CN109180854B - Water-based self-extinction gloss-controllable acrylic resin and preparation method thereof - Google Patents
Water-based self-extinction gloss-controllable acrylic resin and preparation method thereof Download PDFInfo
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- CN109180854B CN109180854B CN201810895196.3A CN201810895196A CN109180854B CN 109180854 B CN109180854 B CN 109180854B CN 201810895196 A CN201810895196 A CN 201810895196A CN 109180854 B CN109180854 B CN 109180854B
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
Abstract
The invention provides a water-based self-extinction gloss-controllable acrylic resin which comprises, by weight, 2-20 parts of seed monomers, 20-50 parts of shell monomers, 0.5-3 parts of emulsifiers, 0.1-1 part of water-based initiators, 40-150 parts of water, 0-0.5 part of buffering agents and 0-5 parts of self-crosslinking monomers. Wherein the shell monomer is an acrylate monomer A; the seed monomer is an acrylate monomer B and an acrylic monomer, the acrylic monomer comprises acrylic acid and an acrylic acid derivative, and the weight of the acrylic acid derivative is greater than or equal to that of the acrylic acid. The content of the organic polymeric flocculant is controlled by controlling different proportions of carboxyl groups in acrylic acid and acrylic acid derivatives, so that the glossiness of the coating is controlled, and ideal coating gloss can be simply obtained. The invention also provides a preparation method of the acrylic resin.
Description
Technical Field
The invention relates to the technical field of acrylic resin, in particular to aqueous self-extinction gloss-controllable acrylic resin and a preparation method thereof.
Background
In recent years, the living standard of people is gradually improved, and people feel that the high-gloss paint with high gloss reflects light seriously after forming a film in the use of wood furniture, so that the damage to the visual ability is great. In addition, people's aesthetic concepts compromise leisure life and fashion taste, and the demand for low-gloss coatings with soft and elegant appearance is greatly increased. Accordingly, matte coatings have received attention. Most of the traditional extinction coatings adopt solvents, and then powder materials are added for extinction, and in recent years, due to the rising of environmental awareness and the establishment of relevant regulations, the traditional extinction coatings do not meet the requirement of environmental protection of the coatings in the current regulations. In addition, the solvent-based matting coatings are volatile and pose safety concerns during the summer days of inflammation.
In particular, the addition of a powdery material in conventional matte coatings results in a decrease in the performance of the coating. Film matting can be roughly classified into two categories, physical matting and chemical matting, according to the principle. The traditional extinction coating is more commonly used for physical extinction, because the added powdery material coating can increase the unevenness of the film surface, enhance the scattering of light and reduce the reflection of light in the film forming process, but the traditional extinction coating is easy to generate the problem of poor dispersion and causes the reduction of the mechanical strength of the whole paint film due to the film forming defect.
In view of the above, it is necessary to develop an aqueous self-extinction gloss-controllable acrylic resin to solve the above technical problems.
Disclosure of Invention
The invention aims to provide a waterborne self-extinction gloss-controllable acrylic resin, which can control the gloss degree of a coating film through the content of an organic polymeric flocculant, can simply obtain ideal coating film gloss, and can improve the water resistance, the wear resistance and higher hardness of the coating film.
The invention also aims to provide a preparation method of the acrylic resin.
In order to achieve the purpose, the invention provides a waterborne self-extinction controlled-gloss acrylic resin which comprises the following components in parts by weight:
wherein the shell monomer is an acrylate monomer A; the seed monomer is an acrylate monomer B and an acrylic monomer, the acrylic monomer comprises acrylic acid and derivatives thereof, and the weight of the acrylic acid derivatives is greater than or equal to that of the acrylic acid.
Compared with the prior art, the acrylic resin with controllable luster and aqueous self-extinction is prepared by introducing acrylic acid derivatives and acrylic acid into seed monomers and forming an organic polymeric flocculant by the acrylic acid derivatives and the acrylic acid monomers. And the weight of the acrylic acid derivative is controlled to be more than or equal to that of acrylic acid, so that the proportion of carboxyl is controlled, the content of the synthetic organic polymeric flocculant is controlled, and the glossiness of the coating is controlled through the content of the organic polymeric flocculant. The mechanism is that the acid contents of acrylic acid derivative and acrylic acid in unit mass are different, and the ratio of carboxyl in acrylic acid derivative and acrylic acid is controlled by the weight ratio of acrylic acid derivative and acrylic acid, so as to control the acid content in seed monomer, thereby controlling the number of macromolecular flocculating agent in seed monomer, determining the flocculation degree and the coating particle size, and influencing the coating film gloss. In addition, this application adopts water as the dispersant, belongs to water based paint, and accords with the environmental protection requirement.
Preferably, the seed monomer can be selected from 2 parts, 5 parts, 10 parts, 15 parts and 20 parts. Specifically, the seed monomer is an acrylate monomer B and an acrylic monomer, the acrylic monomer comprises acrylic acid and derivatives thereof, and the acrylate monomer B comprises one or more of methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl methacrylate, isooctyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and lauryl methacrylate.
Preferably, the weight ratio of acrylic acid derivative to acrylic acid is 5 or less than 5. Preferably, the weight ratio of the acrylic acid derivative to the acrylic acid is 1-5. For example, the weight ratio may be 1:1, 2:1, 3:1, 4:1, 5: 1. The ratio of the acrylic acid derivative to the carboxyl in the acrylic acid is controlled, so that the acid content in the seed monomer is controlled, the content of the synthetic organic polymeric flocculant is controlled, and the glossiness of the coating is controlled through the content of the organic polymeric flocculant. And as the acid content in the seed monomer rises, the number of the synthesized organic polymer flocculant increases and the particle size increases, and simultaneously, because the flocculation effect is a loose structure, the refractive index of the emulsion of air and acrylic ester monomer in the paint film is different, thereby further reducing the gloss of the paint film.
Preferably, the acrylic acid derivative is selected from any one of methacrylic acid, maleic acid and maleic anhydride, the acrylic acid tends to extend the segments outward, and the acrylic acid derivative is restrained from curling inward, thereby effectively forming the organic polymeric flocculant. Especially, the matching of the methacrylic acid and the acrylic acid internal and external structures can easily form the organic polymer flocculant.
Preferably, the seed monomer in the present application comprises, by weight:
for example, methyl methacrylate can be selected from 2 parts, 4 parts, 6 parts and 8 parts; 2-ethylhexyl acrylate can be selected from 0.1 part, 0.5 part, 1 part, 1.5 parts, 2 parts; methacrylic acid can be selected from 0.6 part, 0.7 part, 0.8 part, 0.9 part and 1 part; the acrylic acid may be selected from 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, and 0.6 parts.
Preferably, the shell monomer of the present application may be selected from 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts. Specifically, the shell monomer is an acrylate monomer A, and the acrylate monomer A is selected from two or more of methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl methacrylate, isooctyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and lauryl methacrylate. More preferably, in the present application, the shell monomer comprises, in parts by weight:
for example, methyl methacrylate can be selected from 15 parts, 20 parts, 25 parts and 30 parts; the 2-ethylhexyl acrylate can be selected from 8 parts, 12 parts, 14 parts, 16 parts and 18 parts; the butyl acrylate can be selected from 2 parts, 3 parts and 4 parts; the isooctyl methacrylate can be selected from 0.2 part, 0.3 part, 0.4 part, 0.5 part and 0.6 part; the hydroxyethyl methacrylate can be selected from 1 part, 1.2 parts, 1.4 parts, 1.5 parts and 1.6 parts.
Preferably, the self-crosslinking monomer can be selected from 0 part, 1 part, 2 parts, 3 parts, 4 parts and 5 parts. Specifically, the self-crosslinking monomer includes:
(a) 0.5-1.5 parts of adipic acid dihydrazide;
(b) 0.5-1.5 parts of one or more of N- (2-hydroxyethyl) acrylamide, 1, 6-hexanediol diacrylate and N-hydroxymethyl acrylamide; and
(c) 0.5-1.5 parts of one or more of acetoacetoxyethyl methacrylate and diacetone acrylamide.
The self-crosslinking monomer is introduced into the waterborne self-extinction controllable-gloss acrylic resin, so that the film forming temperature is reduced, and the energy is effectively saved. Especially, the introduction of the self-crosslinking monomer can enable the seed resin containing the organic polymeric flocculant formed by the seed monomer to react with the shell monomer to assist in film formation, and the water resistance, the wear resistance, the storage stability and the hardness of the coating film are improved. Especially, the storage stability of the coating is greatly improved under the combined action of the self-crosslinking monomer and the organic polymeric flocculant.
Preferably, the buffer can be selected from 0 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part and 0.5 part. Specifically, the buffer may be one of sodium hydroxide, potassium hydroxide, sodium bicarbonate, ammonia, diethanolamine, and triethanolamine. The use of the above-mentioned buffers allows a relatively rapid adjustment to the desired pH range.
Preferably, water can be selected from 40 parts, 60 parts, 80 parts, 100 parts, 120 parts, 140 parts and 150 parts; specifically, the water in the present invention may be deionized water, distilled water or purified water.
Preferably, the emulsifier can be selected from 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts and 3 parts. Specifically, the emulsifier is a mixed emulsifier obtained by compounding an anionic emulsifier and a nonionic emulsifier. Wherein the anionic emulsifier is selected from one or more of sodium dodecyl sulfate, propenyl sulfonate and tridecyl sulfonate; the nonionic emulsifier can be tridecyl alcohol polyoxyethylene ether. In a more preferable scheme, the emulsifier is a mixed emulsifier obtained by compounding tridecyl sulfonate, propenyl sulfonate and tridecyl alcohol polyoxyethylene ether, and has good wettability and excellent emulsibility. The tridecyl sulfonate and the propenyl sulfonate are both reactive anionic emulsifiers, and the particle size of the tridecyl sulfonate and the propenyl sulfonate is larger than that of a common anionic emulsifier (sodium dodecyl sulfate), so that the extinction effect of the acrylic resin can be improved.
Preferably, the aqueous initiator is selected from 0.1 part, 0.3 part, 0.5 part, 0.7 part and 1 part, and specifically, the aqueous initiator is any one of potassium persulfate, ammonium persulfate and sodium persulfate.
Correspondingly, the invention also provides a preparation method of the waterborne self-extinction controllable-gloss acrylic resin, which comprises the following steps:
1) preparing seed resin containing organic polymeric flocculant: adding water, an emulsifier and a buffer agent according to the formula amount, adding a water-based initiator under the protection of inert gas, heating and adding a seed monomer, and reacting to obtain seed resin containing an organic polymeric flocculant;
2) heating the seed resin obtained in the step 1), adding a shell monomer, reacting for 1-2 hours, heating to continue the reaction, and adjusting the pH to 7-8 after the reaction is finished to obtain the water-based self-extinction controlled-gloss acrylic resin.
Further, the aqueous initiator is added after the shell monomer is added in the step 2) to promote the reaction to be fully carried out. Further, step 2) may also include the addition of a self-crosslinking system to assist in film formation.
The preparation method of the water-based self-extinction controlled-gloss acrylic resin further comprises the following steps:
1) preparing seed resin containing organic polymeric flocculant: adding water, an emulsifier and a buffer agent according to the formula amount, adding a water-based initiator under the protection of inert gas, adding a seed monomer at the temperature of 70-80 ℃, and reacting for 1-3 hours to obtain seed resin containing the organic polymeric flocculant;
2) heating the seed resin obtained in the step 1) to 70-80 ℃, adding a shell monomer and a water-based initiator, reacting for 1-2 hours, heating to 85 ℃, continuing to react for 1-2 hours, and adjusting the pH to 7-8 after the reaction is finished to obtain the water-based self-extinction controlled-gloss acrylic resin.
The preparation of the water-based self-extinction gloss-controllable acrylic resin does not need to add a solvent, has no volatile smell, and is environment-friendly; and no matting agent is added, so that the good mechanical property of the paint film can be maintained, the characteristics of poor dispersion, smooth film surface, increased matting degree and overall viscosity rise and the like are avoided, and meanwhile, the preparation raw material source is wide, the price is low, the synthesis process is simple, and the preparation cost is low.
Detailed Description
The technical solutions of the present invention are further illustrated by the following specific embodiments, but the present invention is not limited thereto.
Example 1
The preparation raw materials of the aqueous self-extinction controlled-gloss acrylic resin comprise, by weight:
seed monomer: 3.5 parts of methyl methacrylate +0.4 part of 2-ethylhexyl acrylate +0.6 part of methacrylic acid +0.2 part of acrylic acid;
shell monomer: 20 parts of methyl methacrylate, 2.4 parts of butyl acrylate, 10 parts of 2-ethylhexyl acrylate, 0.2 part of isooctyl methacrylate and 1 part of hydroxyethyl methacrylate;
emulsifier: 0.7 part of propenyl sulfonate, 0.2 part of tridecyl sulfonate and 0.1 part of tridecyl alcohol polyoxyethylene ether are compounded to obtain a mixed emulsifier;
aqueous initiator: 0.2 part of potassium persulfate;
buffering agent: 0.05 part of sodium bicarbonate;
40 parts of deionized water.
The composition is adopted to prepare the waterborne self-extinction controlled-gloss acrylic resin:
1) preparing seed resin containing organic polymeric flocculant: adding 40 parts of deionized water, 0.05 part of sodium bicarbonate, 0.7 part of propenyl sulfonate, 0.2 part of tridecyl sulfonate and 0.1 part of tridecyl alcohol polyoxyethylene ether into a four-mouth round bottom reaction bottle provided with a reflux condenser, a mechanical stirrer, a nitrogen conduit, a thermometer and a peristaltic pump, adding potassium persulfate when the temperature is heated to about 75 ℃ under the protection of nitrogen, then adding 3.5 parts of methyl methacrylate, 0.4 part of acrylic acid-2-ethylhexyl ester, 0.6 part of methacrylic acid and 0.2 part of acrylic acid within 3 minutes for reaction, and carrying out heat preservation reaction for 1 hour when a light blue color appears in a system to obtain seed resin containing the organic polymer flocculant;
2) adding 20 parts of methyl methacrylate, 2.4 parts of butyl acrylate, 10 parts of acrylic acid-2-ethylhexyl ester, 0.2 part of isooctyl methacrylate and 1 part of hydroxyethyl methacrylate into the seed resin in the step 1), adding a water-based initiator at proper time during the reaction period according to conditions, keeping the temperature at 75 ℃, keeping the temperature unchanged for about 1 hour, heating to 85 ℃ for continuous reaction for 1 hour, stopping the reaction, cooling to about 50 ℃, adjusting the pH of the system to 7-8 by using ammonia water, and filtering by using 300-mesh filter cloth to obtain the milky water-based self-extinction controlled-gloss acrylic resin.
Example 2
The raw material components for preparing the waterborne self-extinction controlled-gloss acrylic resin of the embodiment are basically the same as those of the embodiment 1, except that:
the emulsifier in the embodiment is a mixed emulsifier obtained by compounding 0.7 part of sodium dodecyl sulfate, 0.2 part of tridecyl sulfonate and 0.1 part of tridecyl alcohol polyoxyethylene ether.
The preparation method of the waterborne self-matting controllable gloss acrylic resin of this example is the same as that of example 1, and will not be described in detail.
Example 3
The raw material components for preparing the waterborne self-extinction controlled-gloss acrylic resin of the embodiment are basically the same as those of the embodiment 1, except that:
the raw material for preparing the acrylic resin in this example further contains a self-crosslinking monomer, specifically, 1.0 part of adipic acid dihydrazide, 1.0 part of acetoacetoxyethyl methacrylate, and 1.0 part of N- (2-hydroxyethyl) acrylamide.
The preparation method of the waterborne self-extinction controlled-gloss acrylic resin of the embodiment is as follows:
1) preparing seed resin containing organic polymeric flocculant: adding 40 parts of deionized water, 0.05 part of sodium bicarbonate, 0.7 part of propenyl sulfonate, 0.2 part of tridecyl sulfonate and 0.1 part of tridecyl alcohol polyoxyethylene ether into a four-mouth round bottom reaction bottle provided with a reflux condenser, a mechanical stirrer, a nitrogen conduit, a thermometer and a peristaltic pump, adding potassium persulfate when the temperature is heated to about 75 ℃ under the protection of nitrogen, then adding 3.5 parts of methyl methacrylate, 0.4 part of acrylic acid-2-ethylhexyl ester, 0.6 part of methacrylic acid and 0.2 part of acrylic acid within 3 minutes for reaction, and carrying out heat preservation reaction for 1 hour when a light blue color appears in a system to obtain seed resin containing the organic polymer flocculant;
2) adding 20 parts of methyl methacrylate, 2.4 parts of butyl acrylate, 10 parts of 2-ethylhexyl acrylate, 0.2 part of isooctyl methacrylate and 1 part of hydroxyethyl methacrylate into the seed resin in the step 1), adding 1.0 part of adipic dihydrazide, 1.0 part of acetoacetoxyethyl methacrylate and 1.0 part of N- (2-hydroxyethyl) acrylamide at proper time during the reaction, keeping the temperature at 75 ℃, heating to 85 ℃ for continuous reaction for 1 hour when the reaction is 1, stopping the reaction, cooling to 50 ℃, adjusting the pH of the system to 7-8 by using ammonia water, and filtering by using a filter cloth of 300 meshes to obtain the milky waterborne self-extinction controlled-gloss acrylic resin.
Example 4
The preparation raw materials of the waterborne self-extinction controlled-gloss acrylic resin comprise, by weight:
seed monomer: 3.5 parts of methyl methacrylate +0.4 part of 2-ethylhexyl acrylate +0.54 part of methacrylic acid +0.27 part of acrylic acid;
shell monomer: 20 parts of methyl methacrylate, 2.4 parts of butyl acrylate, 10 parts of 2-ethylhexyl acrylate, 0.2 part of isooctyl methacrylate and 1 part of hydroxyethyl methacrylate;
emulsifier: 0.7 part of propenyl sulfonate, 0.2 part of tridecyl sulfonate and 0.1 part of tridecyl alcohol polyoxyethylene ether are compounded to obtain a mixed emulsifier;
aqueous initiator: 0.2 part of potassium persulfate;
buffering agent: 0.05 part of sodium bicarbonate;
self-crosslinking monomer: 1.0 part of adipic acid dihydrazide, 1.0 part of acetoacetoxyethyl methacrylate and 1.0 part of N- (2-hydroxyethyl) acrylamide;
40 parts of deionized water.
The preparation method of the waterborne self-matting controllable gloss acrylic resin of this example is the same as that of example 3, and will not be described in detail.
Example 5
The aqueous self-extinction controlled-gloss acrylic resin comprises the following components in parts by weight:
seed monomer: 3.5 parts of methyl methacrylate +0.4 part of 2-ethylhexyl acrylate +0.65 part of methacrylic acid +0.13 part of acrylic acid;
shell monomer: 20 parts of methyl methacrylate, 2.4 parts of butyl acrylate, 10 parts of 2-ethylhexyl acrylate, 0.2 part of isooctyl methacrylate and 1 part of hydroxyethyl methacrylate;
emulsifier: 0.7 part of propenyl sulfonate, 0.2 part of tridecyl sulfonate and 0.1 part of tridecyl alcohol polyoxyethylene ether are compounded to obtain a mixed emulsifier;
aqueous initiator: 0.2 part of potassium persulfate;
buffering agent: 0.05 part of sodium bicarbonate;
self-crosslinking monomer: 1.0 part of adipic acid dihydrazide, 1.0 part of acetoacetoxyethyl methacrylate and 1.0 part of N- (2-hydroxyethyl) acrylamide;
40 parts of deionized water.
The preparation method of the waterborne self-matting controllable gloss acrylic resin of this example is the same as that of example 3, and will not be described in detail.
Example 6
The aqueous self-extinction controlled-gloss acrylic resin comprises the following components in parts by weight:
seed monomer: 4 parts of methyl methacrylate, 1 part of acrylic acid-2-ethylhexyl ester, 0.8 part of maleic acid and 0.2 part of acrylic acid;
shell monomer: 30 parts of methyl methacrylate, 3 parts of butyl acrylate, 15 parts of 2-ethylhexyl acrylate, 0.5 part of isooctyl methacrylate and 1.3 parts of hydroxyethyl methacrylate;
emulsifier: 0.5 part of propenyl sulfonate and 0.5 part of tridecyl alcohol polyoxyethylene ether are compounded to obtain a mixed emulsifier;
aqueous initiator: 0.2 part of ammonium persulfate;
buffering agent: 0.2 part of triethanolamine;
self-crosslinking monomer: 0.5 parts of adipic acid dihydrazide, 1.0 parts of diacetone acrylamide and 1.5 parts of 1, 6-hexanediol diacrylate;
120 parts of deionized water.
The preparation method of the waterborne self-matting controllable gloss acrylic resin of this example is the same as that of example 3, and will not be described in detail.
Example 7
The aqueous self-extinction controlled-gloss acrylic resin comprises the following components in parts by weight:
seed monomer: 7 parts of methyl methacrylate +1.5 parts of acrylic acid-2-ethylhexyl ester +0.9 part of ethacrylic acid +0.3 part of acrylic acid;
shell monomer: 15 parts of methyl methacrylate, 4 parts of butyl acrylate, 8 parts of acrylic acid-2-ethylhexyl ester, 0.6 part of isooctyl methacrylate and 1.6 parts of hydroxyethyl methacrylate;
emulsifier: 0.8 part of tridecyl sulfonate and 0.4 part of tridecyl alcohol polyoxyethylene ether are compounded to obtain a mixed emulsifier;
aqueous initiator: 0.7 part of sodium persulfate;
buffering agent: 0.5 part of ammonia water;
self-crosslinking monomer: 1.5 parts of adipic acid dihydrazide, 0.5 parts of diacetone acrylamide and 0.5 parts of N-methylol acrylamide;
160 parts of deionized water.
The preparation method of the waterborne self-matting controllable gloss acrylic resin of this example is the same as that of example 3, and will not be described in detail.
Comparative example 1
The raw materials for preparing the aqueous self-extinction controllable-gloss acrylic resin of the comparative example comprise the following components in parts by weight:
seed monomer: 3.5 parts of methyl methacrylate +0.4 part of 2-ethylhexyl acrylate +0.8 part of methacrylic acid;
shell monomer: 20 parts of methyl methacrylate, 2.4 parts of butyl acrylate, 10 parts of 2-ethylhexyl acrylate, 0.2 part of isooctyl methacrylate and 1 part of hydroxyethyl methacrylate;
emulsifier: 0.7 part of propenyl sulfonate, 0.2 part of tridecyl sulfonate and 0.1 part of tridecyl alcohol polyoxyethylene ether are compounded to obtain a mixed emulsifier;
aqueous initiator: 0.2 part of potassium persulfate;
buffering agent: 0.05 part of sodium bicarbonate;
40 parts of deionized water.
The aqueous self-extinction controlled-gloss acrylic resin of this comparative example is prepared in the same manner as in example 1 and will not be described in detail herein.
Comparative example 2
The raw materials for preparing the aqueous self-extinction controllable-gloss acrylic resin of the comparative example comprise the following components in parts by weight:
seed monomer: 3.5 parts of methyl methacrylate +0.4 part of 2-ethylhexyl acrylate +0.8 part of acrylic acid;
shell monomer: 20 parts of methyl methacrylate, 2.4 parts of butyl acrylate, 10 parts of 2-ethylhexyl acrylate, 0.2 part of isooctyl methacrylate and 1 part of hydroxyethyl methacrylate;
emulsifier: 0.7 part of propenyl sulfonate, 0.2 part of tridecyl sulfonate and 0.1 part of tridecyl alcohol polyoxyethylene ether are compounded to obtain a mixed emulsifier;
aqueous initiator: 0.2 part of potassium persulfate;
buffering agent: 0.05 part of sodium bicarbonate;
40 parts of deionized water.
The aqueous self-extinction controlled-gloss acrylic resin of this comparative example is prepared in the same manner as in example 1 and will not be described in detail herein.
The aqueous self-extinction controlled-gloss acrylic resins obtained in examples 1 to 7 and comparative examples 1 to 2 were subjected to related performance tests, and the test results are shown in table 1.
And (3) hardness testing: the sample was dried using a pencil hardness test method commonly used in the art, the tip end of the pencil was ground flat using #400 sandpaper, the pencil was placed in a pencil holding groove of a carriage, and the carriage was adjusted to a horizontal state and then locked. The horizontal pad was removed and the trolley was pushed to advance 3cm at a speed of 0.5 mm/s. The carriage was removed and the film was inspected for pencil scratches, if the scratches were not clear, and the film was inspected for scratches after erasing the pencil scratches with a drawing eraser.
And (3) testing the adhesive force: cutting every 1cm on the surface with a hundred-grid cutter2The/100 panels were tested with 3M glue and the degree of adhesion of the paint film to the substrate was assessed by assessing the integrity of the paint film in the panels.
And (3) testing water resistance: according to GB/T9274-1988, absorbent cotton capable of absorbing media is placed on a coating film to be detected, water is added into the absorbent cotton, and the change of the coating film is checked after the required time is reached.
And (4) testing the storage stability: the emulsion is stored in a constant temperature oven with 50 ℃ and stability for 15 days, and whether the emulsion has unstable phenomenon (demulsification, sedimentation and particle enlargement) or not is observed.
And (3) testing the gloss of the coating film: after the light is reflected by the coating film, the amount of the reflected light is detected to confirm the gloss level of the surface of the coating film. Testing an instrument: 60 ℃ gloss meter (HORIBA IG320) and calibration plate, reading accuracy 0.1 gloss units.
Film forming property: whether the film formation was continuous or not was visually observed.
Low-temperature film forming property: forming a proper temperature gradient on an aluminum plate between a heat source and a cold source, coating the emulsion on the plate, drying with dry air, and measuring the limit temperature of the emulsion for forming a continuous and uniform transparent film so as to judge whether the film is continuously formed.
Mechanical stability: in a suitable 100ml container, 400g of emulsion which has passed through a 80 mesh sieve is weighed, fixed on a high-speed dispersion machine, the stirring head is in a disk shape (diameter 40mm), the rotation speed is 2500r/min, dispersion is carried out for 0.5h, filtration is carried out, residues on the inner wall of the container are flushed into the sieve by tap water, the sieve is flushed by the tap water, and whether emulsion breaking and obvious floc are caused or not is observed.
TABLE 1 test results
From the test results of examples 1-7 and comparative examples 1-2, it can be seen that the waterborne self-extinction controlled-gloss acrylic resin of examples 1-7 of the present application has excellent overall performance, especially has low coating film gloss, and the gloss can be simply controlled according to the component content. The reason is that the aqueous self-extinction controlled-gloss acrylic resin of the present invention forms an organic polymeric flocculant by introducing an acrylic acid derivative and acrylic acid into a seed monomer and by the acrylic acid derivative and the acrylic acid monomer. And the weight of the acrylic acid derivative is controlled to be more than or equal to that of acrylic acid, so that the proportion of carboxyl is controlled, the content of the synthetic organic polymeric flocculant is controlled, and the glossiness of the coating is controlled through the content of the organic polymeric flocculant. The seed monomer of comparative example 1 does not contain acrylic acid, only contains acrylic acid derivatives, lacks relatively hydrophilic and outwardly-intertwinable segments, and the coating film gloss is as high as 75, i.e., normal gloss, so that comparative example 1 cannot produce self-matting effect. The seed monomer of comparative example 2 does not contain methacrylic acid, only acrylic acid, although it contains a segment that is hydrophilic and easily entangles outward, easily generates a large amount of aggregates due to excessive entanglements, making the system unstable.
Example 1 the coating film gloss of the acrylic resin in example 2 was higher than that of example 2, probably because sodium lauryl sulfate was a general anionic emulsifier and propenyl sulfonate was a reactive anionic emulsifier, and the particle size of propenyl sulfonate was larger than that of a general anionic emulsifier (sodium lauryl sulfate), and therefore, the matting effect of the acrylic resin was improved.
Example 1 compared with example 3, the hardness of the acrylic resin in example 3 is better than that of example 1, because example 3 contains the self-crosslinking monomer, and the introduction of the self-crosslinking monomer can enable the seed resin containing the organic polymeric flocculant formed by the seed monomer to react with the shell monomer to assist film formation, so that the storage stability of the coating can be greatly improved by the combined action, and the water resistance, the wear resistance, the storage stability and the hardness of the coating film can be improved.
The gloss of the coating films is different in examples 3-5, specifically, the gloss of the coating film of the acrylic resin in example 5 is higher than that of the coating film of example 3, and the gloss of the coating film of the acrylic resin in example 3 is higher than that of the coating film of example 4. The reason is that the weight ratio of methacrylic acid to acrylic acid is different, and the acid content in the final seed unit can be controlled by the difference between the weight ratio of methacrylic acid and acrylic acid because the acid content of methacrylic acid per unit mass is lower than that of acrylic acid. The coating film gloss is different, the coating film gloss is gradually weaker along with the reduction of the content of methacrylic acid, and the carboxyl chain segment of the acrylic acid is hydrophilic along with the increase of the content of the acrylic acid in the seed monomer, and tends to extend, expand and intertwine outwards, so that the number of the synthesized organic polymer flocculant is increased, the particle size is enlarged, and meanwhile, the flocculation effect is a loose structure. Therefore, the paint film has a difference between the refractive index of the emulsion of air and that of the acrylic monomer, and the gloss of the paint film is further reduced.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, the present invention is not limited to the above disclosed embodiments, but should cover various modifications, equivalent combinations, made according to the essence of the present invention.
Claims (6)
1. The water-based self-extinction gloss-controllable acrylic resin is characterized by comprising the following preparation raw materials in parts by weight:
wherein, the shell monomer comprises the following components in parts by weight:
the seed monomer comprises the following components in parts by weight:
2. the aqueous self-matting controlled gloss acrylic resin according to claim 1 wherein the self-crosslinking monomer comprises:
(a) 0.5-1.5 parts of adipic acid dihydrazide;
(b) 0.5-1.5 parts of one or more of N- (2-hydroxyethyl) acrylamide, 1, 6-hexanediol diacrylate and N-hydroxymethyl acrylamide; and
(c) 0.5-1.5 parts of one or two of acetoacetoxyethyl methacrylate and diacetone acrylamide.
3. The aqueous self-matting controllable-gloss acrylic resin according to claim 1, wherein the emulsifier is a mixed emulsifier obtained by compounding an anionic emulsifier and a nonionic emulsifier.
4. The aqueous self-matting controllable-gloss acrylic resin according to claim 1, wherein the emulsifier is a mixed emulsifier obtained by compounding tridecyl sulfonate, propenyl sulfonate and tridecyl alcohol polyoxyethylene ether.
5. The aqueous self-matting controllable gloss acrylic resin according to claim 1 wherein the aqueous initiator is any one of potassium persulfate, ammonium persulfate and sodium persulfate.
6. The method for preparing the aqueous self-dulling controllable gloss acrylic resin according to any one of claims 1 to 5, comprising:
1) preparing seed resin containing organic polymeric flocculant: adding water, an emulsifier and a buffer agent according to the formula amount, adding a water-based initiator under the protection of inert gas, heating and adding a seed monomer, and reacting to obtain seed resin containing an organic polymeric flocculant;
2) heating the seed resin obtained in the step 1), adding a shell monomer, reacting for 1-2 hours, heating to continue the reaction, and adjusting the pH to 7-8 after the reaction is finished to obtain the water-based self-extinction controlled-gloss acrylic resin.
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