阅读说明：本技术 一种apao改性苯丙乳液及其制备方法 (APAO modified styrene-acrylic emulsion and preparation method thereof ) 是由 张武 谢义鹏 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改性苯丙乳液及其制备方法,按重量份计,其组成为：APAO 4.0～8.0份、丙烯酸酯硬单体10.0～25.0份、丙烯酸酯软单体6.0～20.0份、丙烯酸缩水甘油酯2.0～5.0份、苯乙烯20.0～35.0份、交联单体1.5～4.0份、丙烯酸2.5～5.0份、过硫酸铵0.1～0.3份、碳酸氢钠0.5～1.0份、中和剂2.5～6.0份、乳化剂1.5～4.5份、助溶剂5.0～10.0份、去离子水100.0～160.0份；本发明提供一种附着力好、抗流挂性能好的APAO改性苯丙乳液,无需外加抗流挂助剂。本发明制得的APAO改性苯丙乳液具有良好的附着力、耐酸碱性、耐水性、耐盐雾性、抗流挂性能好以及施工简单等性能。(The invention relates to an APAO modified styrene-acrylic emulsion and a preparation method thereof, wherein the APAO modified styrene-acrylic emulsion comprises the following components in parts by weight: 4.0-8.0 parts of APAO, 10.0-25.0 parts of acrylate hard monomer, 6.0-20.0 parts of acrylate soft monomer, 2.0-5.0 parts of glycidyl acrylate, 20.0-35.0 parts of styrene, 1.5-4.0 parts of crosslinking monomer, 2.5-5.0 parts of acrylic acid, 0.1-0.3 part of ammonium persulfate, 0.5-1.0 part of sodium bicarbonate, 2.5-6.0 parts of neutralizer, 1.5-4.5 parts of emulsifier, 5.0-10.0 parts of cosolvent and 100.0-160.0 parts of deionized water; the invention provides the APAO modified styrene-acrylic emulsion with good adhesive force and good anti-sagging performance, and an anti-sagging auxiliary agent is not required to be added. The APAO modified styrene-acrylic emulsion prepared by the invention has the advantages of good adhesive force, acid and alkali resistance, water resistance, salt spray resistance, good anti-sagging performance, simple construction and the like.)

1. An APAO modified styrene-acrylic emulsion, which is characterized in that: the composition comprises the following components in parts by weight: 4.0-8.0 parts of APAO, 10.0-25.0 parts of acrylate hard monomer, 6.0-20.0 parts of acrylate soft monomer, 2.0-5.0 parts of glycidyl acrylate, 20.0-35.0 parts of styrene, 1.5-4.0 parts of crosslinking monomer, 2.5-5.0 parts of acrylic acid, 0.1-0.3 part of ammonium persulfate, 0.5-1.0 part of sodium bicarbonate, 2.5-6.0 parts of neutralizer, 1.5-4.5 parts of emulsifier, 5.0-10.0 parts of cosolvent and 100.0-160.0 parts of deionized water.

2. The APAO-modified styrene-acrylic emulsion of claim 1, wherein: the acrylate hard monomer is one or a combination of methyl acrylate, acrylamide, acrylonitrile, methyl methacrylate, isobornyl acrylate, isobornyl methacrylate and 2-propyl heptyl acrylate.

3. The APAO-modified styrene-acrylic emulsion of claim 1, wherein: the acrylate soft monomer is one or a combination of butyl acrylate, butyl methacrylate, isooctyl methacrylate, lauryl methacrylate, stearyl methacrylate and stearyl acrylate.

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

5. The APAO-modified styrene-acrylic emulsion of claim 1, wherein: the emulsifier is OP-10.

6. The APAO-modified styrene-acrylic emulsion of claim 1, wherein: the cosolvent is one or a combination of more of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and propylene glycol methyl ether acetate.

7. The APAO-modified styrene-acrylic emulsion of claim 1, wherein: the neutralizing agent is one or a combination of triethylamine, ammonia water and dimethylethanolamine.

8. The method of preparing an APAO-modified styrene-acrylic emulsion according to claim 1, wherein: the preparation method comprises the following preparation processes:

1) weighing the components in proportion, sequentially adding an acrylate hard monomer, an acrylate soft monomer, a crosslinking monomer and acrylic acid, and uniformly stirring to obtain a mixed solution I;

2) weighing the raw materials in proportion, sequentially adding styrene, APAO, a cosolvent and glycidyl acrylate, and uniformly stirring to obtain a mixed solution II;

3) preparing a 5% ammonium persulfate aqueous solution in advance, adding an emulsifier, sodium bicarbonate, part of deionized water and 1/6 ammonium persulfate aqueous solution into a multifunctional reaction kettle, starting stirring and heating, heating to 76-80 ℃, adding 1/3 mixed solution I at a constant speed, and stirring for reaction until blue light appears;

4) and simultaneously dropwise adding the mixed solution II, the rest of the mixed solution I and 2/3 ammonium persulfate aqueous solution at a constant speed for 4.0-5.0 h, controlling the temperature at 80-82 ℃ in the dropwise adding process, heating to 84-85 ℃ after the dropwise adding is finished, adding the rest of 1/6 ammonium persulfate aqueous solution, carrying out heat preservation stirring reaction for 1.5-2.0 h, starting cooling water to cool, reducing the temperature to below 45 ℃, adjusting the pH value to 7.5-8.0 by using a neutralizing agent, and adding the rest of deionized water to obtain the APAO modified styrene-acrylic emulsion.

Technical Field

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

Background

The styrene-acrylic emulsion is obtained by emulsion copolymerization of styrene and butyl acrylate monomers. The styrene-acrylic emulsion is a system which is researched more in emulsion polymerization, is an important non-crosslinking emulsion and has very wide application. The water-based styrene-acrylic emulsion has the advantages of good film forming property, good construction property, good alkali resistance and color retention of a coating film, no pollution and the like, and is widely applied at present. However, the styrene-acrylic emulsion product is easy to become brittle at low temperature and poor in high temperature resistance, and the most obvious defects in coating application are high-temperature re-adhesion, which causes the reduction of stain resistance, poor water resistance and weather resistance, poor sag resistance and the like, so that the application range of the styrene-acrylic emulsion product is limited to a certain extent.

At present, people have been focusing on modifying styrene-acrylic emulsion resin in order to obtain styrene-acrylic emulsion paint with excellent performance. In recent years, styrene-acrylic resin is modified by fluorine-containing and silicon-containing monomers, so that the original advantages of the styrene-acrylic emulsion copolymer can be maintained, and the styrene-acrylic emulsion copolymer has the characteristics of excellent weather resistance, water resistance, oil resistance, heat resistance, stain resistance and the like, thereby having wide application prospects.

Chinese patent CN109970900A discloses a preparation method of attapulgite modified cationic styrene-acrylic emulsion, which comprises the following steps: after acid activation is carried out on attapulgite raw ore, surface modification is carried out on the attapulgite raw ore by using a functional organic monomer; then taking modified attapulgite, styrene and acrylic ester as raw materials, taking a cationic surface active-nonionic surfactant as a composite emulsifier, and carrying out emulsion polymerization reaction under the action of an initiator to obtain the attapulgite modified cationic styrene-acrylic emulsion.

Chinese patent CN103923271A discloses an organosilicon modified styrene-acrylic emulsion, 1) firstly putting deionized water, tert-butyl alcohol and isopropanol into a reaction kettle, stirring and mixing uniformly, heating to 60-70 ℃ to prepare a solution a; 2) dissolving styrene, isooctyl acrylate, ethyl silicate, an organic silicon monomer and an anion ring-opening polymerization emulsion into the solution a, fully and uniformly stirring, and preserving heat for 2 hours until the temperature reaches 80-90 ℃ to prepare a solution b; 3) putting vinyl silicone oil, silicon dioxide aerogel and dimethylformamide into the solution b, uniformly stirring, and stirring for 30 minutes to obtain a solution c; 4) controlling the temperature of the solution c to be 60-65 ℃, then dropwise adding potassium persulfate, finishing dropwise adding within 0.5 hour, and cooling to room temperature to obtain a solution d; 5) and adjusting the pH value of the solution d to be neutral by using ammonia water, discharging, and preparing the styrene-acrylic emulsion, wherein the crosslinking degree of the emulsion film is improved, so that the weather resistance of the styrene-acrylic emulsion is greatly improved.

Chinese patent CN102617786A discloses a fluorine monomer modified styrene-acrylic emulsion, which is prepared from the following components in percentage by mass: 1-6% of fluoroalkyl methacrylate, 5-8% of methyl methacrylate, 0.2-0.8% of sodium dodecyl benzene sulfonate, 0.2-0.6% of fatty alcohol polyoxyethylene ester, 20-22% of styrene, 22-25% of butyl acrylate, 1-3% of alkylphenol polyoxyethylene, 0.1-0.5% of sodium bicarbonate, 0.3-1% of potassium persulfate, 0.2-0.8% of ammonia water and the balance of water. The comprehensive performance of the emulsion is improved by utilizing the excellent physicochemical characteristics of C-F bond energy which is larger than Si-O bond energy and C-C bond energy and fluorine atoms.

The invention aims at the styrene-acrylic emulsion to be modified to a certain extent, the performance of the styrene-acrylic emulsion is improved to a certain extent, but the performance is not ideal, and particularly the anti-sagging performance is poor, so that the development of the styrene-acrylic emulsion with good anti-sagging performance meets the urgent requirement of the current market.

Disclosure of Invention

In order to solve the technical problems, the invention adopts APAO to modify styrene-acrylic emulsion, the APAO is a low molecular weight amorphous plastomer material, and the microstructure is an amorphous and irregular arrangement state, so the material has the characteristics which are not possessed by a plurality of crystalline polymers, the processing performance and the compatibility of the material can be effectively improved, the APAO has good viscosity, is difficult to migrate, has good sagging resistance, and can effectively improve the adhesive force and the sagging resistance of the silicone-acrylic emulsion by introducing the APAO through chemical bonds, and has good stability.

The invention aims to provide an APAO modified styrene-acrylic emulsion.

The invention also aims to provide a preparation method of the APAO modified styrene-acrylic emulsion, which has the characteristics of simple and convenient process, easy control and stable polymerization system.

In order to solve the technical problems, the invention adopts the following technical scheme:

the invention relates to an APAO modified styrene-acrylic emulsion, which comprises the following components in parts by weight: 4.0-8.0 parts of APAO, 10.0-25.0 parts of acrylate hard monomer, 6.0-20.0 parts of acrylate soft monomer, 2.0-5.0 parts of glycidyl acrylate, 20.0-35.0 parts of styrene, 1.5-4.0 parts of crosslinking monomer, 2.5-5.0 parts of acrylic acid, 0.1-0.3 part of ammonium persulfate, 0.5-1.0 part of sodium bicarbonate, 2.5-6.0 parts of neutralizer, 1.5-4.5 parts of emulsifier, 5.0-10.0 parts of cosolvent and 100.0-160.0 parts of deionized water.

The acrylate hard monomer is one or a combination of methyl acrylate, acrylamide, acrylonitrile, methyl methacrylate, isobornyl acrylate, isobornyl methacrylate and 2-propyl heptyl acrylate.

The acrylate soft monomer is one or a combination of butyl acrylate, butyl methacrylate, isooctyl methacrylate, lauryl methacrylate, stearyl methacrylate and stearyl acrylate.

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

The emulsifier is OP-10.

The cosolvent is one or a combination of more of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and propylene glycol methyl ether acetate.

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

The invention provides a preparation method of an APAO modified styrene-acrylic emulsion, which comprises the following steps:

1) weighing the components in proportion, sequentially adding an acrylate hard monomer, an acrylate soft monomer, a crosslinking monomer and acrylic acid, and uniformly stirring to obtain a mixed solution I;

2) weighing the raw materials in proportion, sequentially adding styrene, APAO, a cosolvent and glycidyl acrylate, and uniformly stirring to obtain a mixed solution II;

3) preparing a 5% ammonium persulfate aqueous solution in advance, adding an emulsifier, sodium bicarbonate, part of deionized water and 1/6 ammonium persulfate aqueous solution into a multifunctional reaction kettle, starting stirring and heating, heating to 76-80 ℃, adding 1/3 mixed solution I at a constant speed, and stirring for reaction until blue light appears;

4) and simultaneously dropwise adding the mixed solution II, the rest of the mixed solution I and 2/3 ammonium persulfate aqueous solution at a constant speed for 4.0-5.0 h, controlling the temperature at 80-82 ℃ in the dropwise adding process, heating to 84-85 ℃ after the dropwise adding is finished, adding the rest of 1/6 ammonium persulfate aqueous solution, carrying out heat preservation stirring reaction for 1.5-2.0 h, starting cooling water to cool, reducing the temperature to below 45 ℃, adjusting the pH value to 7.5-8.0 by using a neutralizing agent, and adding the rest of deionized water to obtain the APAO modified styrene-acrylic emulsion.

The invention provides the APAO modified styrene-acrylic emulsion with good adhesive force and good anti-sagging performance, and an anti-sagging auxiliary agent is not required to be added. The APAO modified styrene-acrylic emulsion prepared by the invention has the advantages of good adhesive force, good anti-sagging performance, acid and alkali resistance, water resistance, salt mist resistance, simple construction and the like.

Detailed Description

The preparation of an APAO modified styrene-acrylic emulsion is further described in connection with the following 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.