阅读说明：本技术 醇酸-丙烯酸杂化乳液及其制备方法 (Alkyd-acrylic hybrid emulsion and preparation method thereof ) 是由 朱晓亮 刘志刚 陈寿生 于 2021-07-02 设计创作，主要内容包括：本申请涉及涂料技术领域,提供了一种醇酸-丙烯酸杂化乳液,包括如下重量份数的下列组分：300～350份丙烯酸类单体/乙烯类单体；10～50份交联单体；20～80份醇酸预聚体；150～180份稳定剂；360～400份水；10～20份助剂。提供的乳液混合物的丰满度、基材渗透性和颜料润湿性；并且,引入了稳定剂,稳定剂在聚合反应过程中形成胶束,使得体系中含有醇酸预聚体的聚合单体混合溶液在胶束的包围下共聚,从而获得既具有纳米级平均粒径又具有较窄的单峰形态的粒度分布的乳液颗粒,使得到的醇酸-丙烯酸杂化乳液具有零VOC、耐水性较好的特点。(The application relates to the technical field of coatings, and provides an alkyd-acrylic hybrid emulsion which comprises the following components in parts by weight: 300-350 parts of acrylic monomer/vinyl monomer; 10-50 parts of a crosslinking monomer; 20-80 parts of an alkyd prepolymer; 150-180 parts of a stabilizer; 360-400 parts of water; 10-20 parts of an auxiliary agent. The fullness, substrate penetration, and pigment wetting of the provided emulsion mixture; and moreover, a stabilizer is introduced, and the stabilizer forms micelles in the polymerization reaction process, so that a polymerization monomer mixed solution containing the alkyd prepolymer in the system is copolymerized under the surrounding of the micelles, and emulsion particles with a nanoscale average particle size and a narrow monomodal particle size distribution are obtained, and the obtained alkyd-acrylic hybrid emulsion has the characteristics of zero VOC and good water resistance.)

1. The alkyd-acrylic hybrid emulsion is characterized by comprising the following components in parts by weight:

2. the alkyd-acrylic hybrid emulsion according to claim 1, wherein the alkyd prepolymer comprises the following components in parts by weight:

3. the alkyd-acrylic hybrid emulsion according to claim 2, wherein the vegetable oil fatty acid is selected from at least one of refined linoleic acid, high iodine value soybean oleic acid, tall oil acid, dehydrated ricinoleic acid, eleostearic acid; and/or the presence of a gas in the gas,

the dibasic acid is at least one selected from phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, fumaric acid, sebacic acid and pyromellitic anhydride; and/or the presence of a gas in the gas,

the polyhydric alcohol is at least one selected from ethylene glycol, 1, 2-and 1, 3-propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol and trimethylolethane.

4. The alkyd-acrylic hybrid emulsion of claim 2 wherein the catalyst is selected from at least one of monobutyl tin oxide, dibutyl tin oxide chloride, dibutyl tin dilaurate, dibutyl tin diacetate, monobutyl tin trichloride; and/or the presence of a gas in the gas,

the antioxidant is at least one selected from 2, 6-di-tert-butyl-4-methylphenol, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester and phosphite antioxidant; and/or the presence of a gas in the gas,

the polymerization inhibitor is at least one selected from p-hydroxyanisole, hydroquinone, p-benzoquinone, methyl hydroquinone, 2-tert-butyl hydroquinone, 2, 5-di-tert-butyl hydroquinone, phenothiazine, beta-phenyl naphthylamine, p-tert-butyl catechol, 1-diphenyl-2-trinitrophenylhydrazine, 2,6, 6-tetramethyl piperidine nitroxide free radical, polymerization inhibitor-701 and polymerization inhibitor-705.

5. The alkyd-acrylic hybrid emulsion according to any one of claims 1 to 4, wherein the acrylic monomer is at least one selected from acrylic acid, methacrylic acid and alkyl esters of methacrylic acid C1-C20; and/or the presence of a gas in the gas,

the vinyl monomer is selected from at least one of styrene, vinyl acetate, acrylonitrile, vinyl chloride, Veova 9 and Veova 10.

6. The alkyd-acrylic hybrid emulsion of claim 5, wherein the alkyl methacrylate C1-C20 is selected from at least one of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, lauryl acrylate, methyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, itaconic acid, acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate.

7. The alkyd-acrylic hybrid emulsion according to any one of claims 1 to 4, wherein the crosslinking monomer is at least one selected from the group consisting of acrylamide, methylol acrylamide, divinylbenzene, trimethylolpropane triacrylate, vinyltrimethoxysilane, diacetone acrylamide, adipic dihydrazide, ethyl acetoacetate methacrylate, and hexamethylenediamine; and/or the presence of a gas in the gas,

the stabilizer is selected from alkali-soluble resins, and the alkali-soluble resin is selected from solid alkali-soluble resins or solution alkali-soluble resins.

8. The alkyd-acrylic hybrid emulsion according to any one of claims 1 to 4, wherein the auxiliary comprises the following components in parts by weight:

9. the preparation method of the alkyd-acrylic hybrid emulsion is characterized by comprising the following steps:

determining the components and parts of the raw materials according to any one of claims 1 to 8;

carrying out first mixing and heating treatment on a stabilizer and part of water to obtain a first mixture;

carrying out second mixing treatment on the acrylic monomer/vinyl monomer, the crosslinking monomer, the alkyd prepolymer, the auxiliary agent and the remaining water to obtain a second mixture;

and carrying out third mixing heating treatment on the first mixture and the second mixture, and filtering to obtain the alkyd-acrylic hybrid emulsion.

10. The method for preparing the alkyd-acrylic hybrid emulsion according to claim 9, wherein the method for preparing the alkyd prepolymer comprises the following steps:

providing raw materials of an alkyd prepolymer, namely vegetable oil fatty acid, dibasic acid, polyhydric alcohol, maleic anhydride, a catalyst, an antioxidant and a polymerization inhibitor;

heating and stirring the vegetable oil fatty acid, the dibasic acid, the polyol, the catalyst and the antioxidant at 110-140 ℃ under a protective atmosphere to obtain a first component;

carrying out dehydration condensation treatment on the first component at 170-220 ℃ to obtain a second component;

and mixing the second component with the maleic anhydride and the polymerization inhibitor, reacting at 120-150 ℃ for 3-5 hours, and cooling to normal temperature to obtain the alkyd prepolymer.

Technical Field

The application belongs to the technical field of coatings, and particularly relates to an alkyd-acrylic hybrid emulsion and a preparation method thereof.

Background

With government restrictions on the amount of VOC (volatile hazardous substances) emissions, the use of solvent-based resins in the coating field is greatly restricted. More water-based coatings are provided at the present stage, the water-based coatings are novel coatings in the coating market, and compared with solvent paint coatings, the water-based coatings have the following characteristics: firstly, the water-based paint takes water as a solvent, so that a large amount of resources are saved; the water-based paint eliminates the fire hazard during construction; the air pollution is reduced; the water paint only adopts a small amount of low-toxicity alcohol ether organic solvent, thus improving the operating environmental conditions. The organic solvent (accounting for the coating) of the common water-based coating is 10-15%, and the cathodic electrophoretic coating is reduced to below 1.2%, so that the effects of reducing pollution and saving resources are remarkable; secondly, the water-based paint can be directly coated and constructed on a wet surface and in a humid environment; the water-based paint has good adaptability to the surface of the material and strong adhesive force of the coating; thirdly, the water-based paint coating tool can be cleaned by water, so that the consumption of a cleaning solvent is greatly reduced; fourthly, the electrophoretic coating of the water-based paint is uniform and flat. The flattening performance is good; the inner cavity, the welding seam, the edge and the edge part can be coated with a coating film with a certain thickness, so that the protective property is good; the electrophoretic coating has the best corrosion resistance, and the salt spray resistance of the thick-film cathode electrophoretic coating can reach 1200h at most.

The water-based alkyd-acrylic hybrid emulsion has the characteristics of environmental protection, excellent cost performance and the like, and is widely applied to various fields of wood coatings, industrial corrosion prevention and the like at present. However, the existing waterborne alkyd-acrylic hybrid resins are all secondary dispersions, namely, esterification and copolymerization are carried out by a solution polymerization method, and after neutralization and salt formation, water is converted through re-dispersion, so that the existing waterborne alkyd-acrylic hybrid resins inevitably contain more VOC and have the defects of poor water resistance.

Disclosure of Invention

The application aims to provide an alkyd-acrylic hybrid emulsion and a preparation method thereof, and aims to solve the problems that in the prior art, a water-based alkyd-acrylic hybrid emulsion contains a large amount of VOC, is poor in water resistance and large in particle size.

In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:

in a first aspect, the present application provides an alkyd-acrylic hybrid emulsion, comprising the following components in parts by weight:

in a second aspect, the present application provides a method for preparing an alkyd-acrylic hybrid emulsion, comprising the steps of:

determining the components and parts of the raw materials according to the alkyd-acrylic hybrid emulsion;

carrying out first mixing and heating treatment on a stabilizer and part of water to obtain a first mixture;

carrying out second mixing treatment on the acrylic monomer/vinyl monomer, the crosslinking monomer, the alkyd prepolymer, the auxiliary agent and the remaining water to obtain a second mixture;

and carrying out third mixing heating treatment on the first mixture and the second mixture, and filtering to obtain the alkyd-acrylic hybrid emulsion.

According to the alkyd-acrylic hybrid emulsion provided by the first aspect of the application, an acrylic monomer/vinyl monomer is used as a main component in the emulsion mixture, and an alkyd prepolymer containing unsaturated double bonds is introduced as one of polymerization monomers to form the alkyd-acrylic hybrid emulsion, so that the fullness, substrate permeability and pigment wettability of the emulsion are improved; in addition, a stabilizer is introduced, and the stabilizer forms micelles in the polymerization reaction process, so that a polymerization monomer mixed solution containing the alkyd prepolymer in the system is copolymerized under the surrounding of the micelles, thereby obtaining emulsion particles which have a nano-scale average particle size and a narrow monomodal particle size distribution, and obviously improving the problem of larger particle size of the traditional primary dispersion emulsion; meanwhile, through the synergistic effect of the components, the obtained alkyd-acrylic hybrid emulsion has the characteristics of zero VOC and good water resistance, and has the advantages of good fullness, good substrate permeability and good pigment wettability, thereby being beneficial to wide application.

According to the preparation method of the alkyd-acrylic hybrid emulsion provided by the second aspect of the application, the preparation method is simple in process, the alkyd-acrylic hybrid emulsion can be obtained by mixing the components, and a plurality of reaction kettles are provided for acting in the large-scale preparation process, so that the alkyd-acrylic hybrid emulsion with the excellent properties can be prepared.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.

In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.

In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.

It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.

The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.

The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.

The first aspect of the embodiments of the present application provides an alkyd-acrylic hybrid emulsion, which comprises the following components in parts by weight:

according to the alkyd-acrylic hybrid emulsion provided by the first aspect of the application, an acrylic monomer/vinyl monomer is used as a main component in the emulsion mixture, and an alkyd prepolymer containing unsaturated double bonds is introduced as one of polymerization monomers to form the alkyd-acrylic hybrid emulsion, so that the fullness, substrate permeability and pigment wettability of the emulsion are improved; in addition, a stabilizer is introduced, and the stabilizer forms micelles in the polymerization reaction process, so that a polymerization monomer mixed solution containing the alkyd prepolymer in the system is copolymerized under the surrounding of the micelles, thereby obtaining emulsion particles which have a nano-scale average particle size and a narrow monomodal particle size distribution, and obviously improving the problem of larger particle size of the traditional primary dispersion emulsion; meanwhile, through the synergistic effect of the components, the obtained alkyd-acrylic hybrid emulsion has the characteristics of zero VOC and good water resistance, and has the advantages of good fullness, good substrate permeability and good pigment wettability, thereby being beneficial to wide application.

Specifically, the alkyd-acrylic hybrid emulsion comprises 300-350 parts of acrylic monomer/vinyl monomer, and the acrylic monomer/vinyl monomer is used as a main component in the emulsion.

In some embodiments, the acrylic monomer is selected from at least one of acrylic acid, methacrylic acid, and C1-C20 alkyl esters of methacrylic acid. Further, the alkyl ester of methacrylic acid C1-C20 is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, lauryl acrylate, methyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, itaconic acid, acrylamide, methacrylamide, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate. The acrylic monomer is provided as the main component of the emulsion, and the obtained emulsion has the property of aqueous emulsion.

In some embodiments, the vinylic monomer is selected from at least one of styrene, vinyl acetate, acrylonitrile, vinyl chloride, Veova 9, Veova 10. The provided ethylene monomer can be used as the main component of the emulsion, and can ensure that the obtained emulsion has the property of aqueous emulsion.

In the specific examples, the parts of the acrylic monomer/vinyl monomer are selected from 300 parts, 305 parts, 310 parts, 315 parts, 320 parts, 325 parts, 330 parts, 335 parts, 340 parts, 345 parts and 350 parts.

Specifically, the provided alkyd-acrylic hybrid emulsion comprises 10-50 parts of crosslinking monomers, and the provided crosslinking monomers can be beneficial to crosslinking reaction among the monomers, so that the interaction among the monomers is improved.

In some embodiments, the crosslinking monomer is selected from at least one of acrylamide, methylolacrylamide, divinylbenzene, trimethylolpropane triacrylate, vinyltrimethoxysilane, diacetone acrylamide, adipic acid dihydrazide, ethyl acetoacetate methacrylate, and hexamethylenediamine, and provides a crosslinking agent that facilitates crosslinking between the monomers.

In specific embodiments, the addition parts of the crosslinking monomer are selected from: 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts and 50 parts.

Specifically, the provided alkyd-acrylic hybrid emulsion comprises 20-80 parts of alkyd prepolymer, and the provided alkyd prepolymer containing unsaturated double bonds is used as one of polymerization monomers to form the alkyd-acrylic hybrid emulsion, so that the fullness, substrate permeability and pigment wettability of the emulsion are improved.

In some embodiments, the alkyd prepolymer comprises the following components in parts by weight:

in some embodiments, the vegetable oil fatty acid is selected from at least one of refined linoleic acid, high iodine value soy oleic acid, tall oil acid, dehydrated ricinoleic acid, eleostearic acid.

In some embodiments, the dibasic acid is selected from at least one of phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, fumaric acid, sebacic acid, pyromellitic anhydride.

In some embodiments, the polyol is selected from at least one of ethylene glycol, 1, 2-and 1, 3-propanediol, butanediol, hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol, trimethylolethane.

In some embodiments, the provided catalyst is selected from esterification catalysts, which are used to promote the esterification reaction, thereby facilitating an increase in reaction efficiency. In some embodiments, the catalyst is selected from at least one of monobutyl tin oxide, dibutyl tin oxide chloride, dibutyl tin dilaurate, dibutyl tin diacetate, monobutyl tin trichloride. Further in particular embodiments, the catalyst is selected from monobutyl tin oxide, which is provided to facilitate catalyzing the formation of ethers from the polyol.

In some embodiments, antioxidants are provided to inhibit oxidation of the system to avoid darkening of the color of the synthesized alkyd prepolymer.

In some embodiments, the antioxidant is selected from at least one of 2, 6-di-tert-butyl-4-methylphenol, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and phosphite antioxidants. Further, phosphite antioxidants include, but are not limited to, tris (2, 4-di-t-butylphenyl) phosphite (also known as Irgafos 168), bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite (also known as Irgafos 126), hypophosphorous acid. In a further embodiment, the antioxidant is at least one of BHT, hypophosphorous acid and antioxidant 1010, wherein the hypophosphorous acid has the strongest antioxidant capacity, and the BHT and the antioxidant 1010 have lower cost, have the effect of resisting oxidative yellowing and also have a certain polymerization inhibition effect.

Wherein, in order to avoid the polymerization of the double bond of maleic anhydride at high temperature reaction, the formation of alcohol-acid prepolymer can be facilitated by providing polymerization inhibitor. In some embodiments, the polymerization inhibitor is selected from at least one of p-hydroxyanisole, hydroquinone, p-benzoquinone, methylhydroquinone, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, phenothiazine, beta-phenylnaphthylamine, p-tert-butylcatechol, 1-diphenyl-2-trinitrophenylhydrazine, 2,6, 6-tetramethylpiperidine nitroxide free radical, inhibitor-701, and inhibitor-705.

Specifically, the alkyd-acrylic hybrid emulsion comprises 150-180 parts of a stabilizer, wherein the stabilizer is a water-soluble or water-swellable polymer which is converted from a water-insoluble polymer without the activity of a protective colloid in situ into a polymer with the activity of the protective colloid by adding a neutralizing agent.

In some embodiments, the stabilizer is selected from alkali soluble resins provided in solid form, solution form dissolved in an alcohol ether solvent, or aqueous emulsion form, insoluble or present as an emulsion or suspension in an acidic or neutral aqueous medium having a pH of 7 or less, but which, when the aqueous medium is alkaline, will dissolve as a homogeneous, transparent system. In this case, various acid groups contained in the molecular structure are neutralized with cations, and thus, the polymer anionic surfactant can be used.

In some embodiments, the alkali-soluble resin may be a solid alkali-soluble resin that desolventizes by bulk polymerization or solution polymerization, including but not limited to at least one of Joncryl 678, Joncryl 682, Joncryl 586, korean Soluryl 90, and Soluryl 120 of BASF. Meanwhile, solution type alkali soluble resin obtained by a solution polymerization method with alcohol ether solvent as a solvent can be selected, wherein the alcohol ether solvent can be used as a film forming auxiliary agent of the emulsion; emulsion type alkali-soluble resins prepared by emulsion polymerization with or without an emulsifier may also be selected.

Further, the smaller the molecular weight, the lower the glass transition temperature (Tg), and the higher the acid value of the alkali-soluble acrylic resin, the smaller the particle size of the synthesized polyacrylate emulsion, and the better the polymerization stability, film-forming property, and permeability.

In specific examples, the parts of the stabilizer of the alkyd-acrylic hybrid emulsion are selected from 150 parts, 155 parts, 160 parts, 165 parts, 170 parts, 175 parts and 180 parts.

Specifically, the alkyd-acrylic hybrid emulsion comprises 10-20 parts of an auxiliary agent, wherein the auxiliary agent comprises the following components in parts by weight:

in some embodiments, the emulsifier includes, but is not limited to including, at least one of an anionic emulsifier, a nonionic emulsifier, and a reactive emulsifier. Wherein the anionic emulsifier includes, but is not limited to, alkali metal salts or ammonium salts of alkylsulfuric acid having 8 to 22 carbon atoms, alkali metal salts and ammonium salts of sulfuric monoester of ethoxylated alkanol, alkali metal salts and ammonium salts of sulfuric monoester of ethoxylated alkylphenol, alkali metal salts and ammonium salts of alkylsulfonic acid having 12 to 18 carbon atoms, alkali metal salts and ammonium salts of alkylarylsulfonic acid or alkylbenzylsulfonic acid having 9 to 18 carbon atoms, alkali metal salts of alkylbenzenesulfonic acid, sulfonated fatty acid, sulfonated olefin, sulfonated diphenyl ether, yellow succinic acid salt, fatty alcohol sulfate, alkylphenol sulfate, alkyl polyglycol ether sulfate, fatty alcohol phosphate, alkylphenol sulfate, alkyl polyglycol ether phosphate, alkyl polyalkylene oxide phosphate, and fatty alcohol ether phosphate; nonionic emulsifiers include, but are not limited to, ethoxylates of long chain alcohols, homo-and copolymers of polyethylene/polypropylene oxides, ethoxylated monoalkylphenols; the reactive emulsifier includes at least one emulsifying group and at least one free radically polymerizable group (e.g., allyl, acrylate, methacrylate, vinyl ether), including but not limited to SR10, SR1025, ER20, etc. of ADEKA or PAM 100, PAM200, PAM4000 of SOLVAY.

In some embodiments, the buffer is used to stabilize the pH environment of the system, such that the reaction proceeds smoothly. Buffering agents include, but are not limited to, sodium bicarbonate, sodium citrate, sodium dihydrogen phosphate.

In some embodiments, the chain transfer agent helps to adjust the molecular weight of the polyacrylate, so that the molecular weight distribution range of the polyacrylate is reduced, the particle size distribution of the emulsion is improved, and the physical and chemical properties of the paint film are improved. Among them, the chain transfer agent includes, but is not limited to, n-dodecyl mercaptan, t-dodecyl mercaptan, alpha-methylstyrene linear dimer, t-butyl mercaptan, thioglycolic acid, mercaptopropionic acid, butyl mercaptopropionate, 2-ethylhexyl thioglycolate, 2-ethylhexyl mercaptopropionate, isotridecyl thioglycolate, mercaptopropyltrimethoxysilane, and the like.

In a specific embodiment, the chain transfer agent is selected to be alpha-methyl styrene linear dimer (AMDS) and has a low odor, which reduces the odor of the emulsion.

In some embodiments, the initiator is used to initiate polymerization of the monomers of the monomer composition with each other, thereby synthesizing the polyacrylate. In some embodiments, the initiator includes a peroxide initiator and/or a redox initiation system. The peroxide initiator includes, but is not limited to, sodium persulfate, potassium persulfate, ammonium persulfate, tert-butyl hydroperoxide, and cumene hydroperoxide.

In some embodiments, the neutralizing agent is selected from one of ammonia, triethylamine, dimethylethanolamine, potassium hydroxide, sodium hydroxide, and any combination thereof. Provides a system in which the reaction can be preferably regulated by a neutralizing agent.

In some embodiments, the provision of an anti-foaming agent facilitates elimination of foam during the reaction, ensuring that the resulting emulsion does not foam.

In some embodiments, the provision of a preservative is beneficial to ensure that the resulting emulsion has a certain preservative effect, ensuring a longer shelf life.

In a second aspect, the present embodiments provide a method for preparing an alkyd-acrylic hybrid emulsion, comprising the following steps:

s01, determining components and parts of raw materials according to the alkyd-acrylic hybrid emulsion;

s02, carrying out first mixing and heating treatment on a stabilizer and part of water to obtain a first mixture;

s03, carrying out second mixing treatment on the acrylic monomer/vinyl monomer, the crosslinking monomer, the alkyd prepolymer, the auxiliary agent and the remaining water to obtain a second mixture;

and S04, carrying out third mixing and heating treatment on the first mixture and the second mixture, and filtering to obtain the alkyd-acrylic hybrid emulsion.

According to the preparation method of the alkyd-acrylic hybrid emulsion provided by the second aspect of the application, the preparation method is simple in process, the alkyd-acrylic hybrid emulsion can be obtained by mixing the components, and a plurality of reaction kettles are provided for acting in the large-scale preparation process, so that the alkyd-acrylic hybrid emulsion with the excellent properties can be prepared.

In step S01, the components and parts of the alkyd-acrylic hybrid emulsion are provided in accordance with those discussed above, and are not described herein again for the sake of brevity.

In step S02, a first mixture is obtained by subjecting the stabilizer and part of water to a first mixing and heating treatment.

In a specific example, the alkali-soluble acrylic resin, alkali and water are subjected to a first mixing heat treatment in a reaction vessel, and stirred until the system is transparent.

In some embodiments, the alkali-soluble resin may be a solid alkali-soluble resin that desolventizes by bulk polymerization or solution polymerization, including but not limited to at least one of Joncryl 678, Joncryl 682, Joncryl 586, korean Soluryl 90, and Soluryl 120 of BASF. Meanwhile, solution type alkali soluble resin obtained by a solution polymerization method with alcohol ether solvent as a solvent can be selected, wherein the alcohol ether solvent can be used as a film forming auxiliary agent of the emulsion; emulsion type alkali-soluble resins prepared by emulsion polymerization with or without an emulsifier may also be selected.

In step S03, a second mixing process is performed on the acrylic monomer/vinyl monomer, the crosslinking monomer, the alkyd prepolymer, the auxiliary agent, and the remaining water to obtain a second mixture.

In a specific embodiment, a monomer mixture is prepared in an emulsifying kettle, and the monomer mixture comprises at least one acrylic monomer or/and vinyl monomer, a crosslinking monomer, and a mixed monomer of the alkyd prepolymer, and may also comprise components such as water, an emulsifier, a buffering agent, a chain transfer agent and the like; an initiator solution system was prepared in the dropping tank.

In step S04, the first mixture and the second mixture are subjected to a third mixing heating treatment, and are subjected to a filtering treatment, so as to obtain an alkyd-acrylic hybrid emulsion.

In some embodiments, the manner of adding the acrylic acid mixed monomer includes the following various forms, and is not limited to the enumerated range, and falls within the scope of the present invention.

The first form: the acrylic acid mixed monomer is designed as a component, a certain proportion is added into a reaction kettle for seed polymerization, and then the rest part is dripped;

the second form: the acrylic acid mixed monomer is designed into at least more than two components with different monomer types and proportions, the first component with a certain proportion is added into a reaction kettle for seed polymerization, and then the rest part and the rest components are sequentially dripped, so that a special multilayer core-shell structure is formed;

the third form: the acrylic mixed monomer is designed into at least more than two components with different monomer types and proportions, the first component with a certain proportion is firstly added into a reaction kettle for seed polymerization, then the rest part is dripped, and meanwhile, the other component mixed monomer is dripped into the component and uniformly mixed, thereby forming a special progressive structure;

in the above form, the mixed monomer of a certain component can be added into the reaction kettle in a dropwise manner, or can be added into the reaction kettle at one time or added into the reaction kettle for multiple times.

In a specific embodiment, after heating the bottom material of the reaction kettle to a certain temperature, the monomer mixture and the initiator system are added into the reaction kettle in a certain manner to carry out polymerization reaction. Further, after a residual monomer eliminating stage which may be needed, adding an auxiliary agent, filtering and discharging to obtain the final alkyd-acrylic hybrid emulsion.

In some embodiments, the method of preparing the alkyd prepolymer comprises the steps of:

G01. providing raw materials of an alkyd prepolymer, namely vegetable oil fatty acid, dibasic acid, polyhydric alcohol, maleic anhydride, a catalyst, an antioxidant and a polymerization inhibitor;

G02. under the protective atmosphere, heating and stirring vegetable oil fatty acid, dibasic acid, polyhydric alcohol, a catalyst and an antioxidant at 110-140 ℃ to obtain a first component;

G03. dehydrating and condensing the first component at 170-220 ℃ to obtain a second component;

G04. and mixing the second component with maleic anhydride and a polymerization inhibitor, reacting at 120-150 ℃ for 3-5 hours, and cooling to normal temperature to obtain the alkyd prepolymer.

Wherein, the acid value of the obtained component is ensured to be lower than 10 mgKOH/g.

The following description will be given with reference to specific examples.

Example 1

(1) Preparation of alkyd prepolymer

75g of soybean oil fatty acid with high iodine value, 25g of phthalic anhydride, 32g of neopentyl glycol and 12g of trimethylolpropane are added into a reaction kettle, and N is introduced₂Then adding 0.35g of hypophosphorous acid, heating to 150 ℃, starting stirring, slowly heating (below 5 ℃/min) to 220 ℃, keeping the temperature for reaction, and stopping heating when the acid value is less than 10 mgKOH/g; when the temperature is reduced to 150 ℃, 10g of maleic anhydride is added, the mixture is continuously stirred, the reaction is carried out at the temperature of 150 ℃, and when the acid value is 10mgKOH/g, the temperature is reduced to 70 ℃, and then the mixture is discharged for standby.

(2) Preparation of alkyd-acrylic hybrid emulsion

Putting 360g of pure water and 180g of solid alkali-soluble acrylic resin Joncryl 678 into a reaction kettle, starting stirring, and heating to 80 ℃; then adding 60g of ammonia water (with the concentration of 25-28%) for three times, and stirring for 1 hour to prepare an alkali-soluble aqueous solution.

Preparing a pre-emulsion A in an emulsifying kettle: 160g of pure water, 10g of ADEKA reactive emulsifier SR1025, 4g of DOW emulsifier 2A1, 220g of methyl methacrylate, 20g of butyl acrylate, 60g of styrene, 80g of the above alkyd prepolymer and 1.2g of trimethylolpropane triacrylate were added and emulsified for 30min with high-speed stirring. 5 wt% of the pre-emulsion A was charged into a reaction vessel, and then 1g of an initiator sodium persulfate solution dissolved in 10g of pure water was added to carry out seed polymerization. After 15min, the remaining pre-emulsion A was added dropwise, while 0.72g of initiator sodium persulfate solution dissolved in 80g of pure water was added dropwise, after 90min, the temperature was maintained for 0.5 h. Preparing pre-emulsion B in an emulsifying kettle: 60g of pure water, 5g of ADEKA reactive emulsifier SR1025, 2g of DOW emulsifier 2A1, 20g of methyl methacrylate, 60g of styrene, 120g of the above alkyd prepolymer, 10g of methacrylic acid and 20g of diacetone acrylamide solution dissolved in 30g of pure water were added, and the mixture was stirred and emulsified at high speed for 30 min. After the heat preservation is finished, the pre-emulsion B is dripped, 0.5g of initiator sodium persulfate solution dissolved by 60g of pure water is dripped at the same time, the dripping is finished in 60min, and then the heat preservation is carried out for 1 h. After the heat preservation is finished, cooling to 70 ℃, and adding 0.5g of oxidant tert-butyl hydroperoxide solution dissolved by 10g of pure water; then 0.4g of sodium metabisulfite reducing agent solution dissolved by 10g of pure water is dripped, the dripping is finished for 15min, and then the temperature is kept for 15 min. Cooling to 65 deg.C, adding 0.5g oxidant tert-butyl hydroperoxide solution dissolved by 10g pure water; then 0.3g of sodium metabisulfite reducing agent solution dissolved by 10g of pure water is dripped, the dripping is finished for 15min, and then the temperature is kept for 30 min.

The temperature was reduced to 45 ℃ or below, and 9.2g of a solution of adipic dihydrazide as a crosslinking agent dissolved in 100g of pure water was added and stirred uniformly. Adding a preservative and a defoaming agent, adjusting solid content with pure water, filtering and discharging to obtain the alkyd-acrylic hybrid emulsion.

Example 2

(1) Preparation of alkyd prepolymer

Adding 70g of tall oil acid, 5g of phthalic anhydride, 20g of isophthalic acid, 5g of diethylene glycol, 26g of neopentyl glycol, 10g of trimethylolpropane and 0.18g of monobutyl tin oxide into a reaction kettle, introducing N2, adding 0.3g of hypophosphorous acid, heating to 150 ℃, starting stirring, slowly heating (below 5 ℃/min) to 220 ℃, carrying out heat preservation reaction, and stopping heating when the acid value is less than 10 mgKOH/g; when the temperature is reduced to 150 ℃, 12g of maleic anhydride is added, the mixture is continuously stirred, the reaction is carried out at the temperature of 150 ℃, and when the acid value is 10mgKOH/g, the temperature is reduced to 70 ℃, and then the mixture is discharged for standby.

(2) Preparation of alkyd-acrylic hybrid emulsion

300g of pure water and 100g of solid alkali-soluble acrylic resin Joncryl 586 and 37g of Joncryl 671 were put into a reaction kettle, stirred and heated to 80 ℃; then adding 45g of ammonia water (with the concentration of 25-28%) diluted by 120g of pure water into the solution for three times, and stirring the solution for 1 hour to prepare an alkali-soluble semitransparent water solution.

Preparing a monomer mixture in a dropping kettle: 158g of methyl methacrylate, 45g of styrene, 78.5g of butyl acrylate, 150g of the alkyd prepolymer and 32.6g of diacetone acrylamide are added and stirred until the components are completely and uniformly dissolved. Beginning to drop the mixed monomers into the reaction kettle: wherein the first 10 percent is dripped in 30min, and simultaneously 0.45g of initiator ammonium persulfate solution dissolved by 45g of pure water is dripped; after the last 90% of the solution was added dropwise over 60min, 1.8g of initiator ammonium persulfate solution dissolved in 120g of pure water was added dropwise, and the initiator solution was added dropwise over 90 min. Then preserving heat for 30min, after the heat preservation is finished, cooling to 70 ℃, and adding 0.38g of oxidant tert-butyl hydroperoxide solution dissolved by 7.5g of pure water; then 0.23g of a reducing agent German Bruggolite FF6M dissolved in 7.5g of pure water is added dropwise, the addition is completed within 15min, and then the temperature is maintained for 15 min. Cooling to 65 deg.C, adding 0.38g oxidant tert-butyl hydroperoxide solution dissolved by 7.5g pure water; then 0.23g of a reducing agent German Bruggolite FF6M dissolved in 7.5g of pure water is added dropwise, the addition is completed within 15min, and then the temperature is maintained for 30 min.

The temperature was reduced to 45 ℃ or below, and 13.5g of a solution of adipic dihydrazide as a crosslinking agent dissolved in 135g of pure water was added thereto and stirred uniformly. Adding a preservative and a defoaming agent, adjusting solid content with pure water, filtering and discharging to prepare the water-based alkyd-acrylic hybrid fine-particle size emulsion.

Example 3

(1) Preparation of alkyd prepolymer

Same as example 2

(2) Preparation of alkyd-acrylic hybrid emulsion

Adding 90g of dipropylene glycol methyl ether and 20g of ethanol into a high-pressure reaction kettle, closing an emptying valve to form a closed system, and heating to 130 ℃. Preparing a monomer mixture in a dropping kettle: 196g of methyl methacrylate, 30g of butyl acrylate, 33.6g of methacrylic acid, 40g of the above alkyd prepolymer, 24g of diacetone acrylamide, 3.2g of alpha-methylstyrene linear dimer and 6g of azobisisobutyronitrile solution as an initiator dissolved in 16g of ethanol were added and stirred for 30 min. After the mixture is completely and uniformly dissolved, dropping the mixed monomer into the reaction kettle by using a diaphragm pump, and dropping by using 120 mn. Preserving the temperature for 30min, then dropwise adding 0.8g of initiator tert-butyl peroxy-2-ethylhexanoate solution dissolved by 10g of ethanol into the reaction kettle by using a diaphragm pump, and dropwise adding for 15 min. Keeping the temperature for 2h, and then cooling to 50 ℃. Under the condition of continuous stirring, 40g of ammonia water (with the concentration of 25-28%) solution diluted by 60g of pure water is dripped for 30 min; thereafter, 800g of pure water was dropped within 30min, and stirred at high speed for 1 hour to prepare an alkali-soluble translucent aqueous solution.

Preparing a monomer mixture in a dropping kettle: 196g of methyl methacrylate, 104g of butyl acrylate, 172g of the alkyd prepolymer and 36.6g of diacetone acrylamide are added and stirred until the components are completely and uniformly dissolved. Heating the reaction kettle to 50 ℃, adding half of the monomer mixed solution into the reaction kettle, stirring for 30min, adding 0.6g of ammonium persulfate dissolved by 10g of pure water, 1g of ferrous sulfate heptahydrate dissolved by 10g of pure water and 6g of sodium pyrophosphate dodecahydrate dissolved by 10g of pure water, violently reacting and releasing heat, controlling the reaction temperature to be 65 +/-5 ℃, and keeping the temperature for 30 min. Then, the temperature is reduced to 50 ℃, 10g of vinyltriethoxysilane is mixed in the rest monomer mixed solution, the mixture is uniformly stirred and then added into a reaction kettle, after stirring for 30min, 0.6g of ammonium persulfate dissolved by 10g of pure water, 1g of ferrous sulfate heptahydrate dissolved by 10g of pure water and 6g of sodium pyrophosphate dodecahydrate dissolved by 10g of pure water are added, the reaction releases heat violently, the reaction temperature is controlled to be 65 +/-5 ℃, and the temperature is kept for 1 h.

Cooling to below 45 deg.C, adding 27g of adipic dihydrazide as crosslinking agent, and stirring. Adding a preservative and a defoaming agent, adjusting solid content with pure water, filtering and discharging to obtain the alkyd-acrylic hybrid emulsion.

Example 4

(1) Preparation of alkyd prepolymer

Same as example 1

(2) Preparation of alkyd-acrylic hybrid emulsion

Adding 280g of pure water, 2.8g of loyalty chemical industry anionic emulsifier A6828 and 0.5g of sodium bicarbonate into a reaction kettle, starting stirring, and heating to 85 ℃. Preparing a pre-emulsion A in an emulsifying kettle: adding 65g of pure water, 4.5g of loyalty chemical reaction type emulsifier A2405, 2g of anionic emulsifier A-6828, 92g of methyl methacrylate, 28g of butyl acrylate, 16.8g of methacrylic acid, 15g of the alkyd prepolymer, 12g of diacetone acrylamide and 1.8g of butyl mercaptopropionate, and stirring at high speed for emulsification for 30 min.

8 wt% of the pre-emulsion A was charged into a reaction vessel, and then 0.26g of an initiator ammonium persulfate solution dissolved in 6g of pure water was added to carry out seed polymerization. After 15min, the remaining pre-emulsion A was added dropwise, while 0.45g of initiator ammonium persulfate solution dissolved in 45g of pure water was added dropwise, after 90min, the temperature was maintained for 0.5 h. Under continuous high-speed stirring, 20g of ammonia water (with the concentration of 25-28%) diluted by 35g of pure water is dripped for 30min, and then the solution is subjected to heat preservation for 1h to prepare an alkali-soluble semitransparent water solution.

Preparing a pre-emulsion B in an emulsion kettle I: 40g of pure water, 1.8g of anionic emulsifier A-6828, 67.5g of methyl methacrylate, 15g of styrene, 3g of allyl methacrylate and 28g of the alkyd prepolymer are added, and stirred at high speed for emulsification for 30 min. Preparing a pre-emulsion C in an emulsifying kettle II: 55g of pure water, 2.6g of a reactive emulsifier A-2405, 56g of methyl methacrylate, 18g of butyl acrylate, 60g of the alkyd prepolymer, 6g of methacrylic acid, 15g of diacetone acrylamide and 0.28g of n-dodecyl mercaptan are added, and the mixture is stirred at a high speed and emulsified for 30 min. Heating the reaction kettle to 60 ℃, dropwise adding the pre-emulsion B into the reaction kettle, and simultaneously dropwise adding 0.5g of tert-butyl hydroperoxide solution dissolved by 40g of pure water and 0.45g of ferrous chloride solution dissolved by 40g of pure water respectively; meanwhile, the pre-emulsion C in the emulsifying kettle II is dripped into the emulsifying kettle I, and the mixture is continuously stirred and uniformly mixed. The materials in the emulsifying kettle I and the emulsifying kettle II are dripped within 120min, the tert-butyl hydroperoxide solution and the ferrous chloride solution are dripped within 150min, and then 60

Keeping the temperature at +/-1 ℃ for 30 min.

Cooling to below 45 deg.C, adding 13.5g of adipic dihydrazide as cross-linking agent, and stirring. Adding bactericide and defoamer, adjusting solid content with pure water, filtering and discharging to obtain the alkyd-acrylic hybrid emulsion.

Comparative example 1

Preparation of acrylic ester emulsion with common core-shell structure

260g of pure water, 6g of BASF anionic emulsifier LDBS, and 0.6g of sodium bicarbonate were put into a reaction vessel, stirred, and heated to 80 ℃. Preparing a pre-emulsion A in an emulsifying kettle: 80g of pure water, 5g of ADEKA reactive emulsifier SR1025, 2g of BASF anionic emulsifier LDBS, 143g of methyl methacrylate, 21g of butyl acrylate, 30g of styrene, 5g of methacrylic acid and 0.6g of trimethylolpropane triacrylate were added, and the mixture was stirred and emulsified at high speed for 30 min. 5 wt% of the pre-emulsion A was taken and added to a reaction vessel, and then 0.5g of an initiator ammonium persulfate solution dissolved in 5g of pure water was added to carry out seed polymerization. After 15min, the remaining pre-emulsion A was added dropwise, while 0.36g of initiator ammonium persulfate solution dissolved in 40g of pure water was added dropwise, after 90min, the temperature was maintained for 0.5 h. Preparing pre-emulsion B in an emulsifying kettle: 65g of pure water, 5g of ADEKA reactive emulsifier SR1025, 2g of BASF anionic emulsifier LDBS, 63g of methyl methacrylate, 80g of butyl acrylate, 26.8g of isooctyl acrylate, 13g of methacrylic acid and 15g of diacetone acrylamide solution dissolved in 15g of pure water were added thereto, and emulsified for 30min with high-speed stirring. After the heat preservation is finished, the pre-emulsion B is dripped, 0.25g of initiator ammonium persulfate solution dissolved by 30g of pure water is dripped at the same time, the dripping is finished in 60min, and then the heat preservation is carried out for 1 h. After the heat preservation is finished, cooling to 70 ℃, and adding 0.25g of oxidant tert-butyl hydroperoxide solution dissolved by 5g of pure water; then 0.2g of rongalite reducing agent solution dissolved by 5g of pure water is dripped, the dripping is finished for 15min, and then the temperature is kept for 15 min. Cooling to 65 deg.C, adding 0.25g oxidant tert-butyl hydroperoxide solution dissolved by 5g pure water; then 0.15g of rongalite reducing agent solution dissolved by 5g of pure water is dripped, the dripping is finished for 15min, and then the temperature is kept for 30 min.

The temperature is reduced to below 45 ℃, 7g of a crosslinking agent adipic dihydrazide solution dissolved by 50g of pure water is added, and the mixture is stirred uniformly. Adding bactericide and defoamer, adjusting solid content with pure water, filtering and discharging to obtain the conventional acrylate emulsion.

Comparative example 2

Preparation of traditional waterborne alkyd-acrylic hybrid resin

(1) Preparation of alkyd prepolymer

Same as example 2

(2) Preparation of two-stage dispersion water-based alkyd-acrylic hybrid resin

350g of the alkyd prepolymer and 162g of butyl cellosolve are added into a reaction kettle, stirring is started, and the temperature is raised to 138 ℃. Preparing a monomer mixture in a dropping kettle: 16g of methyl methacrylate, 143g of styrene, 21.6g of acrylic acid, and 6g of a t-butyl peroxybenzoate solution as an initiator dissolved in 10g of butyl cellosolve were added and stirred for 30 min. After the mixture is completely and uniformly dissolved, the mixed monomer is dripped into the reaction kettle, and the dripping is finished in 180 min. Preserving the temperature for 30min, then dropwise adding 0.8g of initiator tert-butyl peroxybenzoate solution dissolved by 5g of ethylene glycol butyl ether into the reaction kettle, and dropwise adding for 15 min. Keeping the temperature for 2h, and then cooling to 50 ℃. Then 23g N, N-dimethylethanolamine is added dropwise for 30 min; 460g of pure water is dripped in 30min under continuous high-speed stirring to prepare the secondary dispersion water-based alkyd-acrylic hybrid resin.

Property testing and results analysis

Samples of the emulsions of examples 1 to 4 and comparative examples 1 and 2 were taken, observed for appearance, odor, and tested for solids and viscosity. The emulsion sample is matched with matte varnish and sprayed on a cherry wood board, and the fullness, the hole penetration and the water resistance are compared.

TABLE 1

Note: the rating is 1-5, 1 represents the best, 5 represents the worst, and + represents slightly good and-represents slightly poor.

As can be seen from the above example and comparative example formulations and Table 1 above, the samples prepared in examples 1,2 and 4 contained no organic solvent and had zero VOC; example 3 a small amount of dipropylene glycol methyl ether, which is an alcohol ether solvent with a relatively high boiling point, is introduced during the synthesis of the alkali-soluble resin, and a film-forming aid commonly used for waterborne coatings is helpful for forming a continuous paint film from a waterborne alkyd-acrylic hybrid fine-particle-size emulsion; in contrast, in comparative example B, it was inevitable to add more alcohol ether solvent, such as butyl cellosolve, to achieve a VOC content of 150 g/L.

Tests of the water-based resin samples prepared in examples 1-4 and comparative examples 1 and 2 after paint preparation and spraying show that the water-based alkyd-acrylic hybrid fine-particle size emulsion of the primary dispersion disclosed by the invention has better fullness, more excellent substrate permeability and pigment wettability than common acrylic emulsion; compared with the traditional two-stage dispersion water-based alkyd-acrylic hybrid resin, the waterborne alkyd-acrylic hybrid resin has lower VOC content and better water resistance.

The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.