阅读说明：本技术 一种双键化丁香酚改性苯丙乳液及其制备方法 (Double-bonded eugenol modified styrene-acrylic emulsion and preparation method thereof ) 是由 马建中 张雷 吕斌 张跃宏 刘晨阳 于 2019-09-29 设计创作，主要内容包括：本发明公开了一种双键化丁香酚改性苯丙乳液及其制备方法,首先以甲基丙烯酸酐为双键化改性试剂,以生物质原料丁香酚分子结构中的羟基为改性位点,通过酯化反应对丁香酚进行双键化改性,制备出双键化丁香酚,然后以双键化丁香酚作为传统苯丙乳液制备过程中使用的石油基毒性单体苯乙烯的替代物,通过细乳液聚合法与丙烯酸丁酯发生自由基共聚,制备出双键化丁香酚改性苯丙乳液。本发明采用改性天然产物双键化丁香酚替代石油基毒性单体苯乙烯,制得双键化丁香酚改性苯丙乳液。改性苯丙乳液与传统苯丙乳液相比,具有生产原料安全环保、来源广泛,挥发性低,乳液具有较低的VOC含量,使用过程中对周围环境及人体危害性小。(The invention discloses a double-bonded eugenol modified styrene-acrylic emulsion and a preparation method thereof. The invention adopts double-bonded eugenol which is a modified natural product to replace petroleum-based toxic monomer styrene to prepare the double-bonded eugenol modified styrene-acrylic emulsion. Compared with the traditional styrene-acrylic emulsion, the modified styrene-acrylic emulsion has the advantages of safe and environment-friendly production raw materials, wide sources, low volatility, lower VOC content of the emulsion and small harm to the surrounding environment and human bodies in the using process.)

1. A preparation method of double-bonded eugenol modified styrene-acrylic emulsion is characterized by comprising the following steps:

the method comprises the following steps of:

(1) adding 0.120-0.140 part of sodium dodecyl sulfate, 0.06-0.07 part of branched secondary alcohol polyoxyethylene ether and 0.20-0.30 part of n-butyl alcohol into 20-23 parts of deionized water, stirring and dissolving to obtain a uniform and transparent solution, then adding diacetone acrylamide into the solution, and stirring to completely dissolve;

(2) uniformly mixing 3.0-4.0 parts of double-bonded eugenol, 6.0-7.0 parts of butyl acrylate and 0.3-0.4 part of glycidyl methacrylate, adding the mixture into the aqueous solution of the surfactant prepared in the step (1), and performing ultrasonic treatment to obtain uniform and stable pre-emulsion;

(3) dissolving 0.13-0.15 part of ammonium persulfate in 13.0-14.0 parts of deionized water to obtain a first part of initiator aqueous solution; dissolving 0.50-0.60 part of ammonium persulfate in 23.0-24.0 parts of deionized water to obtain a second part of initiator aqueous solution; adding the first part of initiator aqueous solution into a 100 ml three-neck flask, heating to 76.0-78.0 ℃, mechanically stirring for 5.0 min, simultaneously dropwise adding the pre-emulsion prepared in the step (2) and the second part of initiator aqueous solution into a reaction system, dropwise adding for 2.0-3.0 h, after dropwise adding is finished, keeping the temperature for reaction for 2.0-3.0 h, cooling to room temperature, adjusting the pH of the reaction system to be 7-8 by using ammonia water, adding adipic dihydrazide into the reaction system, mechanically stirring for 30 min, filtering and discharging to obtain the double-bonded eugenol modified styrene-acrylic emulsion.

2. The preparation method of the double-bonded eugenol modified styrene-acrylic emulsion as claimed in claim 1, wherein the preparation method comprises the following steps:

in the step (1), the adding amount of the diacetone acrylamide is 0.15-0.25 part.

3. The preparation method of the double-bonded eugenol modified styrene-acrylic emulsion as claimed in claim 2, wherein the method comprises the following steps:

in the step (2), the power of ultrasonic treatment is 300W, ultrasonic work is carried out for 2 s, the interval is 5 s, ultrasonic treatment is carried out for 3 times, each time is 5.0 min, and the ultrasonic time is 15 min.

4. The preparation method of the double-bonded eugenol modified styrene-acrylic emulsion as claimed in claim 3, wherein the method comprises the following steps:

in the step (3), the addition amount of the adipic acid dihydrazide is 0.18-0.20 part.

5. The double-bonded eugenol modified styrene-acrylic emulsion prepared by the preparation method of claims 1-4.

Technical Field

The invention belongs to the technical field of preparation of biomass material modified styrene-acrylic emulsion, and particularly relates to double-bonded eugenol modified styrene-acrylic emulsion and a preparation method thereof.

Background

The styrene-acrylic emulsion is a polyacrylate emulsion widely used at present, is mainly prepared from styrene and acrylate monomers by an emulsion polymerization method, has the advantages of good film forming property, high film forming stiffness, light resistance and aging resistance of a coating, wide raw material source, low cost and the like, and is widely applied to the fields of adhesives, coatings, fabric finishing agents, leather finishing agents, papermaking sizing agents and the like. However, styrene is used as a main raw material in the preparation process of the styrene-acrylic emulsion, is mainly derived from non-renewable petrochemical resources, has certain toxicity and potential carcinogenicity, and is in a category 2B carcinogen list according to the precautionary reference of a carcinogen list published by international cancer research institution of world health organization 2017, 10 months and 27 days. Meanwhile, styrene is extremely volatile and can be rapidly volatilized at room temperature, and the new release standard of the composite material processing industry also divides styrene into a high Volatile Organic Compound (VOC) and a Harmful Air Pollutant (HAP), so that the styrene-acrylic emulsion has high VOC content in the use process, seriously influences the human health and pollutes the construction surrounding environment. The modified biomass material has the performance advantages of wide source, environmental protection, renewability and the like. The double-bonded eugenol serving as a modified biomass material can be prepared by performing double-bonded modification on a biomass raw material eugenol by using methacrylic anhydride as a double-bonded modification reagent, and is currently applied to the preparation of partial high polymer materials.

The invention provides a method for preparing double-bonded eugenol modified styrene-acrylic emulsion by adopting a modified biomass material to replace petroleum-based toxic monomer styrene used in the traditional preparation process of styrene-acrylic emulsion and copolymerizing the double-bonded eugenol modified styrene-acrylic emulsion with an acrylate monomer through a miniemulsion polymerization method. The modified styrene-acrylic emulsion has low VOC content, safe and environment-friendly production raw materials, wide sources and low volatility, thereby effectively overcoming the defects of high VOC content, harm to the surrounding environment and human bodies and the like in the use process of the traditional styrene-acrylic emulsion.

Disclosure of Invention

The invention aims to provide a double-bonded eugenol modified styrene-acrylic emulsion and a preparation method thereof, namely double-bonded eugenol is used as a substitute of petroleum-based toxic monomer styrene used in the preparation process of the traditional styrene-acrylic emulsion, and the double-bonded eugenol modified styrene-acrylic emulsion is prepared by carrying out free radical copolymerization with butyl acrylate through a miniemulsion polymerization method. Compared with the traditional styrene-acrylic emulsion, the styrene-acrylic emulsion has the advantages of safe and environment-friendly production raw materials, wide sources, low volatility, low VOC content of products, no harm to the surrounding environment and human bodies in the using process and the like.

The technical scheme of the invention is as follows:

the preparation method of the double-bonded eugenol modified styrene-acrylic emulsion comprises the following steps of:

(1) adding 0.120-0.140 part of sodium dodecyl sulfate, 0.06-0.07 part of branched secondary alcohol polyoxyethylene ether and 0.20-0.30 part of n-butyl alcohol into 20-23 parts of deionized water, stirring and dissolving to obtain a uniform and transparent solution, then adding diacetone acrylamide into the solution, and stirring to completely dissolve;

(2) uniformly mixing 3.0-4.0 parts of double-bonded eugenol, 6.0-7.0 parts of butyl acrylate and 0.3-0.4 part of glycidyl methacrylate, adding the mixture into the aqueous solution of the surfactant prepared in the step (1), and performing ultrasonic treatment to obtain uniform and stable pre-emulsion;

(3) dissolving 0.13-0.15 part of ammonium persulfate in 13.0-14.0 parts of deionized water to obtain a first part of initiator aqueous solution; dissolving 0.50-0.60 part of ammonium persulfate in 23.0-24.0 parts of deionized water to obtain a second part of initiator aqueous solution; adding the first part of initiator aqueous solution into a 100 ml three-neck flask, heating to 76.0-78.0 ℃, mechanically stirring for 5.0 min, simultaneously dropwise adding the pre-emulsion prepared in the step (2) and the second part of initiator aqueous solution into a reaction system, dropwise adding for 2.0-3.0 h, after dropwise adding is finished, keeping the temperature for reaction for 2.0-3.0 h, cooling to room temperature, adjusting the pH of the reaction system to be 7-8 by using ammonia water, adding adipic dihydrazide into the reaction system, mechanically stirring for 30 min, filtering and discharging to obtain the double-bonded eugenol modified styrene-acrylic emulsion.

In the step (1), the adding amount of the diacetone acrylamide is 0.15-0.25 part.

In the step (2), the power of ultrasonic treatment is 300W, ultrasonic work is carried out for 2 s, the interval is 5 s, ultrasonic treatment is carried out for 3 times, each time is 5.0 min, and the ultrasonic time is 15 min.

In the step (3), the addition amount of the adipic acid dihydrazide is 0.18-0.20 part.

The double-bonded eugenol modified styrene-acrylic emulsion is prepared by the preparation method.

The invention has the following advantages:

the double-bonded eugenol modified styrene-acrylic emulsion is prepared by using a modified biomass material to double bond eugenol, replacing petroleum-based toxic monomer styrene used in the traditional preparation process of the styrene-acrylic emulsion, and performing free radical copolymerization reaction with butyl acrylate through a miniemulsion polymerization method. Compared with the traditional styrene-acrylic emulsion, the double-bonded eugenol modified styrene-acrylic emulsion has lower VOC content, safe and environment-friendly production raw materials, wide sources and low volatility, thereby effectively overcoming the defects of high VOC content, harm to the surrounding environment and human bodies and the like in the use process of the traditional styrene-acrylic emulsion.

Drawings

FIG. 1 shows a chemical reaction formula for preparing a double-bonded eugenol modified styrene-acrylic emulsion (ME-BA) by using double-bonded eugenol (ME) and Butyl Acrylate (BA) as raw materials.

Detailed Description

The present invention will be described in detail with reference to specific embodiments.

The invention relates to a preparation method of double-bonded eugenol modified styrene-acrylic emulsion, which comprises the following steps:

the following are all prepared by mass portion,

(1) adding 0.120-0.140 part of sodium dodecyl sulfate, 0.06-0.07 part of branched secondary alcohol polyoxyethylene ether and 0.20-0.30 part of n-butyl alcohol into 20-23 parts of deionized water, stirring and dissolving to obtain a uniform and transparent solution, then adding 0.15-0.25 part of diacetone acrylamide into the solution, and stirring to completely dissolve.

(2) Uniformly mixing 3.0-4.0 parts of double-bonded eugenol, 6.0-7.0 parts of butyl acrylate and 0.3-0.4 part of glycidyl methacrylate, adding the mixture into the aqueous solution of the surfactant prepared in the step (1), and performing ultrasonic treatment to obtain uniform and stable pre-emulsion. Wherein the power of ultrasonic treatment is 300W, ultrasonic work is carried out for 2 s, the interval is 5 s, ultrasonic treatment is carried out for 3 times, each time is 5min, and the total ultrasonic time is 15 min.

(3) Dissolving 0.13-0.15 part of ammonium persulfate in 13.0-14.0 parts of deionized water to obtain a first part of initiator aqueous solution; dissolving 0.50-0.60 part of ammonium persulfate in 23.0-24.0 parts of deionized water to obtain a second part of initiator aqueous solution; adding a first part of initiator aqueous solution into a 100 ml three-neck flask, heating to 76.0-78.0 ℃, mechanically stirring for 5.0 min, simultaneously dropwise adding the pre-emulsion prepared in the step (2) and a second part of initiator aqueous solution into a reaction system, dropwise adding for 2.0-3.0 h, after dropwise adding is finished, keeping the temperature for reaction for 2.0-3.0 h, cooling to room temperature, adjusting the pH of the reaction system to 7-8 by using ammonia water, adding 0.18-0.20 part of adipic acid dihydrazide into the reaction system, mechanically stirring for 30 min, filtering and discharging to obtain the double-bonded eugenol modified styrene-acrylic emulsion.

The double-bonded eugenol modified styrene-acrylic emulsion can be prepared according to the preparation method.