CN113603833B

CN113603833B - Alkyd-acrylic hybrid emulsion and preparation method thereof

Info

Publication number: CN113603833B
Application number: CN202110752677.0A
Authority: CN
Inventors: 朱晓亮; 刘志刚; 陈寿生
Original assignee: Zhuhai Zhanchen New Material Co ltd
Current assignee: Zhuhai Zhanchen New Material Co ltd
Priority date: 2021-07-02
Filing date: 2021-07-02
Publication date: 2024-09-03
Anticipated expiration: 2041-07-02
Also published as: CN113603833A

Abstract

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 crosslinking monomer; 20-80 parts of alkyd prepolymer; 150-180 parts of stabilizer; 360-400 parts of water; 10-20 parts of auxiliary agent. Providing the emulsion mixture with fullness, substrate permeability and pigment wetting properties; and a stabilizer is introduced, and forms a micelle in the polymerization reaction process, so that a polymerization monomer mixed solution containing an alkyd prepolymer in a system is copolymerized under the surrounding of the micelle, emulsion particles with the nano-grade average particle size and narrow particle size distribution of a unimodal form are obtained, and the obtained alkyd-acrylic hybrid emulsion has the characteristics of zero VOC and good water resistance.

Description

Alkyd-acrylic hybrid emulsion and preparation method thereof

Technical Field

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

Background

With government restrictions on VOC (volatile hazardous substances) emissions, the use of solvent-based resins in the coating field is greatly restricted. The water-based paint is more water-based paint, is a relatively novel paint on the paint market, and has the following characteristics compared with solvent paint: 1. the water-based paint uses water as a solvent, so that a large amount of resources are saved; the fire hazard in construction is eliminated by the water-based paint; the pollution to the atmosphere is reduced; the water paint adopts only a small amount of low-toxicity alcohol ether organic solvent, thereby improving the operation environment condition. The organic solvent (accounting for the paint) of the general water paint is between 10 percent and 15 percent, and the cathode electrophoresis paint is reduced to below 1.2 percent, so that the pollution reduction and resource saving effects are remarkable; 2. the water-based paint can be directly coated and constructed on wet surfaces and in a wet environment; the water-based paint has good adaptability to the surface of the material and strong coating adhesive force; 3. the water-based paint coating tool can be cleaned by water, so that the consumption of cleaning solvent is greatly reduced; 4. the electrophoretic coating of the water-based paint is uniform and smooth. The flattening performance is good; the inner cavity, the welding line, the edges and the edges can be coated with a coating film with a certain thickness, so that the protective performance is good; the electrophoretic coating has the best corrosion resistance, and the highest salt fog resistance of the thick film cathode electrophoretic coating can reach 1200h.

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 coating, industrial corrosion prevention and the like. However, the current aqueous alkyd-acrylic hybrid resin is two-stage dispersion, namely, esterification and copolymerization are carried out by a solution polymerization method, and water is converted by redispersion after neutralization to form salt, so that the aqueous alkyd-acrylic hybrid resin inevitably contains more VOC and has the defect 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 the waterborne alkyd-acrylic hybrid emulsion in the prior art contains a large amount of VOC, has poor water resistance and has large particle size.

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

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

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

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

carrying out first mixing heating treatment on the 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 rest of water to obtain a second mixture;

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

According to the alkyd-acrylic hybrid emulsion provided by the first aspect of the application, in the emulsion mixture, acrylic monomers/vinyl monomers are used as main components, 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, the substrate permeability and the 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 the mixed solution of the polymerization monomers containing alkyd prepolymer in the system is copolymerized under the surrounding of the micelles, thereby obtaining emulsion particles with the nano-grade average particle size and the particle size distribution of narrower unimodal morphology, and obviously solving the problem of larger particle size of the traditional primary dispersion emulsion; meanwhile, the alkyd-acrylic hybrid emulsion has the characteristics of zero VOC and better water resistance through the synergistic effect of the components, has the advantages of good fullness, good substrate permeability and good pigment wettability, and is favorable for wide use.

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 in the large-scale preparation process, a plurality of reaction kettles are provided for action, so that the alkyd-acrylic hybrid emulsion with the excellent properties can be prepared.

Detailed Description

In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.

In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.

In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of 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, c may be single or multiple, respectively.

It should be understood that, in various embodiments of the present application, the sequence number of each process described above does not mean that the execution sequence of 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 functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in 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 weights of the relevant components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present application are scaled up or down within the scope of the disclosure of the embodiments of the present application. Specifically, the mass described in the specification of the embodiment of the application can be a mass unit which is known in the chemical industry field such as mu g, mg, g, kg.

The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. 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 application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.

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

Specifically, the alkyd-acrylic hybrid emulsion comprises 300-350 parts of acrylic monomer/vinyl monomer, wherein 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 C1-C20 alkyl methacrylate 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 a main component of the emulsion, and can ensure that the obtained emulsion has aqueous emulsion properties.

In some embodiments, the vinyl 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 a main component of emulsion, and can ensure that the obtained emulsion has aqueous emulsion property.

In specific embodiments, the acrylic monomer/vinyl monomer is added in a portion selected from 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350.

Specifically, the alkyd-acrylic hybrid emulsion comprises 10-50 parts of crosslinking monomers, and the crosslinking monomers can be favorable for crosslinking reaction among the monomers and improve interaction among the monomers.

In some embodiments, the crosslinking monomer is selected from at least one of acrylamide, methylolacrylamide, divinylbenzene, trimethylolpropane triacrylate, vinyltrimethoxysilane, diacetone acrylamide, adipic acid dihydrazide, acetoacetoxymethacrylate, hexamethylenediamine, and the crosslinking agent is provided to facilitate crosslinking between the monomers.

In a specific embodiment, the crosslinking monomer is added in parts selected from the group consisting of: 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts.

Specifically, the alkyd-acrylic hybrid emulsion comprises 20-80 parts of alkyd prepolymer, and the alkyd prepolymer containing unsaturated double bonds is used as one of polymerization monomers to form the alkyd-acrylic hybrid emulsion, so that the fullness, the substrate permeability and the 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 number soy oleic acid, tall oil acid, dehydrated ricinoleic acid, eleostearic acid.

In some embodiments, the diacid 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 catalyst provided is selected from an esterification catalyst that is used to promote the esterification reaction, thereby facilitating improved 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 specific embodiments, the catalyst is selected from monobutyl tin oxide, which is provided to facilitate the catalysis of the polyol to form ethers.

In some embodiments, an antioxidant is provided to inhibit the oxidation reaction of the system to avoid darkening of the synthesized alkyd prepolymer.

In some embodiments, the antioxidant is selected from at least one of 2, 6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-stearyl 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 selected from the group consisting of BHT, hypophosphorous acid and antioxidant 1010, wherein the hypophosphorous acid has the strongest antioxidant capacity, and the BHT and antioxidant 1010 have lower cost and have a certain polymerization inhibition effect besides the antioxidant yellowing effect.

Wherein, in order to avoid the double bond of maleic anhydride from polymerizing during high temperature reaction, the provision of a polymerization inhibitor can facilitate the formation of alcohol-acid prepolymer. In some embodiments, the polymerization inhibitor is selected from at least one of para-hydroxyanisole, hydroquinone, p-benzoquinone, methylhydroquinone, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, phenothiazine, β -phenylnaphthylamine, p-tert-butylcatechol, 1-diphenyl-2-trinitrophenylhydrazine, 2, 6-tetramethylpiperidine nitroxide, polymerization inhibitor-701, and polymerization inhibitor-705.

Specifically, the alkyd-acrylic hybrid emulsion provided includes 150-180 parts of a stabilizer, which is a water-soluble or water-swellable polymer that is converted in situ from a water-insoluble polymer that is not active with a protective colloid to an active water-soluble or water-swellable polymer that is active with a protective colloid by addition of a neutralizing agent.

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

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

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

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

Specifically, the alkyd-acrylic hybrid emulsion comprises 10-20 parts of auxiliary agents, wherein the auxiliary agents comprise 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 emulsifiers include, but are not limited to, alkali metal or ammonium salts of alkyl sulfates having 8 to 22 carbon atoms, alkali metal and ammonium salts of sulfuric monoesters of ethoxylated alkanols, alkali metal and ammonium salts of sulfuric monoesters of ethoxylated alkylphenols, alkali metal and ammonium salts of alkyl sulfonates having 12 to 18 carbon atoms, alkali metal and ammonium salts of alkylaryl sulfonates or alkylbenzyl sulfonates having 9 to 18 carbon atoms, alkali metal salts of alkylbenzene sulfonates, sulfonated fatty acids, sulfonated olefins, sulfonated diphenyl ethers, xantho succinates, fatty alcohol sulfates, alkylphenol sulfates, alkylpolyethylene glycol ether sulfates, fatty alcohol phosphates, alkylphenol sulfates, alkylpolyethylene glycol ether phosphates, alkylpolyalkylene oxide phosphates and fatty alcohol ether phosphates; nonionic emulsifiers include, but are not limited to, ethoxylates of long chain alcohols, homo-and copolymers of polyethylene oxide/polypropylene oxide, ethoxylated monoalkylphenols; reactive emulsifiers include at least one emulsifying group and at least one free radical polymerizable group (e.g., allyl, acrylate, methacrylate, vinyl ether) including, but not limited to, SR10 of ADEKA, SR1025, ER20, etc., or PAM 100, PAM200, PAM4000 of SOLVAY.

In some embodiments, a buffer is used to stabilize the pH environment of the system so that the reaction proceeds smoothly. Buffers 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, reduce its molecular weight distribution, and improve the particle size distribution of the emulsion, thereby further contributing to the physical and chemical properties of the paint film. Among these chain transfer agents include, but are not limited to, n-dodecyl mercaptan, t-dodecyl mercaptan, alpha-methyl styrene linear dimer, t-butyl mercaptan, mercaptoacetic acid, mercaptopropionic acid, butyl mercaptopropionate, 2-ethylhexyl mercaptoacetate, 2-ethylhexyl mercaptopropionate, isotridecyl mercaptoacetate, mercaptopropyl trimethoxysilane, and the like.

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

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

In some embodiments, the neutralizing agent is selected from one of ammonia, triethylamine, dimethylethanolamine, potassium hydroxide, sodium hydroxide, and any combination thereof. The neutralizing agent can be provided for better regulating the reaction system.

In some embodiments, providing an antifoaming agent helps to eliminate foaming during the reaction, ensuring that the resulting emulsion does not foam.

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

The second aspect of the embodiment of the application provides a preparation method of an alkyd-acrylic hybrid emulsion, which comprises the following steps:

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

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

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

s04, carrying out third mixing and heating treatment on the first mixture and the second mixture, and carrying out filtering treatment to obtain the alkyd-acrylic hybrid emulsion.

In step S01, the raw material components and parts of the alkyd-acrylic hybrid emulsion provided are the same as those discussed above, and for the sake of economy, details are not repeated here.

In step S02, the stabilizer and a part of water are subjected to a first mixing heat treatment to obtain a first mixture.

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

In step S03, the acrylic monomer/vinyl monomer, the crosslinking monomer, the alkyd prepolymer, the auxiliary agent and the rest of water are subjected to a second mixing treatment to obtain a second mixture.

In a specific embodiment, preparing a monomer mixture in an emulsifying kettle, wherein the monomer mixture comprises at least one acrylic monomer or/and vinyl monomer, a crosslinking monomer, and mixed monomers of the alkyd prepolymer, and the components of water, an emulsifying agent, a buffering agent, a chain transfer agent and the like; an initiator solution system was prepared in a drop tank.

In step S04, the first mixture and the second mixture are subjected to third mixing and heating treatment, and filtering treatment is carried out, so that the alkyd-acrylic hybrid emulsion is obtained.

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

Form one: the acrylic acid mixed monomer is designed as a component, a certain proportion is added into a reaction kettle to carry out seed polymerization, and then the rest part is added dropwise;

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

Form three: the acrylic acid mixed monomer is designed into at least more than two components with different monomer types and proportions, a first component with a certain proportion is added into a reaction kettle for seed polymerization, then the rest part is dripped, and at the same time, the other component mixed monomer is dripped into the component for uniform mixing, so that a special progressive structure is formed;

in the above mode, the mixed monomer for 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 in multiple times.

In a specific embodiment, after the bottom material of the reaction kettle is heated to a certain temperature, the monomer mixture and the initiator system are added into the reaction kettle in a certain mode to carry out polymerization reaction. Further, after the possibly needed post-elimination residual monomer stage, 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 alkyd prepolymer, namely vegetable oil fatty acid, dibasic acid, polyalcohol, maleic anhydride, catalyst, antioxidant and polymerization inhibitor;

G02. Heating and stirring vegetable oil fatty acid, dibasic acid, polyalcohol, catalyst and antioxidant at 110-140 ℃ under protective atmosphere to obtain a first component;

G03. carrying out dehydration condensation treatment on the first component at 170-220 ℃ to obtain a second component;

G04. Mixing the second component with maleic anhydride and polymerization inhibitor, reacting at 120-150 deg.c for 3-5 hr, and cooling to normal temperature to obtain alkyd prepolymer.

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

The following description is made with reference to specific embodiments.

Example 1

(1) Preparation of alkyd prepolymers

Adding 75g of soybean oil fatty acid with high iodine value, 25g of phthalic anhydride, 32g of neopentyl glycol and 12g of trimethylolpropane into a reaction kettle, introducing N ₂ g of hypophosphorous acid, heating to 150 ℃, starting stirring, slowly heating (below 5 ℃/min) to 220 ℃ for heat preservation reaction, and stopping heating when the acid value is less than 10 mgKOH/g; when the temperature is reduced to 150 ℃,10 g of maleic anhydride is added, stirring is continued, the temperature is kept at 150 ℃ for reaction, 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

360G of pure water and 180g of solid alkali-soluble acrylic resin Joncryl 678 are put into a reaction kettle, stirring is started, and the mixture is heated to 80 ℃; then 60g ammonia water (concentration 25-28%) solution is added three times, and the mixture is stirred for 1h to prepare 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 alkyd prepolymer and 1.2g of trimethylolpropane triacrylate are added and are stirred and emulsified at high speed for 30min. 5wt% of the pre-emulsion A was added to the reaction vessel, and then 1g of an initiator sodium persulfate solution dissolved in 10g of pure water was added to conduct seed polymerization. After 15min, the remaining pre-emulsion A was added dropwise, while 0.72g of an initiator sodium persulfate solution dissolved in 80g of pure water was added dropwise, after completion of 90min, followed by heat preservation for 0.5h. Preparing a 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 alkyd prepolymer, 10g of methacrylic acid and 20g of diacetone acrylamide solution dissolved by 30g of pure water are added, and the mixture is stirred and emulsified at a high speed for 30min. After the completion of the heat preservation, the pre-emulsion B was added dropwise, while 0.5g of an initiator sodium persulfate solution dissolved in 60g of pure water was added dropwise, after completion of the 60min addition, followed by heat preservation for 1 hour. After the heat preservation is finished, the temperature is reduced to 70 ℃, and 0.5g of oxidant tert-butyl hydroperoxide solution dissolved by 10g of pure water is added; then, 0.4g of sodium metabisulfite reducing agent solution dissolved in 10g of pure water was added dropwise, and after completion of the addition for 15 minutes, the mixture was incubated for 15 minutes. Cooling to 65 ℃, and adding 0.5g of oxidant tert-butyl hydroperoxide solution dissolved by 10g of pure water; then, 0.3g of sodium metabisulfite reducing agent solution dissolved in 10g of pure water was added dropwise, and after completion of the addition for 15 minutes, the mixture was kept at a temperature for 30 minutes.

Cooling to below 45 ℃, adding 9.2g of cross-linking agent adipic dihydrazide solution dissolved by 100g of pure water, and stirring uniformly. Adding preservative and defoamer, adjusting solid content by pure water, filtering and discharging to obtain the alkyd-acrylic hybrid emulsion.

Example 2

(1) Preparation of alkyd prepolymers

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 ℃ for 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, stirring is continued, the temperature is kept at 150 ℃ for reaction, 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 are put into a reaction kettle, stirring is started, and the mixture is heated to 80 ℃; then, 45g of aqueous ammonia (concentration 25-28%) diluted with 120g of pure water was added three times and stirred for 1 hour to prepare an alkali-soluble semitransparent aqueous solution.

Preparing monomer mixed solution in a dripping kettle: 158g of methyl methacrylate, 45g of styrene, 78.5g of butyl acrylate, 150g of the alkyd prepolymer, 32.6g of diacetone acrylamide are added and stirred until complete and uniform dissolution is achieved. Dropwise adding the mixed monomers into the reaction kettle: wherein the first 10% was completely added dropwise over 30 minutes while adding dropwise a solution of 0.45g of initiator ammonium persulfate dissolved in 45g of pure water; the latter 90% was completely added dropwise over 60 minutes, while 1.8g of an initiator ammonium persulfate solution dissolved in 120g of pure water was added dropwise, and the initiator solution was added dropwise over 90 minutes. Then preserving the heat for 30min, cooling to 70 ℃ after the heat preservation is finished, and adding 0.38g of oxidant tert-butyl hydroperoxide solution dissolved by 7.5g of pure water; then, 0.23g of a Bulgerman Bruggolite FF M solution of a reducing agent dissolved in 7.5g of pure water was added dropwise thereto, followed by 15 minutes of heat preservation. Cooling to 65 ℃, and adding 0.38g of oxidant tert-butyl hydroperoxide solution dissolved by 7.5g of pure water; then, 0.23g of a Bulgerman Bruggolite FF M solution of a reducing agent dissolved in 7.5g of pure water was added dropwise thereto, followed by heat preservation for 30 minutes after completion of the dropwise addition for 15 minutes.

Cooling to below 45 ℃, adding 13.5g of cross-linking agent adipic dihydrazide solution dissolved by 135g of pure water, and stirring uniformly. Adding preservative and defoamer, adjusting solid content by pure water, filtering and discharging to obtain the water-based alkyd-acrylic hybrid fine particle size emulsion.

Example 3

(1) Preparation of alkyd prepolymers

Same as in example 2

(2) Preparation of alkyd-acrylic hybrid emulsion

90G of dipropylene glycol methyl ether and 20g of ethanol are added into a high-pressure reaction kettle, an emptying valve is closed to form a closed system, and the temperature is raised to 130 ℃. Preparing monomer mixed solution in a dripping kettle: 196g of methyl methacrylate, 30g of butyl acrylate, 33.6g of methacrylic acid, 40g of the alkyd prepolymer, 24g of diacetone acrylamide, 3.2g of alpha-methylstyrene linear dimer and 6g of initiator azobisisobutyronitrile solution dissolved in 16g of ethanol are added and stirred for 30min. After complete dissolution, the mixed monomers were added dropwise to the reaction vessel using a diaphragm pump, and the addition was completed using 120 mn. After the temperature was kept for 30 minutes, 0.8g of t-butyl peroxy-2-ethylhexanoate solution, which was an initiator dissolved in 10g of ethanol, was added dropwise to the reaction vessel with a diaphragm pump for 15 minutes. The temperature is kept for 2 hours, and then the temperature is reduced to 50 ℃. Under continuous stirring, 40g of ammonia water (with the concentration of 25-28%) diluted by 60g of pure water is dropwise added for 30min; then, 800g of pure water was added dropwise over 30 minutes, and the mixture was stirred at high speed for 1 hour to prepare an alkali-soluble semitransparent aqueous solution.

Preparing monomer mixed solution in a dripping kettle: 196g of methyl methacrylate, 104g of butyl acrylate, 172g of the alkyd prepolymer described above and 36.6g of diacetone acrylamide are added and stirred until completely dissolved homogeneously. The reaction vessel was heated to 50℃and half of the monomer mixture was added to the reaction vessel, after stirring for 30 minutes, 0.6g of ammonium persulfate dissolved in 10g of pure water, 1g of ferrous sulfate heptahydrate dissolved in 10g of pure water, and 6g of sodium pyrophosphate dodecahydrate dissolved in 10g of pure water were added, and the reaction was vigorously exothermic, and the reaction temperature was controlled at 65.+ -. 5℃and kept at that temperature for 30 minutes. Then, the temperature is reduced to 50 ℃,10 g of vinyltriethoxysilane is mixed in the residual monomer mixed solution, the mixture is added into a reaction kettle after being stirred uniformly, after being stirred 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 is vigorously exothermic, the reaction temperature is controlled to be 65+/-5 ℃, and the temperature is kept for 1h.

Cooling to below 45 ℃, adding 27g of cross-linking agent adipic dihydrazide, and uniformly stirring. Adding preservative and defoamer, adjusting solid content by pure water, filtering and discharging to obtain the alkyd-acrylic hybrid emulsion.

Example 4

(1) Preparation of alkyd prepolymers

Same as in example 1

(2) Preparation of alkyd-acrylic hybrid emulsion

280G of pure water 2.8g of loyalty chemical anionic emulsifier A6828 and 0.5g of sodium bicarbonate are put into a reaction kettle, stirring is started and heated to 85 ℃. Preparing a pre-emulsion A in an emulsifying kettle: 65g of pure water, 4.5g of loyalty chemical reactive emulsifier A2405, 2g of anionic emulsifier A-6828, 92g of methyl methacrylate, 28g of butyl acrylate, 16.8g of methacrylic acid, 15g of alkyd prepolymer, 12g of diacetone acrylamide and 1.8g of butyl mercaptopropionate are added, and the mixture is stirred and emulsified at a high speed for 30min.

8Wt% of the pre-emulsion A was added to the reaction vessel, and then 0.26g of an initiator ammonium persulfate solution dissolved in 6g of pure water was added to conduct seed polymerization. After 15min, the remaining pre-emulsion A was added dropwise, while simultaneously adding 0.45g of an initiator ammonium persulfate solution dissolved in 45g of pure water, after completion of the addition for 90min, followed by heat preservation for 0.5h. Under continuous high-speed stirring, 20g of ammonia water (25-28% concentration) diluted by 35g of pure water is added dropwise, 30min is added dropwise, and then the mixture is kept for 1h to prepare an alkali-soluble semitransparent aqueous solution.

Preparing a pre-emulsion B in an emulsifying 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 the mixture is stirred and emulsified for 30min at a high speed. Preparing a pre-emulsion C in an emulsifying kettle II: 55g of pure water, 2.6g of 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 and emulsified at a high speed for 30min. 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 added dropwise within 120min, the tert-butyl hydroperoxide solution and the ferrous chloride solution are added dropwise within 150min, and then the mixture is added dropwise within 60min

Keep the temperature at + -1 ℃ for 30min.

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

Comparative example 1

Preparation of acrylate 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 kettle, stirring was started, and the mixture was 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 are added and emulsified by high-speed stirring for 30min. 5wt% of the pre-emulsion A was added to the reaction vessel, and then 0.5g of an initiator ammonium persulfate solution dissolved in 5g of pure water was added to conduct seed polymerization. After 15min, the remaining pre-emulsion A was added dropwise, while simultaneously adding 0.36g of an initiator ammonium persulfate solution dissolved in 40g of pure water, after completion of the addition for 90min, followed by heat preservation for 0.5h. Preparing a 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 with 15g of pure water are added, and the mixture is stirred and emulsified at high speed for 30min. After the completion of the heat preservation, the pre-emulsion B was added dropwise, while 0.25g of an initiator ammonium persulfate solution dissolved in 30g of pure water was added dropwise, after 60 minutes of completion of the dropwise addition, followed by heat preservation for 1 hour. After the heat preservation is finished, the temperature is reduced to 70 ℃, and 0.25g of oxidant tert-butyl hydroperoxide solution dissolved by 5g of pure water is added; then, 0.2g of rongalite reducing agent solution dissolved by 5g of pure water was added dropwise, and after completion of the addition for 15 minutes, the mixture was kept warm for 15 minutes. Cooling to 65 ℃, and adding 0.25g of oxidant tert-butyl hydroperoxide solution dissolved by 5g of pure water; then, 0.15g of rongalite reducing agent solution dissolved by 5g of pure water was added dropwise, and after completion of the addition for 15 minutes, the mixture was kept warm for 30 minutes.

Cooling to below 45 ℃, adding 7g of cross-linking agent adipic dihydrazide solution dissolved by 50g of pure water, and stirring uniformly. Adding bactericide and defoamer, adjusting solid content with pure water, filtering and discharging to obtain conventional acrylate emulsion.

Comparative example 2

Preparation of traditional waterborne alkyd-acrylic hybrid resin

(1) Preparation of alkyd prepolymers

Same as in example 2

(2) Preparation of two-stage aqueous alkyd-acrylic hybrid resin

350G of the alkyd prepolymer and 162g of ethylene glycol butyl ether are added into a reaction kettle, stirring is started, and the temperature is raised to 138 ℃. Preparing monomer mixed solution in a dripping kettle: 16g of methyl methacrylate, 143g of styrene, 21.6g of acrylic acid and 6g of a solution of tert-butyl peroxybenzoate as initiator dissolved in 10g of ethylene glycol butyl ether are added and stirred for 30min. After complete dissolution, the mixed monomers were started to be added dropwise into the reaction kettle for 180 min. After 30min of incubation, 0.8g of t-butyl peroxybenzoate as initiator dissolved in 5g of ethylene glycol butyl ether was added dropwise to the reaction vessel, followed by 15min of addition. The temperature is kept for 2 hours, and then the temperature is reduced to 50 ℃. Then 23g of N, N-dimethylethanolamine is added dropwise for 30min; 460g of pure water was added dropwise over 30min with continuous high-speed stirring to prepare a two-stage aqueous alkyd-acrylic hybrid resin.

Property testing and results analysis

Samples of the emulsions of examples 1-4 and comparative examples 1, 2 were taken, observed for appearance, odor, and tested for solids content and viscosity. The emulsion sample is used for preparing matte varnish, and the varnish is sprayed on cherry wood boards to compare fullness, hole-entering performance and water resistance.

TABLE 1

Note that: ① The ratings 1-5, 1 representing best, 5 representing worst, + representing slightly better, -representing slightly worse.

As can be seen from the above examples and comparative examples formulations and table 1, the samples prepared in examples 1,2 and 4 contain no organic solvent and have zero VOC; example 3a small amount of dipropylene glycol methyl ether, an alcohol ether solvent with a higher boiling point, is introduced in the process of synthesizing the alkali-soluble resin, and a film forming aid commonly used for a real paint is used for helping the formation of a continuous paint film by the aqueous alkyd-acrylic hybrid fine particle size emulsion; in comparative example B, however, it is unavoidable to add more alcohol ether solvent, such as ethylene glycol butyl ether, and the VOC content reaches 150g/L.

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

The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.

Claims

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

the preparation method of the alkyd-acrylic hybrid emulsion comprises the following steps:

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

wherein the acid value of the alkyd prepolymer is lower than 10mgKOH/g;

The stabilizer is selected from alkali-soluble resin, and the alkali-soluble resin is selected from solid alkali-soluble resin or solution alkali-soluble resin or emulsion alkali-soluble resin, is insoluble in acidic or neutral aqueous medium with pH less than or equal to 7 or exists in emulsion or suspension, but when the aqueous medium is alkaline, the stabilizer is dissolved into a uniform transparent system, and various acid groups contained in a molecular structure are neutralized by cations to serve as a high-molecular anionic surfactant.

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

3. The alkyd-acrylic hybrid emulsion of claim 2, wherein 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; and/or the number of the groups of groups,

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 number of the groups of groups,

The polyalcohol 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 according to 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 number of the groups of groups,

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-stearyl alcohol ester and phosphite antioxidants; and/or the number of the groups of groups,

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

5. The alkyd-acrylic hybrid emulsion of any one of claims 1-4, wherein the acrylic monomer is selected from at least one of acrylic acid, methacrylic acid, and C1-C20 alkyl methacrylate; and/or the number of the groups of groups,

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

6. The alkyd-acrylic hybrid emulsion of claim 5, wherein the C1-C20 alkyl methacrylate 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 hybrid alkyd-acrylic 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, methylolacrylamide, divinylbenzene, trimethylolpropane triacrylate, vinyltrimethoxysilane, diacetone acrylamide, adipic acid dihydrazide, acetoacetoxymethacrylate, hexamethylenediamine.

8. The alkyd-acrylic hybrid emulsion according to any 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 raw materials according to the alkyd-acrylic hybrid emulsion of any one of claims 1 to 8;

wherein the acid value of the alkyd prepolymer is lower than 10mgKOH/g;

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

providing raw materials of alkyd prepolymer, namely vegetable oil fatty acid, dibasic acid, polyalcohol, maleic anhydride, catalyst, antioxidant and 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 a polymerization inhibitor, reacting for 3-5 hours at 120-150 ℃, and cooling to normal temperature to obtain the alkyd prepolymer.