CN110563881A - double-bonded vanillyl alcohol modified styrene-acrylic emulsion and preparation method thereof - Google Patents

Abstract

The invention discloses a double-bond vanillyl alcohol modified styrene-acrylic emulsion and a preparation method thereof. Firstly, methacrylic anhydride is used as a double bond modification reagent, and the hydroxyl group in the molecular structure of biomass raw material vanillyl alcohol is used as a modification site. point, vanillyl alcohol is double-bonded modified by esterification to prepare double-bonded vanillyl alcohol. Using double-bonded vanillyl alcohol as a substitute for the petroleum-based toxic monomer styrene used in the preparation of traditional styrene-acrylic emulsions, the double-bonded vanillyl alcohol modified Styrene acrylic emulsion. The invention adopts the modified natural product double-bonded vanillyl alcohol to replace the petroleum-based toxic monomer styrene used in the preparation process of the traditional styrene-acrylic emulsion, and prepares the double-bonded vanillyl alcohol-modified styrene-acrylic emulsion. Compared with the traditional styrene-acrylic emulsion, the modified styrene-acrylic emulsion has renewable raw materials, wide sources, low cost, safety and environmental protection, low volatility, low VOC content of the emulsion, and little harm to the surrounding environment and human body.

Description

A kind of double-bonded vanillyl alcohol 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 vanillyl alcohol-modified styrene-acrylic emulsion and a preparation method thereof.

Background technique

Styrene-acrylic emulsion is the most widely used polyacrylate emulsion. Its synthetic raw materials mainly include styrene and acrylate monomers, and various products can be prepared by emulsion polymerization. Styrene-acrylic emulsion has the advantages of good film-forming property, high film-forming stiffness, light resistance and aging resistance of latex film, wide source of raw materials, and low cost. It is widely used in adhesives, coatings, fabric finishing agents, leather finishing agents and paper-making sizing agents. and other fields. However, styrene-acrylic emulsion needs to use a large amount of styrene monomer in the preparation process. Styrene mainly comes from non-renewable petrochemical resources. At the same time, it has certain toxicity and potential carcinogenicity, which has great harm to human health and the surrounding environment of construction. influences. According to the preliminary list of carcinogens released by the International Agency for Research on Cancer of the World Health Organization on October 27, 2017, styrene is included in the list of 2B carcinogens, which further restricts the application of styrene and seriously affects the downstream Product production and application. At the same time, styrene is extremely volatile and has a high volatilization rate at room temperature. The new release standard of the composite material processing industry also classifies styrene as a highly volatile organic compound (VOC) and a harmful 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. As a modified biomass material, double-bonded vanillyl alcohol can be obtained by double-bonding modification of biomass raw material vanillyl alcohol by using methacrylic anhydride as a double-bonding modifying reagent. It has been applied to some polymers in the preparation of materials.

Based on the above problems, the present invention proposes to use modified biomass material double-bonded vanillyl alcohol to replace the petroleum-based toxic monomer styrene used in the preparation process of traditional styrene-acrylic emulsion, and to copolymerize with acrylate monomer through miniemulsion polymerization to prepare A double-bonded vanillyl alcohol modified styrene-acrylic emulsion. The double-bonded vanillyl alcohol modified styrene-acrylic emulsion has a low VOC content. The production raw materials are safe and environmentally friendly, have a wide range of sources, are renewable, and have low volatility, thus effectively overcoming the high VOC content of traditional styrene-acrylic emulsions during use. There are disadvantages such as harm to the surrounding environment and human body.

Contents of the invention

The purpose of the present invention is to provide a kind of double-bonded vanillyl alcohol modified styrene-acrylic emulsion and preparation method thereof, promptly use double-bonded vanillyl alcohol as the substitute of petroleum-based toxic monomer styrene used in the preparation process of traditional styrene-acrylic emulsion , the double-bonded vanillyl alcohol modified styrene-acrylic emulsion was prepared by free-radical copolymerization with butyl acrylate by miniemulsion polymerization. Compared with the traditional styrene-acrylic emulsion, the modified styrene-acrylic emulsion has many properties such as safe and environmentally friendly raw materials, wide sources, renewable, low volatility, low VOC content, and little harm to the surrounding environment and human body during use. Advantage.

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

(1) Add 0.145-0.160 parts of sodium lauryl sulfate, 0.08-0.10 parts of branched chain secondary alcohol polyoxyethylene ether and 0.30-0.35 parts of n-butanol to 24-25 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 2.0-3.0 parts of double-bonded vanillyl alcohol prepared in step 1, 7.0-8.0 parts of butyl acrylate and 0.40-0.50 parts of glycidyl methacrylate, and then add the mixture to step ( 1) In the prepared surfactant aqueous solution, ultrasonic treatment is used to obtain a uniform and stable pre-emulsion;

(3) Dissolve 0.15-0.16 parts of ammonium persulfate in 15.0-16.0 parts of deionized water to obtain the first initiator aqueous solution; dissolve 0.40-0.50 parts of ammonium persulfate in 24.0-25.0 parts of deionized water , to obtain the second aqueous initiator solution; add the first aqueous initiator solution to a 100 ml three-necked flask, then raise the temperature to 75-77 °C, stir mechanically for 5 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. Adipic acid dihydrazide was added to the mixture, mechanically stirred for 30 min, and the material was filtered to obtain a double-bonded vanillyl alcohol-modified styrene-acrylic emulsion.

In step (1), the added amount of diacetone acrylamide is 0.20-0.30 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 0.16-0.18 parts.

A kind of double-bonded vanillyl alcohol modified styrene-acrylic emulsion prepared according to the above-mentioned preparation method.

The present invention has the following advantages:

The invention replaces the petroleum-based toxic monomer styrene used in the preparation process of the traditional styrene-acrylic emulsion by using the modified biomass material to double-bond vanillyl alcohol, and undergoes a free radical copolymerization reaction with butyl acrylate through a miniemulsion polymerization method. A double bonded vanillyl alcohol modified styrene-acrylic emulsion was prepared. Double-bonded vanillyl alcohol modified styrene-acrylic emulsion has low VOC content compared with traditional styrene-acrylic emulsion. The VOC content in the product is high, the production raw materials are not renewable, 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 vanillyl alcohol modified styrene-acrylic emulsion (MVA-BA) using double-bonded vanillyl alcohol (MVA) 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 vanillyl alcohol modified styrene-acrylic emulsion, comprising the following steps:

The following are in parts by mass,

(1) Add 0.145-0.160 parts of sodium lauryl sulfate, 0.08-0.10 parts of branched chain secondary alcohol polyoxyethylene ether and 0.30-0.35 parts of n-butanol to 24-25 parts of deionized water, stir Dissolve to a uniform and transparent solution, then add 0.20-0.30 parts of diacetone acrylamide to the solution, and stir until completely dissolved.

(2) Mix 2.0-3.0 parts of double-bonded vanillyl alcohol prepared in step 1, 7.0-8.0 parts of butyl acrylate and 0.40-0.50 parts of glycidyl methacrylate, and then add the mixture to step ( 1) In the prepared surfactant aqueous solution, ultrasonic treatment is used to obtain 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 0.15-0.16 parts of ammonium persulfate in 15.0-16.0 parts of deionized water to obtain the first initiator aqueous solution; dissolve 0.40-0.50 parts of ammonium persulfate in 24.0-25.0 parts of deionized water , to obtain the second aqueous initiator solution; add the first aqueous initiator solution to a 100 ml three-necked flask, then raise the temperature to 75-77 °C, stir mechanically for 5 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 0.16-0.18 parts of adipic acid dihydrazide to the mixture, stir mechanically for 30 min, filter and discharge the material, and obtain double-bonded vanillyl alcohol modified styrene-acrylic emulsion.

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

Example 1:

Preparation of Double Bonded Vanillyl Alcohol Modified Styrene Acrylic Emulsion

The following are in parts by mass,

(1) Add 0.145 parts of sodium lauryl sulfate, 0.10 parts of branched chain secondary alcohol polyoxyethylene ether and 0.30 parts of n-butanol to 25 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 2.0 parts of the double-bonded vanillyl alcohol prepared in step 1, 8.0 parts of butyl acrylate and 0.40 parts of glycidyl methacrylate, and then add the mixture to the surfactant prepared in step (1). In the aqueous solution of the solvent, 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 0.16 parts of ammonium persulfate in 15.0 parts of deionized water to obtain the first aqueous initiator solution; dissolve 0.40 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 75 °C, stir mechanically for 5 min, and 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 2.0 h. After the dropwise addition was completed, the reaction was kept for 2.0 h and cooled to room temperature. The pH of the reaction system was adjusted to 7 with ammonia water, and 0.16 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 vanillyl alcohol-modified styrene-acrylic emulsion.

Example 2:

Preparation of Double Bonded Vanillyl Alcohol Modified Styrene Acrylic Emulsion

The following are in parts by mass,

(1) Add 0.160 parts of sodium lauryl sulfate, 0.10 parts of branched chain secondary alcohol polyoxyethylene ether and 0.35 parts of n-butanol to 25 parts of deionized water, stir and dissolve to a uniform and transparent solution, and then Add 0.30 parts of diacetone acrylamide to the solution and stir until completely dissolved.

(2) Mix 3.0 parts of the double-bonded vanillyl alcohol prepared in step 1, 7.0 parts of butyl acrylate and 0.50 parts of glycidyl methacrylate, and then add the mixture to the surfactant prepared in step (1). In the aqueous solution of the solvent, 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 0.16 parts of ammonium persulfate in 16.0 parts of deionized water to obtain the first initiator aqueous solution; dissolve 0.40 parts of ammonium persulfate in 25.0 parts of deionized water to obtain the second initiator aqueous 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 minutes, and 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 reaction was kept for 2.0 h and cooled to room temperature. The pH of the reaction system was adjusted to 8 with ammonia water, and 0.18 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 vanillyl alcohol-modified styrene-acrylic emulsion.

Example 3:

Preparation of Double Bonded Vanillyl Alcohol Modified Styrene Acrylic Emulsion

The following are in parts by mass,

(1) Add 0.150 parts of sodium lauryl sulfate, 0.09 parts of branched chain secondary alcohol polyoxyethylene ether and 0.30 parts of n-butanol to 25 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 2.5 parts of the double-bonded vanillyl alcohol prepared in step 1, 7.5 parts of butyl acrylate and 0.45 parts of glycidyl methacrylate, and then add the mixture to the surfactant prepared in step (1). In the aqueous solution of the solvent, 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 0.16 parts of ammonium persulfate in 15.0 parts of deionized water to obtain the first aqueous initiator solution; dissolve 0.45 parts of ammonium persulfate in 25.0 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 76 °C, stir mechanically for 5 minutes, and 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 2.0 h. After the dropwise addition was completed, the heat preservation reaction was carried out for 3.0 h, and cooled to room temperature. The pH of the reaction system was adjusted to 7 with ammonia water, and 0.17 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 vanillyl alcohol-modified styrene-acrylic emulsion.

The VOC content of double-bonded vanillyl alcohol (MVA) modified styrene-acrylic emulsion (MVA-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 vanillyl alcohol-modified styrene-acrylic emulsion prepared by using modified biomass materials to double-bond vanillyl alcohol replaces the petroleum-based toxic monomer styrene used in the preparation of traditional styrene-acrylic emulsions. Compared with traditional styrene-acrylic emulsion, its VOC content is significantly reduced, from 2375 ppm to 358.8 ppm.

Table 1 VOC content of double bonded vanillyl alcohol modified styrene-acrylic emulsion (MVA-BA) and commercially available styrene-acrylic emulsion

Test Results

Sample type Double-bonded vanillyl alcohol modified styrene-acrylic emulsion (MVA-BA) Commercially available styrene-acrylic emulsion VOC content/ppm 358.8 2375

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 vanillyl alcohol modified styrene-acrylic emulsion, characterized in that: Include the following steps, the following are by mass parts: (1) Add 0.145-0.160 parts of sodium lauryl sulfate, 0.08-0.10 parts of branched chain secondary alcohol polyoxyethylene ether and 0.30-0.35 parts of n-butanol to 24-25 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 2.0-3.0 parts of double-bonded vanillyl alcohol prepared in step 1, 7.0-8.0 parts of butyl acrylate and 0.40-0.50 parts of glycidyl methacrylate, and then add the mixture to step ( 1) In the prepared surfactant aqueous solution, ultrasonic treatment is used to obtain a uniform and stable pre-emulsion; (3) Dissolve 0.15-0.16 parts of ammonium persulfate in 15.0-16.0 parts of deionized water to obtain the first initiator aqueous solution; dissolve 0.40-0.50 parts of ammonium persulfate in 24.0-25.0 parts of deionized water , to obtain the second aqueous initiator solution; add the first aqueous initiator solution to a 100 ml three-necked flask, then raise the temperature to 75-77 °C, stir mechanically for 5 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. Adipic acid dihydrazide was added to the mixture, mechanically stirred for 30 min, and the material was filtered to obtain a double-bonded vanillyl alcohol-modified styrene-acrylic emulsion. 2. the preparation method of a kind of double-bonded vanillyl alcohol modified styrene-acrylic emulsion according to claim 1, is characterized in that: In step (1), the added amount of diacetone acrylamide is 0.20-0.30 parts. 3. the preparation method of a kind of double-bonded vanillyl alcohol 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 vanillyl alcohol modified styrene-acrylic emulsion according to claim 3, is characterized in that: In step (3), the added amount of adipic acid dihydrazide is 0.16-0.18 parts. 5. A kind of double bonded vanillyl alcohol modified styrene-acrylic emulsion prepared by the preparation method described in claim 1-4.