and application thereof |
| CN102827322A (en) * | 2012-08-14 | 2012-12-19 | 华南理工大学 | Preparation method and application of internal-external dual cross-linked core-shell structured acrylic acid emulsion |
| CN109439124A (en) * | 2018-10-04 | 2019-03-08 | 湖北嘉德普安涂料股份有限公司 | Woodcare paint aqueous dumb light self-crosslinking acrylic lotion and its synthetic method |
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