CN110563880A - double-bond vanillin-modified styrene-acrylic emulsion and preparation method thereof - Google Patents
double-bond vanillin-modified styrene-acrylic emulsion and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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Abstract
The invention discloses a double-bond vanillin modified styrene-acrylic emulsion and a preparation method thereof. The invention adopts the double-bond vanillin which is a modified natural product to replace a petroleum-based toxic monomer styrene to prepare the double-bond vanillin-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.
Description
Technical Field
The invention belongs to the technical field of preparation of biomass material modified styrene-acrylic emulsion, and particularly relates to a preparation method of double-bond vanillin-modified styrene-acrylic emulsion.
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-bond vanillin is used as a modified biomass material, methacrylic anhydride can be used as a double-bond modifying reagent, and the double-bond vanillin is prepared from a biomass raw material by double-bond modification, and is currently applied to preparation of partial high polymer materials.
the invention provides a double-bond vanillin-modified styrene-acrylic emulsion prepared by copolymerizing a modified biomass material double-bond vanillin with an acrylate monomer by a miniemulsion polymerization method instead of a petroleum-based toxic monomer styrene used in the traditional preparation process of styrene-acrylic emulsion. 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 preparation method of double-bond vanillin modified styrene-acrylic emulsion, namely double-bond vanillin modified styrene-acrylic emulsion is prepared by taking the double-bond vanillin as a substitute of petroleum-based toxic monomer styrene used in the traditional preparation process of styrene-acrylic emulsion and 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 preparation method of the double-bond vanillin modified styrene-acrylic emulsion comprises the following steps of:
(1) adding 0.270-0.280 part of sodium dodecyl sulfate, 0.130-0.140 part of branched secondary alcohol polyoxyethylene ether and 0.40-0.45 part of n-butyl alcohol into 30-35 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 6.0-7.0 parts of the double-bond vanillin prepared in the step one, 14.0-15.0 parts of butyl acrylate and 0.80-0.85 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 0.20-0.25 part of ammonium persulfate in 16.0-17.0 parts of deionized water to obtain a first part of initiator aqueous solution; dissolving 0.70-0.75 part of ammonium persulfate in 26.0-27.0 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 77.0-78.0 ℃, 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 1.5-2.0 h, after dropwise adding is finished, keeping the temperature for reaction for 1.5-2.0 h, cooling to room temperature, adjusting the pH of the reaction system to 7-8 by using ammonia water, adding adipic acid dihydrazide into the reaction system, mechanically stirring for 30 min, filtering and discharging to obtain the double-bonded vanillin modified styrene-acrylic emulsion.
in the step (1), the adding amount of the diacetone acrylamide is 0.40-0.45 part.
In the step (2), the power of ultrasonic treatment is 300W, ultrasonic work is carried out for 2 s, the intermission is 5s, ultrasonic treatment is carried out for 3 times, each time is 10 min, and the total ultrasonic time is 30 min.
in the step (3), the addition amount of the adipic acid dihydrazide is 0.35-0.40 part.
The double-bond vanillin-modified styrene-acrylic emulsion is prepared by the preparation method.
The invention has the following advantages:
The double-bond vanillin-modified styrene-acrylic emulsion is prepared by using a modified biomass material, replacing a 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-bond vanillin 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-bond vanillin-modified styrene-acrylic emulsion (MV-BA) by using double-bond vanillin (MV) 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-bond vanillin modified styrene-acrylic emulsion, which comprises the following steps:
the following are all prepared by mass portion,
(1) Adding 0.270-0.280 part of sodium dodecyl sulfate, 0.130-0.140 part of branched secondary alcohol polyoxyethylene ether and 0.40-0.45 part of n-butyl alcohol into 30-35 parts of deionized water, stirring and dissolving to obtain a uniform and transparent solution, then adding 0.40-0.45 part of diacetone acrylamide into the solution, and stirring to completely dissolve.
(2) Uniformly mixing 6.0-7.0 parts of the double-bond vanillin prepared in the step one, 14.0-15.0 parts of butyl acrylate and 0.80-0.85 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 a uniform and stable pre-emulsion. Wherein the power of ultrasonic treatment is 300W, ultrasonic work is carried out for 2 s, the interval is 5s, ultrasonic treatment is carried out for 3 times, each time is 10 min, and the total ultrasonic time is 30 min.
(3) dissolving 0.20-0.25 part of ammonium persulfate in 16.0-17.0 parts of deionized water to obtain a first part of initiator aqueous solution; dissolving 0.70-0.75 part of ammonium persulfate in 26.0-27.0 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 77.0-78.0 ℃, 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 1.5-2.0 h, after dropwise adding is finished, keeping the temperature for reaction for 1.5-2.0 h, cooling to room temperature, adjusting the pH of the reaction system to 7-8 by using ammonia water, adding 0.35-0.40 part of adipic acid dihydrazide into the reaction system, mechanically stirring for 30 min, filtering and discharging to obtain the double-bond vanillin modified styrene-acrylic emulsion.
The double-bond vanillin modified styrene-acrylic emulsion can be prepared according to the preparation method.
Example 1:
Preparation of double-bond vanillin modified styrene-acrylic emulsion
The following are all prepared by mass portion,
(1) adding 0.270 parts of sodium dodecyl sulfate, 0.130 parts of branched secondary alcohol polyoxyethylene ether and 0.40 parts of n-butanol into 30 parts of deionized water, stirring and dissolving to obtain a uniform and transparent solution, then adding 0.45 parts of diacetone acrylamide into the solution, and stirring until the diacetone acrylamide is completely dissolved.
(2) And (2) uniformly mixing 6.0 parts of the double-bond vanillin obtained in the step one, 14.0 parts of butyl acrylate and 0.85 part of glycidyl methacrylate, adding the mixture into the surfactant aqueous solution prepared in the step (1), and performing ultrasonic treatment to obtain a uniform and stable pre-emulsion. Wherein the power of ultrasonic treatment is 300W, ultrasonic work is carried out for 2 s, the interval is 5s, ultrasonic treatment is carried out for 3 times, each time is 10 min, and the total ultrasonic time is 30 min.
(3) Dissolving 0.20 part of ammonium persulfate in 17.0 parts of deionized water to obtain a first part of initiator aqueous solution; dissolving 0.70 part of ammonium persulfate in 26.0 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 77.0 ℃, 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 1.5 h, after dropwise adding, keeping the temperature for reaction for 2.0 h, cooling to room temperature, adjusting the pH of the reaction system to 7 by using ammonia water, adding 0.35 part of adipic acid dihydrazide into the reaction system, mechanically stirring for 30 min, filtering and discharging to obtain the double-bonded vanillin modified styrene-acrylic emulsion.
Example 2:
preparation of double-bond vanillin modified styrene-acrylic emulsion
The following are all prepared by mass portion,
(1) 0.275 part of sodium dodecyl sulfate, 0.130 part of branched secondary alcohol polyoxyethylene ether and 0.40 part of n-butanol are added into 35 parts of deionized water, stirred and dissolved until the solution is uniform and transparent, then 0.43 part of diacetone acrylamide is added into the solution, and stirred until the diacetone acrylamide is completely dissolved.
(2) And (2) uniformly mixing 6.5 parts of the double-bond vanillin obtained in the step one, 14.5 parts of butyl acrylate and 0.80 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 a uniform and stable pre-emulsion. Wherein the power of ultrasonic treatment is 300W, ultrasonic work is carried out for 2 s, the interval is 5s, ultrasonic treatment is carried out for 3 times, each time is 10 min, and the total ultrasonic time is 30 min.
(3) Dissolving 0.23 part of ammonium persulfate in 16.5 parts of deionized water to obtain a first part of initiator aqueous solution; dissolving 0.75 part of ammonium persulfate in 26.0 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 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 h, after dropwise adding, keeping the temperature for reaction for 1.5 h, cooling to room temperature, adjusting the pH of the reaction system to 8 by using ammonia water, adding 0.37 part of adipic acid dihydrazide into the reaction system, mechanically stirring for 30 min, filtering and discharging to obtain the double-bonded vanillin modified styrene-acrylic emulsion.
Example 3:
Preparation of double-bond vanillin modified styrene-acrylic emulsion
The following are all prepared by mass portion,
(1) Adding 0.280 part of sodium dodecyl sulfate, 0.140 part of branched secondary alcohol polyoxyethylene ether and 0.43 part of n-butanol into 33 parts of deionized water, stirring and dissolving to obtain a uniform and transparent solution, then adding 0.45 part of diacetone acrylamide into the solution, and stirring until the diacetone acrylamide is completely dissolved.
(2) and (2) uniformly mixing 6.5 parts of the double-bond vanillin obtained in the step one, 14.0 parts of butyl acrylate and 0.85 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 a uniform and stable pre-emulsion. Wherein the power of ultrasonic treatment is 300W, ultrasonic work is carried out for 2 s, the interval is 5s, ultrasonic treatment is carried out for 3 times, each time is 10 min, and the total ultrasonic time is 30 min.
(3) Dissolving 0.25 part of ammonium persulfate in 17.0 parts of deionized water to obtain a first part of initiator aqueous solution; dissolving 0.75 part of ammonium persulfate in 26.5 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 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 h, after dropwise adding, keeping the temperature for reaction for 2.0 h, cooling to room temperature, adjusting the pH of the reaction system to 8 by using ammonia water, adding 0.40 part of adipic acid dihydrazide into the reaction system, mechanically stirring for 30 min, filtering and discharging to obtain the double-bonded vanillin modified styrene-acrylic emulsion.
The VOC content of the double-bonded vanillin (MV) modified styrene-acrylic emulsion (MV-BA) and the commercial styrene-acrylic emulsion is tested by a gas chromatograph, and the test results are shown in Table 1. The test result shows that the double-bond vanillin modified styrene-acrylic emulsion prepared by using the modified biomass material to double-bond vanillin replaces petroleum-based toxic monomer styrene used in the traditional styrene-acrylic emulsion preparation process has the VOC content remarkably reduced from 2516 ppm to 339.6 ppm compared with the traditional styrene-acrylic emulsion.
TABLE 1 VOC content of double-bond vanillin-modified styrene-acrylic emulsion (MV-BA) and commercial styrene-acrylic emulsion
Test results
| kind of sample | Double bond vanillin modified styrene-acrylic emulsion (MV-BA) | commercially available styrene-acrylic emulsion |
| VOC content/ppm | 339.6 | 2516 |
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (5)
1. A preparation method of double-bond vanillin-modified styrene-acrylic emulsion is characterized by comprising the following steps:
the method comprises the following steps of:
(1) Adding 0.270-0.280 part of sodium dodecyl sulfate, 0.130-0.140 part of branched secondary alcohol polyoxyethylene ether and 0.40-0.45 part of n-butyl alcohol into 30-35 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 6.0-7.0 parts of the double-bond vanillin prepared in the step one, 14.0-15.0 parts of butyl acrylate and 0.80-0.85 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 0.20-0.25 part of ammonium persulfate in 16.0-17.0 parts of deionized water to obtain a first part of initiator aqueous solution; dissolving 0.70-0.75 part of ammonium persulfate in 26.0-27.0 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 77.0-78.0 ℃, 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 1.5-2.0 h, after dropwise adding is finished, keeping the temperature for reaction for 1.5-2.0 h, cooling to room temperature, adjusting the pH of the reaction system to 7-8 by using ammonia water, adding adipic acid dihydrazide into the reaction system, mechanically stirring for 30 min, filtering and discharging to obtain the double-bonded vanillin modified styrene-acrylic emulsion.
2. The preparation method of the double-bonded vanillin-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 0.40-0.45 part.
3. The preparation method of the double-bonded vanillin-modified styrene-acrylic emulsion as claimed in claim 2, wherein the preparation 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 intermission is 5s, ultrasonic treatment is carried out for 3 times, each time is 10 min, and the total ultrasonic time is 30 min.
4. The preparation method of the double-bonded vanillin-modified styrene-acrylic emulsion as claimed in claim 3, wherein the preparation method comprises the following steps:
In the step (3), the addition amount of the adipic acid dihydrazide is 0.35-0.40 part.
5. The double-bond vanillin-modified styrene-acrylic emulsion prepared by the preparation method as claimed in claims 1-4.
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Application publication date: 20191213 |