阅读说明：本技术 一种apao改性水性丙烯酸树脂及其制备方法 (APAO modified waterborne acrylic resin and preparation method thereof ) 是由 张武 康伦国 姚东生 于 2019-11-19 设计创作，主要内容包括：本发明涉及一种APAO改性水性丙烯酸树脂及其制备方法,按重量份计,其组分为：APAO 4.0～8.0份、交联单体3.0～6.0份、偶氮二异丁腈0.6～1.2份、丙烯酸2.5～6.5份、二乙二醇单丁醚20.0～40.0份、丙烯酸硬单体40.0～70.0份、丙烯酸软单体10.0～30.0份、中和剂4.0～10.0份、去离子水60.0～100.0份；本发明制得的APAO改性水性丙烯酸树脂,具有优异的附着力、耐水性以及优良的防流挂性能；可配制成单组分、双组分水性涂料,广泛用于水性木器涂料、水性金属涂料、水性工程涂料等。(The invention relates to an APAO modified waterborne acrylic resin and a preparation method thereof, wherein the APAO modified waterborne acrylic resin comprises the following components in parts by weight: 4.0-8.0 parts of APAO, 3.0-6.0 parts of crosslinking monomer, 0.6-1.2 parts of azodiisobutyronitrile, 2.5-6.5 parts of acrylic acid, 20.0-40.0 parts of diethylene glycol monobutyl ether, 40.0-70.0 parts of acrylic hard monomer, 10.0-30.0 parts of acrylic soft monomer, 4.0-10.0 parts of neutralizer and 60.0-100.0 parts of deionized water; the APAO modified waterborne acrylic resin prepared by the invention has excellent adhesive force, water resistance and excellent sagging resistance; can be prepared into single-component and double-component water-based coatings, and can be widely used for water-based wood coatings, water-based metal coatings, water-based engineering coatings and the like.)

1. An APAO modified waterborne acrylic resin, which is characterized in that: the APAO modified waterborne acrylic resin comprises the following components in parts by weight: 4.0 to 8.0 parts of APAO, 3.0 to 6.0 parts of crosslinking monomer, 0.6 to 1.2 parts of azodiisobutyronitrile, 2.5 to 6.5 parts of acrylic acid, 20.0 to 40.0 parts of diethylene glycol monobutyl ether, 40.0 to 70.0 parts of acrylic acid hard monomer, 10.0 to 30.0 parts of acrylic acid soft monomer, 4.0 to 10.0 parts of neutralizer and 60.0 to 100.0 parts of deionized water.

2. The APAO-modified waterborne acrylic resin of claim 1, wherein: the APAO has the average molecular weight of 1500-3000.

3. The APAO-modified waterborne acrylic resin of claim 1, wherein: the acrylic hard monomer is one or a combination of methyl acrylate, methyl methacrylate, acrylamide, isobornyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate and 2-propylheptyl acrylate.

4. The APAO-modified waterborne acrylic resin of claim 1, wherein: the acrylic soft monomer is one or a combination of butyl acrylate, butyl methacrylate, isooctyl methacrylate, lauryl methacrylate, tridecyl methacrylate, n-hexyl methacrylate, stearyl acrylate and glycidyl methacrylate.

5. The APAO-modified waterborne acrylic resin of claim 1, wherein: the crosslinking monomer is one or a combination of more of hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.

6. The APAO-modified waterborne acrylic resin of claim 1, wherein: the neutralizing agent is one or a combination of more of triethylamine, ammonia water and dimethylethanolamine.

7. The APAO-modified waterborne acrylic resin of claim 1, wherein: the preparation method of the APAO modified waterborne acrylic resin comprises the following steps:

a) in a storage tank, according to the weight parts of the formula, 1/3 diethylene glycol monobutyl ether, APAO and azobisisobutyronitrile are uniformly stirred to obtain a mixed solution I;

b) uniformly stirring a crosslinking monomer, azodiisobutyronitrile, acrylic acid, an acrylic acid hard monomer and an acrylic acid soft monomer in the storage tank according to the weight part of the formula to obtain a mixed monomer II;

c) introducing nitrogen into the multifunctional reaction kettle, adding the remaining 2/3 diethylene glycol monobutyl ether, heating to 80-82 ℃, then adding 1/4 mixed monomer II, stirring and reacting for 0.5-1.0 h until blue light appears, then simultaneously dropwise adding the mixed solution I and the remaining mixed monomer II, wherein the dropwise adding time is 3.0-4.0 h, after the dropwise adding is finished, heating to 88-90 ℃, adding a proper amount of azobisisobutyronitrile, keeping the temperature and reacting for 1.0-1.5 h, and finishing the reaction;

d) cooling to below 45 ℃, adding a neutralizing agent, stirring at a high speed for dispersing for 0.5h, adding deionized water with the formula amount, stirring for dispersing for 1.0h until the solution is completely dispersed, adding deionized water to remove specified solid content, and filtering to obtain the APAO modified waterborne acrylic resin.

Technical Field

The invention relates to a modified waterborne acrylic resin, in particular to an APAO modified waterborne acrylic resin and a preparation method thereof, belonging to the technical field of synthetic waterborne resin.

Background

Along with the development of economy, people pay more and more attention to the problem of environmental protection, in the coating resin industry, water-based resin is a novel resin type, and compared with solvent-based resin, the main solvent used by the water-based resin is water, so that the water-based resin is more environment-friendly and more economical, and is popular among more and more people, and is a leading role in the research field of the coating resin in the 21 st century.

The acrylic resin paint has excellent gloss and color retention, good mechanical property, good chemical stability, strong film forming capability, heat resistance, chemical resistance and the like. The acrylic resin is prepared by copolymerizing acrylic ester, methacrylate ester and other olefinic monomers, and can be synthesized into acrylic resins with different types, different performances and different application occasions by selecting different resin structures, different formulas, different production processes and different solvents.

The acrylic resin is not further crosslinked in the film forming process, so that the corresponding adhesive force is poor, and a paint film is easy to fall off when the acrylic resin is collided; the glass transition temperature of the resin used in the acrylic resin is high. The glass transition temperature of the acrylic resin influences the hardness and the flexibility of the quick-drying paint, the glass transition temperature is too high, and the hardness and the flexibility of the quick-drying paint are not enough; the glass transition temperature is too low, and the quick-drying paint has good flexibility and low hardness.

With the continuous expansion and deepening of the research of the water-based acrylic resin, various synthetic processes, abundant raw material selection and functional professional products are combined with the water-based acrylic resin. In order to improve the performance of the acrylic resin; chinese patent CN109081884A discloses a cross-linking modified high-gloss water-based acrylic resin and a preparation method thereof. The resin comprises methyl methacrylate, styrene, butyl acrylate, 2-hydroxyethyl methacrylate, ethyl acrylate, acrylic acid, ethylene glycol dimethacrylate, propylene glycol methyl ether, dipropylene glycol methyl ether, an initiator, N-dimethylethanolamine and deionized water. The resin adopts water as a diluent, does not contain benzene solvents, belongs to water-based resin, and has no harm and pollution to human bodies and the environment.

Chinese patent CN108178812A discloses a fluorine-silicon modified acrylic resin and preparation and application thereof, wherein the fluorine-silicon modified acrylic resin is prepared from the following raw materials in parts by mass: 1-8% of fluorine monomer, 1-5% of silicon monomer, 5-13% of monomer containing tertiary amine group, 7-22% of monomer containing hydroxyl group, 22-71% of methacrylic acid monomer mixture, 0.5-6% of initiator, 25-35% of solvent and 1-5% of organic acid, wherein the total amount of all the components is 100%; most of fluorine and silicon are enriched on the outer surface of the coating film after being crosslinked with an isocyanate curing agent to form a film, and the coating film has excellent hydrophobicity, corrosion resistance and chemical resistance due to the unique characteristics of C-F and Si-O; the addition of the organosilicon monomer reduces the consumption of fluorine, reduces the production cost and does not influence the corrosion resistance and the hydrophobicity of the coating film.

Chinese patent CN109796555A discloses a preparation method of a high-performance water-based acrylic resin, which comprises the following raw materials, by mass, 25-35 parts of hydroxyl-containing unsaturated monomers, 20-40 parts of hard monomers, 20-40 parts of soft monomers, 8-15 parts of unsaturated carboxylic acids, 3-5 parts of initiators, 0.5-2 parts of organosilicon modifiers, 0.5-1.5 parts of chain transfer agents and 80-90 parts of solvents; by adopting solution copolymerization, colorless and transparent acrylate prepolymer with the hydroxyl content of 2.5mmol/g and the solid content of 60 +/-1 percent is synthesized, and then the water-based acrylic resin is obtained by a salt formation method. The water-based acrylic resin with excellent performance is prepared by a simple method, cheap and easily-obtained raw materials and conventional equipment, the product has high glossiness, high drying speed, excellent mechanical property and good water resistance, weather resistance and solvent resistance, and the coating requirements of most workpieces are met.

The existing waterborne acrylic resin and modified waterborne acrylic resin have a plurality of problems, such as: many synthesis processes are too complicated and harsh, the repeatability is poor, the stability of products is influenced, equipment needs to be specifically improved, the energy consumption is high, the cost is increased, the adhesion force is poor, the sagging resistance is not good, and the like; many raw materials are expensive and cannot be supplied stably, affecting normal production cycle and product supply.

From the global perspective, the core technology of water-based resin is mainly mastered by coating enterprises across countries and is widely applied in markets in Europe and America. The industries have carried out strict technical blockade on national coating enterprises, and some domestic related enterprises and research institutes can only develop new products by means of autonomous innovation.

Disclosure of Invention

The invention aims to provide an APAO modified waterborne acrylic resin.

Another object of the present invention is to provide a method for preparing an APAO modified waterborne acrylic resin.

APAO (amorphous α -olefin copolymer) is a low molecular weight amorphous plastomer material formed from the polymerization of a-olefins and is microscopically an amorphous, random arrangement, and therefore has many properties not possessed by crystalline polymers and is also unique in its applications.

The APAO can effectively improve the processing performance and compatibility of the material, has good fluidity, good viscosity, difficult migration and good sagging resistance, and can be used as a good dispersant because the APAO has good wetting and flowing properties.

The invention introduces APAO into the molecular structure of the water-based acrylic resin through chemical bonds, and can effectively improve the adhesive force and the anti-sagging performance of the water-based acrylic resin.

The APAO modified waterborne acrylic resin adopts the following technical scheme: the composition comprises the following components in parts by weight: 4.0 to 8.0 parts of APAO, 3.0 to 6.0 parts of crosslinking monomer, 0.6 to 1.2 parts of azodiisobutyronitrile, 2.5 to 6.5 parts of acrylic acid, 20.0 to 40.0 parts of diethylene glycol monobutyl ether, 40.0 to 70.0 parts of acrylic acid hard monomer, 10.0 to 30.0 parts of acrylic acid soft monomer, 4.0 to 10.0 parts of neutralizer and 60.0 to 100.0 parts of deionized water.

Wherein the APAO has the average molecular weight of 1500-3000.

The acrylic hard monomer is one or a combination of methyl acrylate, methyl methacrylate, acrylamide, isobornyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate and 2-propylheptyl acrylate.

The acrylic soft monomer is one or a combination of butyl acrylate, butyl methacrylate, isooctyl methacrylate, lauryl methacrylate, tridecyl methacrylate, n-hexyl methacrylate, stearyl acrylate and glycidyl methacrylate.

The crosslinking monomer is one or a combination of more of hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.

The neutralizing agent is one or a combination of more of triethylamine, ammonia water and dimethylethanolamine.

The invention provides a preparation method of an APAO modified waterborne acrylic resin, which comprises the following steps:

a) in a storage tank, according to the weight parts of the formula, 1/3 diethylene glycol monobutyl ether, APAO and azobisisobutyronitrile are uniformly stirred to obtain a mixed solution I;

b) uniformly stirring a crosslinking monomer, azodiisobutyronitrile, acrylic acid, an acrylic acid hard monomer and an acrylic acid soft monomer in the storage tank according to the weight part of the formula to obtain a mixed monomer II;

c) introducing nitrogen into the multifunctional reaction kettle, adding the remaining 2/3 diethylene glycol monobutyl ether, heating to 80-82 ℃, then adding 1/4 mixed monomer II, stirring and reacting for 0.5-1.0 h until blue light appears, then simultaneously dropwise adding the mixed solution I and the remaining mixed monomer II, wherein the dropwise adding time is 3.0-4.0 h, after the dropwise adding is finished, heating to 88-90 ℃, adding a proper amount of azobisisobutyronitrile, keeping the temperature and reacting for 1.0-1.5 h, and finishing the reaction;

d) cooling to below 45 ℃, adding a neutralizing agent, stirring at a high speed for dispersing for 0.5h, adding deionized water with the formula amount, stirring for dispersing for 1.0h until the deionized water is completely dispersed, adding deionized water until the deionized water reaches the specified solid content, and filtering to obtain the APAO modified waterborne acrylic resin.

The APAO modified waterborne acrylic resin prepared by the invention has excellent adhesive force, water resistance and excellent sagging resistance; can be prepared into single-component and double-component water-based coatings, and can be widely used for water-based wood coatings, water-based metal coatings, water-based engineering coatings and the like.

Detailed Description

An APAO-modified waterborne acrylic resin of the present invention is further described below with reference to the examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.