CN110627948A - A kind of double-bonded eugenol modified styrene-acrylic emulsion and preparation method thereof - Google Patents

Abstract

The invention discloses a double-bond eugenol modified styrene-acrylic emulsion and a preparation method thereof. First, methacrylic anhydride is used as a double bond modification reagent, and the hydroxyl group in the molecular structure of biomass raw material eugenol is used as a modification site. At this point, eugenol is double bonded and modified by esterification to prepare double bonded eugenol, and then double bonded eugenol is used as a substitute for petroleum-based toxic monomer styrene used in the preparation of traditional styrene-acrylic emulsion The product was radically copolymerized with butyl acrylate by miniemulsion polymerization to prepare a double bonded eugenol modified styrene-acrylic emulsion. The invention adopts modified natural product double-bonded eugenol to replace petroleum-based toxic monomer styrene to prepare double-bonded eugenol-modified styrene-acrylic emulsion. Compared with the traditional styrene-acrylic emulsion, the modified styrene-acrylic emulsion has safe and environmentally friendly production raw materials, wide sources, low volatility, low VOC content in the emulsion, and little harm to the surrounding environment and human body during use.

Description

A kind of double-bonded eugenol modified styrene-acrylic emulsion and preparation method thereof

technical field

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

Background technique

Styrene-acrylic emulsion is a polyacrylate emulsion widely used at present. It is mainly prepared from styrene and acrylate monomers by emulsion polymerization. It has good film-forming properties, high film-forming stiffness, and the coating is light-resistant and aging-resistant. , wide source of raw materials, low cost and other advantages, widely used in adhesives, coatings, fabric finishing agents, leather finishing agents and paper sizing agents and other fields. However, one of the main raw materials used in the preparation of styrene-acrylic emulsion is styrene. Styrene is mainly derived from non-renewable petrochemical resources. At the same time, it has certain toxicity and potential carcinogenicity. According to the World Health Organization International Agency for Research on Cancer 2017 In the preliminary collation reference of the list of carcinogens released on October 27, 2010, styrene was included in the list of 2B carcinogens. At the same time, styrene is extremely volatile and evaporates quickly at room temperature. The new emission standards for the composites processing industry also classify styrene as a highly volatile organic compound (VOC) and a hazardous air pollutant (HAP ), which makes styrene-acrylic emulsion have high VOC content during use, which seriously affects human health and pollutes the surrounding environment of construction. Modified biomass materials have a wide range of sources, green environmental protection, renewable and other performance advantages. Double-bonded eugenol, as a modified biomass material, can be obtained by double-bonding modification of biomass raw material eugenol by using methacrylic anhydride as a double-bonding modifying reagent. It has been applied to some polymers The material is being prepared.

The present invention proposes to replace the petroleum-based toxic monomer styrene used in the preparation process of traditional styrene-acrylic emulsion by using modified biomass material double-bonded eugenol, and to prepare double-bonded Eugenol modified styrene-acrylic emulsion. The modified styrene-acrylic emulsion has a low VOC content, and the production raw materials are safe and environmentally friendly, with a wide range of sources and low volatility, thus effectively overcoming the high VOC content of the traditional styrene-acrylic emulsion during use, which is harmful to the surrounding environment and human body. shortcoming.

Contents of the invention

The purpose of the present invention is to provide a double-bonded eugenol modified styrene-acrylic emulsion and a preparation method thereof, that is, to use double-bonded eugenol as a substitute for petroleum-based toxic monomer styrene used in the preparation process of traditional styrene-acrylic emulsion , by free radical copolymerization with butyl acrylate by miniemulsion polymerization to prepare double bonded eugenol modified styrene-acrylic emulsion. Compared with the traditional styrene-acrylic emulsion, the styrene-acrylic emulsion has many performance advantages such as safe and environmentally friendly raw materials, wide sources, low volatility, low VOC content, and no harm to the surrounding environment and human body during use.

Technical scheme of the present invention is as follows:

A preparation method of double bonded eugenol modified styrene-acrylic emulsion, comprising the following steps, all in parts by mass:

(1) Add 0.120-0.140 parts of sodium lauryl sulfate, 0.06-0.07 parts of branched chain secondary alcohol polyoxyethylene ether and 0.20-0.30 parts of n-butanol to 20-23 parts of deionized water, stir Dissolve to a uniform and transparent solution, then add diacetone acrylamide to the solution, and stir until completely dissolved;

(2) Mix 3.0-4.0 parts of double-bonded eugenol, 6.0-7.0 parts of butyl acrylate and 0.3-0.4 parts of glycidyl methacrylate, and then add the mixture to the surface prepared in step (1) In the aqueous solution of the active agent, ultrasonic treatment is used to obtain a uniform and stable pre-emulsion;

(3) Dissolve 0.13-0.15 parts of ammonium persulfate in 13.0-14.0 parts of deionized water to obtain the first initiator aqueous solution; dissolve 0.50-0.60 parts of ammonium persulfate in 23.0-24.0 parts of deionized water , to obtain the second initiator aqueous solution; add the first initiator aqueous solution to a 100 ml three-necked flask, then raise the temperature to 76.0-78.0°C, stir mechanically for 5.0 min, and then add step (2) dropwise to the reaction system at the same time The prepared pre-emulsion and the second initiator aqueous solution were added dropwise for 2.0-3.0 h. After the dropwise addition was completed, the insulation reaction was carried out for 2.0-3.0 h, cooled to room temperature, and the pH of the reaction system was adjusted to 7-8 with ammonia water. The adipic acid dihydrazide added in the mixture was mechanically stirred for 30 min, and the material was filtered to obtain a double-bonded eugenol modified styrene-acrylic emulsion.

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

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

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

A double bonded eugenol modified styrene-acrylic emulsion prepared by the above preparation method.

The present invention has the following advantages:

The present invention replaces the petroleum-based toxic monomer styrene used in the preparation process of the traditional styrene-acrylic emulsion by using the double-bonded eugenol of the modified biomass material, and undergoes a free-radical copolymerization reaction with butyl acrylate through the miniemulsion polymerization method. A double bonded eugenol modified styrene-acrylic emulsion was prepared. Compared with traditional styrene-acrylic emulsion, double-bonded eugenol modified styrene-acrylic emulsion has lower VOC content. The VOC content is high, and there are disadvantages such as harm to the surrounding environment and human body.

Description of drawings

Figure 1 is the chemical reaction formula for preparing double-bonded eugenol modified styrene-acrylic emulsion (ME-BA) using double-bonded eugenol (ME) and butyl acrylate (BA) as raw materials.

Detailed ways

The present invention will be described in detail below in combination with specific embodiments.

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

The following are in parts by mass,

(1) Add 0.120-0.140 parts of sodium lauryl sulfate, 0.06-0.07 parts of branched chain secondary alcohol polyoxyethylene ether and 0.20-0.30 parts of n-butanol to 20-23 parts of deionized water, stir Dissolve to a uniform and transparent solution, then add 0.15-0.25 parts of diacetone acrylamide to the solution, and stir until completely dissolved.

(2) Mix 3.0-4.0 parts of double-bonded eugenol, 6.0-7.0 parts of butyl acrylate and 0.3-0.4 parts of glycidyl methacrylate, and then add the mixture to the surface prepared in step (1) In the aqueous solution of the active agent, a uniform and stable pre-emulsion was obtained by ultrasonic treatment. Among them, the power of ultrasonic treatment is 300 W, the ultrasonic work is 2 s, the interval is 5 s, ultrasonic is 3 times, each time is 5 min, and the total ultrasonic time is 15 min.

(3) Dissolve 0.13-0.15 parts of ammonium persulfate in 13.0-14.0 parts of deionized water to obtain the first initiator aqueous solution; dissolve 0.50-0.60 parts of ammonium persulfate in 23.0-24.0 parts of deionized water , to obtain the second initiator aqueous solution; add the first initiator aqueous solution to a 100 ml three-necked flask, then raise the temperature to 76.0-78.0°C, stir mechanically for 5.0 min, and then add step (2) dropwise to the reaction system at the same time The prepared pre-emulsion and the second initiator aqueous solution were added dropwise for 2.0-3.0 h. After the dropwise addition was completed, the insulation reaction was carried out for 2.0-3.0 h, cooled to room temperature, and the pH of the reaction system was adjusted to 7-8 with ammonia water. Add 0.18-0.20 parts of adipic acid dihydrazide to the mixture, stir mechanically for 30 min, and filter the material to obtain a double-bonded eugenol modified styrene-acrylic emulsion.

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

Example 1:

The following are in parts by mass,

(1) Add 0.120 parts of sodium lauryl sulfate, 0.07 parts of branched chain secondary alcohol polyoxyethylene ether and 0.20 parts of n-butanol to 23 parts of deionized water, stir and dissolve to a uniform and transparent solution, and then Add 0.15 parts of diacetone acrylamide to the solution and stir until completely dissolved.

(2) Mix 4.0 parts of double-bonded eugenol, 7.0 parts of butyl acrylate and 0.4 parts of glycidyl methacrylate, and then add the mixture to the aqueous surfactant solution prepared in step (1), and ultrasonically The treatment produces a uniform and stable pre-emulsion. Among them, the power of ultrasonic treatment is 300 W, the ultrasonic work is 2 s, the interval is 5 s, ultrasonic is 3 times, each time is 5 min, and the total ultrasonic time is 15 min.

(3) Dissolve 0.13 parts of ammonium persulfate in 14.0 parts of deionized water to obtain the first aqueous initiator solution; dissolve 0.50 parts of ammonium persulfate in 23.0 parts of deionized water to obtain the second aqueous initiator solution ; Add the first aqueous solution of the initiator to a 100 ml three-neck flask, then raise the temperature to 76.0, stir mechanically for 5.0 min, and then add the pre-emulsion and the second initiator prepared in step (2) dropwise to the reaction system at the same time The aqueous solution was added dropwise for 2.0 h. After the dropwise addition was completed, the reaction was incubated for 3.0 h, cooled to room temperature, and the pH of the reaction system was adjusted to 7 with ammonia water. 0.18 parts of adipic acid dihydrazide was added to the reaction system, and mechanically stirred for 30 min. The material is filtered out to obtain a double bonded eugenol modified styrene-acrylic emulsion.

Example 2:

The following are in parts by mass,

(1) Add 0.140 parts of sodium lauryl sulfate, 0.07 parts of branched chain secondary alcohol polyoxyethylene ether and 0.25 parts of n-butanol to 22 parts of deionized water, stir and dissolve to a uniform and transparent solution, and then Add 0.25 parts of diacetone acrylamide to the solution and stir until completely dissolved.

(2) Mix 3.0 parts of double-bonded eugenol, 7.0 parts of butyl acrylate and 0.3 parts of glycidyl methacrylate, and then add the mixture to the aqueous surfactant solution prepared in step (1), and ultrasonically The treatment produces a uniform and stable pre-emulsion. Among them, the power of ultrasonic treatment is 300 W, the ultrasonic work is 2 s, the interval is 5 s, ultrasonic is 3 times, each time is 5 min, and the total ultrasonic time is 15 min.

(3) Dissolve 0.15 parts of ammonium persulfate in 13.0 parts of deionized water to obtain the first aqueous initiator solution; dissolve 0.60 parts of ammonium persulfate in 24.0 parts of deionized water to obtain the second aqueous initiator solution ; Add the first initiator aqueous solution into a 100 ml three-neck flask, then raise the temperature to 77 °C, stir mechanically for 5.0 min, then add the pre-emulsion prepared in step (2) and the second initiator dropwise to the reaction system at the same time Aqueous solution of adipic acid was added dropwise for 3.0 h. After the dropwise addition was completed, the heat preservation reaction was carried out for 2.0 h, and cooled to room temperature. The pH of the reaction system was adjusted to 8 with ammonia water, and 0.20 parts of adipic acid dihydrazide was added to the reaction system, and mechanically stirred for 30 min. , and the material was filtered to obtain a double-bonded eugenol-modified styrene-acrylic emulsion.

Example 3:

The following are in parts by mass,

(1) Add 0.130 parts of sodium lauryl sulfate, 0.065 parts of branched chain secondary alcohol polyoxyethylene ether and 0.30 parts of n-butanol to 23 parts of deionized water, stir and dissolve to a uniform and transparent solution, and then Add 0.20 parts of diacetone acrylamide to the solution and stir until completely dissolved.

(2) Mix 3.5 parts of double-bonded eugenol, 6.5 parts of butyl acrylate and 0.35 parts of glycidyl methacrylate, and then add the mixture to the surfactant aqueous solution prepared in step (1), and ultrasonically The treatment produces a uniform and stable pre-emulsion. Among them, the power of ultrasonic treatment is 300 W, the ultrasonic work is 2 s, the interval is 5 s, ultrasonic is 3 times, each time is 5 min, and the total ultrasonic time is 15 min.

(3) Dissolve 0.14 parts of ammonium persulfate in 14.0 parts of deionized water to obtain the first aqueous initiator solution; dissolve 0.55 parts of ammonium persulfate in 23.5 parts of deionized water to obtain the second aqueous initiator solution ; Add the first initiator aqueous solution into a 100 ml three-necked flask, then raise the temperature to 78.0°C, stir mechanically for 5.0 min, then add the pre-emulsion prepared in step (2) and the second initiator dropwise to the reaction system at the same time solution, add dropwise for 2.5 h, after the dropwise addition, keep warm for 2.5 h, cool to room temperature, use ammonia water to adjust the pH of the reaction system to 7, add 0.19 parts of adipic acid dihydrazide to the reaction system, and mechanically stir for 30 min , and the material was filtered to obtain a double-bonded eugenol-modified styrene-acrylic emulsion.

The VOC content of double-bonded eugenol modified styrene-acrylic emulsion (ME-BA) and commercially available styrene-acrylic emulsion was tested by gas chromatography. The test results are shown in Table 1. The test results show that the double-bonded eugenol-modified styrene-acrylic emulsion prepared by using modified biomass materials to double-bond eugenol replaces the petroleum-based toxic monomer styrene used in the preparation process of traditional styrene-acrylic emulsions. Compared with traditional styrene-acrylic emulsion, its VOC content is significantly reduced, from 2568 ppm to 326.7 ppm.

Table 1 Test results of VOC content of double bonded eugenol modified styrene-acrylic emulsion (ME-BA) and commercially available styrene-acrylic emulsion

The content of the present invention is not limited to the examples listed, and any equivalent transformation of the technical solution of the present invention adopted by those of ordinary skill in the art by reading the description of the present invention is covered by the claims of the present invention.

Claims (5)

1. a preparation method of double bonded eugenol modified styrene-acrylic emulsion, characterized in that: Include the following steps, the following are by mass parts: (1) Add 0.120-0.140 parts of sodium lauryl sulfate, 0.06-0.07 parts of branched chain secondary alcohol polyoxyethylene ether and 0.20-0.30 parts of n-butanol to 20-23 parts of deionized water, stir Dissolve to a uniform and transparent solution, then add diacetone acrylamide to the solution, and stir until completely dissolved; (2) Mix 3.0-4.0 parts of double-bonded eugenol, 6.0-7.0 parts of butyl acrylate and 0.3-0.4 parts of glycidyl methacrylate, and then add the mixture to the surface prepared in step (1) In the aqueous solution of the active agent, ultrasonic treatment is used to obtain a uniform and stable pre-emulsion; (3) Dissolve 0.13-0.15 parts of ammonium persulfate in 13.0-14.0 parts of deionized water to obtain the first initiator aqueous solution; dissolve 0.50-0.60 parts of ammonium persulfate in 23.0-24.0 parts of deionized water , to obtain the second initiator aqueous solution; add the first initiator aqueous solution to a 100 ml three-necked flask, then raise the temperature to 76.0-78.0°C, stir mechanically for 5.0 min, and then add step (2) dropwise to the reaction system at the same time The prepared pre-emulsion and the second initiator aqueous solution were added dropwise for 2.0-3.0 h. After the dropwise addition was completed, the insulation reaction was carried out for 2.0-3.0 h, cooled to room temperature, and the pH of the reaction system was adjusted to 7-8 with ammonia water. The adipic acid dihydrazide added in the mixture was mechanically stirred for 30 min, and the material was filtered to obtain a double-bonded eugenol modified styrene-acrylic emulsion. 2. the preparation method of a kind of double bonded eugenol modified styrene-acrylic emulsion according to claim 1, is characterized in that: In step (1), the added amount of diacetone acrylamide is 0.15-0.25 parts. 3. the preparation method of a kind of double bonded eugenol modified styrene-acrylic emulsion according to claim 2, is characterized in that: In step (2), the power of the ultrasonic treatment was 300 W, the ultrasonic was operated for 2 s, the interval was 5 s, and the ultrasonic was 3 times, 5.0 min each time, and the ultrasonic time was 15 min. 4. the preparation method of a kind of double bonded eugenol modified styrene-acrylic emulsion according to claim 3, is characterized in that: In step (3), the added amount of adipic acid dihydrazide is 0.18-0.20 parts. 5. a kind of double bonded eugenol modified styrene-acrylic emulsion that preparation method makes as described in claim 1-4.