CN114456299A - Preparation method and application of polyacrylic acid thickening agent - Google Patents

Preparation method and application of polyacrylic acid thickening agent Download PDF

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Publication number
CN114456299A
CN114456299A CN202111643743.7A CN202111643743A CN114456299A CN 114456299 A CN114456299 A CN 114456299A CN 202111643743 A CN202111643743 A CN 202111643743A CN 114456299 A CN114456299 A CN 114456299A
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polyacrylic acid
reaction
initiator
thickener
ammonium chloride
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周华
裴小朋
项盛
冯艳
谭颖
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Wenzhou Research Institute Of Guoke Wenzhou Institute Of Biomaterials And Engineering
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Wenzhou Research Institute Of Guoke Wenzhou Institute Of Biomaterials And Engineering
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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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a preparation method and application of a polyacrylic acid thickener, which comprises the following steps: s1, mixing and dissolving acrylic acid, a comonomer, a dispersant, a cationic modifier and a crosslinking agent in an organic solvent under an inert atmosphere to obtain a mixed solution; s2, stirring and heating the mixed solution, dropwise adding an initiator, keeping the temperature for reaction, and cooling to obtain a reaction crude product; and S3, distilling the reaction crude product under reduced pressure, drying in vacuum to obtain the polyacrylic acid thickener, introducing cations on the basis of introducing long-chain alkyl and neutral side groups into an acrylic acid monomer, so that the polyacrylic acid thickener has good thickening performance and is convenient to transport.

Description

Preparation method and application of polyacrylic acid thickening agent
Technical Field
The invention relates to the technical field of thickening agents, and particularly relates to a preparation method and application of a polyacrylic acid thickening agent.
Technical Field
Polyacrylic acid thickening agent (trade name carbomer) is a high molecular polymer with a certain cross-linking structure, and the homopolymer and the copolymer thereof swell in water and form hydrogel after alkali neutralization, so that the polyacrylic acid thickening agent has excellent thickening and suspending effects, high stability and good transparency, and is widely applied to the fields of daily chemicals, medicines, foods and the like.
At present, anionic polyacrylate thickeners are widely used in China, and for example, Chinese patent with publication number CN101619543A discloses an acrylate synthetic thickener and a preparation method thereof, wherein the acrylate synthetic thickener is composed of acrylic acid, acrylamide, 25% ammonia water, a functional monomer, EDTA, deionized water, odorless kerosene, 3# white oil, dipropylene phthalate, ammonium persulfate, span 80 and isomeric hexadecanol polyoxyethylene ether, wherein the functional monomer is prepared from fatty amine polyoxyethylene ether, methyl methacrylate, nitroxide free radical piperidinol and sodium methoxide, the thickening performance of the thickener still needs to be improved, and the finished product is in an emulsion state and is inconvenient to transport.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a polyacrylic acid thickening agent and application thereof, which have good thickening performance and are convenient to transport.
According to a first aspect of the present invention, there is provided a method for preparing a polyacrylic acid thickener, comprising the steps of:
s1, mixing and dissolving acrylic acid, a comonomer, a dispersant, a cationic modifier and a crosslinking agent in an organic solvent under an inert atmosphere to obtain a mixed solution;
s2, stirring and heating the mixed solution, dropwise adding an initiator, carrying out heat preservation reaction, and then cooling to obtain a reaction crude product;
and S3, distilling the reaction crude product under reduced pressure, and drying in vacuum to obtain the polyacrylic acid thickening agent.
Preferably, the comonomer comprises one or more of maleic acid, fumaric acid, itaconic acid, lauryl acrylate, cetyl acrylate, stearyl acrylate.
Preferably, the dispersing agent comprises one or more of sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester and polyether polyol, wherein the dispersing agent belongs to a surfactant, and the dispersing agent is added to enable the raw materials with different solubilities to be stably dispersed in the medium due to the large difference of the solubilities of the raw materials used in the scheme.
Preferably, the cross-linking agent comprises one or more of pentaerythritol triallyl ether, polyethylene glycol diacrylate, tripropylene glycol diacrylate, sucrose allyl ether and sucrose allyl ester.
Preferably, the initiator comprises one or more of lauroyl peroxide, benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, and the initiator is used to promote the copolymer formation reaction.
Preferably, the cation modifier comprises one or more of ammonium salt, lactate and pyridinium salt, and cations are introduced to enable the prepared polyacrylic acid thickener to have certain reverse electrolyte performance, improve electrolyte resistance, change product state and enhance thickening effect, and the ammonium salt, the lactate and the pyridinium salt belong to weak cations, so that the polyacrylic acid thickener can be converted from a solid to an aqueous phase in a neutral environment, and the application range is expanded while the transportation effect is ensured.
Preferably, the ammonium salt comprises one or more of dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, hexadecyl trimethyl ammonium bromide, dodecyl-dimethyl-2-phenoxy-ethyl ammonium bromide, behenyl-2-hydroxypropyl trimethyl ammonium chloride, didecyl dimethyl ammonium chloride, methyl diethyl polypropoxy ammonium chloride, lauryl dimethyl ammonium oxide.
Preferably, the lactate comprises one or more of cocamidopropyl dimethylamine lactate, isostearamidopropyl morpholine lactate.
Preferably, the pyridinium salt is pyridinium lauryl chloride.
According to the second aspect of the invention, the application of a polyacrylic acid thickener in a neutral aqueous solution is provided, wherein the polyacrylic acid thickener accounts for 0.1-0.2% of the mass of the neutral aqueous solution, and the concrete steps comprise: adding the polyacrylic acid thickener into a sodium chloride solution according to the mass fraction of 0.1-0.2%, and neutralizing with triethanolamine to neutrality to obtain a thickening liquid.
The invention has the beneficial effects that:
1. by adding the comonomer and the cross-linking agent, the thickening effect is improved;
2. the prepared polyacrylic acid thickening agent has certain anti-electrolyte performance, can improve electrolyte resistance, improve thickening effect, and control product form to facilitate transportation;
3. weak cations are selected as cation modifiers, and the polyacrylic acid thickening agent can be converted from a solid to a water phase in a neutral environment, so that the transportation effect is ensured, and the application range is expanded;
4. the polyacrylic acid thickener obtained by the process has high aqueous solution viscosity and high light transmittance;
5. the preparation process is simple and easy to implement, aromatic hydrocarbon solvents such as benzene and the like are not used, the toxicity is low, the environment is protected, the boiling point of the solvents is moderate, the solvents are convenient to recover, and the solvents are easy to completely remove from products.
Detailed Description
The present invention will be described in further detail with reference to examples.
It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available by purchase.
The preparation method of the polyacrylic acid thickener comprises the following steps:
preparing raw materials: the raw materials comprise acrylic acid, a comonomer, a dispersant, a cation modifier, a cross-linking agent, an organic solvent and an initiator;
the comonomer comprises one or more of maleic acid, fumaric acid, itaconic acid, lauryl acrylate, cetyl acrylate and octadecyl acrylate;
the dispersing agent comprises one or more of sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester and polyether polyol;
the cross-linking agent comprises one or more of pentaerythritol triallyl ether, polyethylene glycol diacrylate, tripropylene glycol diacrylate, sucrose allyl ether and sucrose allyl ester;
the initiator comprises one or more of lauroyl peroxide, benzoyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile;
the cation modifier comprises one or more of dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, hexadecyl trimethyl ammonium bromide, dodecyl-dimethyl-2-phenoxy-ethyl ammonium bromide, behenic acid-2-hydroxypropyl trimethyl ammonium chloride, didecyl dimethyl ammonium chloride, methyl diethyl polypropoxy ammonium chloride, lauryl dimethyl ammonium oxide, cocoamidopropyl dimethyl amine lactate, isostearamidopropyl morpholine lactate and lauryl pyridinium chloride;
the organic solvent comprises one or more of n-hexane, cyclohexane, heptane, methyl acetate, ethyl acetate, isopropanol, tetrahydrofuran and 1, 2-dioxane;
the mass parts of the materials are as follows: 50-85 parts of organic solvent, 5-20 parts of acrylic acid, 1-10 parts of comonomer, 0.01-1 part of dispersant, 0.1-1 part of assistant, 0.01-1 part of cross-linking agent and 0.01-1% of initiator.
Copolymerization modification reaction: according to the types and the reaction proportion of the raw materials, sequentially adding an organic solvent, acrylic acid, a comonomer, a dispersant, an auxiliary agent and a crosslinking agent into a reaction kettle, and introducing nitrogen for 20-40 minutes to replace oxygen in the system; then stirring, heating to 60-80 ℃, dropwise adding the initiator solution into the reaction kettle within 30-60 minutes, carrying out heat preservation reaction for 3-8 hours, then cooling to 30-50 ℃, carrying out vacuum concentration at 2000-5000 Pa to recover the solvent, and carrying out vacuum drying at 50-80 ℃ at 0-300 Pa for 3-10 hours after no organic solvent is recoverable to obtain white powder, namely the polyacrylic acid thickener.
And the polyacrylic acid thickener is applied to a sodium chloride solution, and the application steps comprise: adding the polyacrylic acid thickener into a sodium chloride solution according to the mass fraction of 0.1-0.2%, and neutralizing with triethanolamine to neutrality to obtain a thickening liquid, wherein preferably, the concentration of the sodium chloride solution is 5-20 mol/L.
The present invention will be described in detail below by way of examples, but the scope of the present invention is not limited thereto.
Example 1
A thermometer, a mechanical stirring paddle, a reflux condenser tube and a constant-pressure dropping funnel are sequentially arranged on a 1000 ml four-mouth glass bottle, nitrogen is led into a reaction bottle from the upper end of the funnel, and is led out from the upper end of the reflux condenser tube to enter a bubbler.
80 g of acrylic acid, 1g of maleic acid, 0.5 g of hexadecyltrimethylammonium chloride, 360 g of n-hexane, 200 g of ethyl acetate, 0.81 g of pentaerythritol triallyl ether and 0.80 g of sorbitan fatty acid ester are sequentially added into a four-mouth reaction bottle, nitrogen is introduced, stirring is carried out, and the temperature is raised. When the temperature of the system reached 60 ℃, a solution of 0.20 g of initiator lauroyl peroxide dissolved in 20 ml of ethyl acetate was added dropwise to the reaction system over 1 hour, and the reaction system became cloudy after about 20 minutes. After the initiator is added dropwise, keeping the temperature at 60 ℃ for reaction for 5 hours, stopping heating, reducing the temperature to 45 ℃, concentrating under reduced pressure at 2000-5000 Pa, and recovering the solvent; when no solvent can be recovered, increasing the vacuum degree to 0-300 Pa, and continuously drying the materials at 50-80 ℃ for 4 hours to obtain white powdery solid. A0.2% aqueous solution was prepared, neutralized to pH6.64 with triethanolamine, and had a viscosity of 32500 mPa.s and a light transmittance of 94.0% as measured with an NDJ-5S viscometer.
Example 2
A thermometer, a mechanical stirring paddle, a reflux condenser tube and a constant-pressure dropping funnel are sequentially arranged on a 1000 ml four-mouth glass bottle, nitrogen is led into a reaction bottle from the upper end of the funnel, and is led out from the upper end of the reflux condenser tube to enter a bubbler. Adding 80 g of acrylic acid, 2g of fumaric acid, 400 g of cyclohexane, 200 g of ethyl acetate, 0.81 g of pentaerythritol triallyl ether, 1.6 g of dodecyl dimethyl benzyl ammonium chloride and 0.80 g of polyoxyethylene sorbitan fatty acid ester into a four-mouth reaction bottle in sequence, introducing nitrogen, stirring and heating. When the temperature of the system reached 65 ℃, a solution of 0.20 g of the initiator benzoyl peroxide dissolved in 20 ml of ethyl acetate was added dropwise to the reaction system over 1 hour, and the reaction system became cloudy after about 20 minutes. After the initiator is added dropwise, keeping the temperature of 65 ℃ for reaction for 5 hours, stopping heating, reducing the temperature to 43 ℃, concentrating under reduced pressure at 2000-5000 Pa, and recovering the solvent; when no solvent can be recovered, increasing the vacuum degree to 0-300 Pa, and continuously drying the materials at 50-80 ℃ for 3 hours to obtain white powdery solid. A0.1% aqueous solution was prepared, neutralized to pH6.46 with triethanolamine, and measured to have a viscosity of 38400 Pa.s and a light transmittance of 93.7% using an NDJ-5S viscometer. Example 3
A thermometer, a mechanical stirring paddle, a reflux condenser tube and a constant-pressure dropping funnel are sequentially arranged on a 1000 ml four-mouth glass bottle, nitrogen is led into a reaction bottle from the upper end of the funnel, and is led out from the upper end of the reflux condenser tube to enter a bubbler. Adding 80 g of acrylic acid, 10g of itaconic acid, 0.80 g of dodecyl-dimethyl-2-phenoxy-ethyl ammonium bromide, 400 g of heptane, 200 g of ethyl acetate, 0.40 g of sucrose-based allyl ether and 0.50 g of polyether polyol into a four-mouth reaction bottle in sequence, introducing nitrogen, stirring and heating. When the temperature of the system reached 70 ℃, a solution of 0.10 g of azobisisobutyronitrile as an initiator dissolved in 60 ml of ethyl acetate was added dropwise to the reaction system over 1 hour, and the reaction system became cloudy after about 20 minutes. After the initiator is added dropwise, keeping the temperature at 70 ℃ for reacting for 6 hours, stopping heating, reducing the temperature to 45 ℃, concentrating under reduced pressure at 2000-5000 Pa, and recovering the solvent; when no solvent can be recovered, increasing the vacuum degree to 0-300 Pa, and continuously drying the materials at 50-80 ℃ for 4 hours to obtain white powdery solid. A0.2% aqueous solution was prepared, neutralized to pH6.49 with triethanolamine, and had a viscosity of 36800 Pa.s and a light transmittance of 92.4% as measured by an NDJ-5S viscometer.
Example 4
A thermometer, a mechanical stirring paddle, a reflux condenser tube and a constant-pressure dropping funnel are sequentially arranged on a 1000 ml four-mouth glass bottle, nitrogen is led into a reaction bottle from the upper end of the funnel, and is led out from the upper end of the reflux condenser tube to enter a bubbler. 80 g of acrylic acid, 3g of hexadecyl acrylate, 0.50 g of cocamidopropyl dimethylamine lactate, 430 g of n-hexane, 200 g of methyl acetate, 0.50 g of tripropylene glycol diacrylate and 0.50 g of polyoxyethylene sorbitan fatty acid ester are sequentially added into a four-mouth reaction bottle, nitrogen is introduced, stirring is carried out, and the temperature is raised. When the temperature of the system reached 60 ℃, a solution of 0.20 g of azobisisobutyronitrile as an initiator dissolved in 60 ml of methyl acetate was added dropwise to the reaction system over 1 hour, and the reaction system became cloudy after about 20 minutes. After the initiator is added dropwise, keeping the temperature of 60 ℃ for reaction for 4 hours, stopping heating, reducing the temperature to 40 ℃, concentrating under reduced pressure at 2000-5000 Pa, and recovering the solvent; when no solvent can be recovered, increasing the vacuum degree to 0-300 Pa, and continuously drying the materials at 50-80 ℃ for 4 hours to obtain white powdery solid. A0.2% aqueous solution was prepared, neutralized to pH6.57 with triethanolamine, and measured by NDJ-5S viscometer to have a viscosity of 36000 Pa.s and a light transmittance of 93.5%.
Example 5
A thermometer, a mechanical stirring paddle, a reflux condenser tube and a constant-pressure dropping funnel are sequentially arranged on a 1000 ml four-mouth glass bottle, nitrogen is led into a reaction bottle from the upper end of the funnel, and is led out from the upper end of the reflux condenser tube to enter a bubbler. 80 g of acrylic acid, 2g of octadecyl acrylate, 0.50 g of isostearamidopropyl morpholine lactate, 400 g of ethyl acetate, 100 g of isopropanol, 0.50 g of octadecyl acrylate and 0.50 g of polyoxyethylene sorbitan fatty acid ester are sequentially added into a four-mouth reaction bottle, nitrogen is introduced, stirring is carried out, and the temperature is raised. When the temperature of the system reached 65 ℃, a solution of 0.20 g of the initiator azobisisoheptonitrile dissolved in 20 ml of isopropanol was added dropwise to the reaction system over 1 hour, and the reaction system became cloudy after about 20 minutes. After the initiator is added dropwise, keeping the temperature of 65 ℃ for reaction for 4 hours, stopping heating, reducing the temperature to 40 ℃, concentrating under reduced pressure at 2000-5000 Pa, and recovering the solvent; when no solvent can be recovered, increasing the vacuum degree to 0-300 Pa, and continuously drying the materials at 50-80 ℃ for 6 hours to obtain white powdery solid. A0.2% aqueous solution was prepared, neutralized to pH6.67 with triethanolamine, and had a viscosity of 32800 Pa.s and a light transmittance of 93.1% as measured with an NDJ-5S viscometer.
Example 6
A thermometer, a mechanical stirring paddle, a reflux condenser tube and a constant-pressure dropping funnel are sequentially arranged on a 1000 ml four-mouth glass bottle, nitrogen is led into a reaction bottle from the upper end of the funnel, and is led out from the upper end of the reflux condenser tube to enter a bubbler. 80 g of acrylic acid, 3g of lauryl acrylate, 0.60 g of lauryl pyridinium chloride, 400 g of n-hexane, 200 g of tetrahydrofuran, 0.70 g of tripropylene glycol diacrylate and 0.60 g of polyether polyol are sequentially added into a four-port reaction bottle, nitrogen is introduced, stirring is carried out, and the temperature is raised. When the temperature of the system reached 60 ℃, a solution of 0.15 g of azobisisobutyronitrile as an initiator dissolved in 60 ml of tetrahydrofuran was added dropwise to the reaction system over 1 hour, and the reaction system became cloudy after about 20 minutes. After the initiator is added dropwise, keeping the temperature of 60 ℃ for reaction for 4 hours, stopping heating, reducing the temperature to 40 ℃, concentrating under reduced pressure at 2000-5000 Pa, and recovering the solvent; when no solvent can be recovered, increasing the vacuum degree to 0-300 Pa, and continuously drying the materials at 50-80 ℃ for 4 hours to obtain white powdery solid. A0.2% aqueous solution was prepared, neutralized to pH6.91 with triethanolamine, and measured to have a viscosity of 33600 Pa.s and a light transmittance of 93.0% by means of an NDJ-5S viscometer.
Example 7
A thermometer, a mechanical stirring paddle, a reflux condenser tube and a constant-pressure dropping funnel are sequentially arranged on a 1000 ml four-mouth glass bottle, nitrogen is led into a reaction bottle from the upper end of the funnel, and is led out from the upper end of the reflux condenser tube to enter a bubbler. 78 g of acrylic acid, 2.00 g of hexadecyl acrylate, 0.60 g of methyl diethyl poly (propoxy) ammonium chloride, 400 g of cyclohexane, 200 g of ethyl acetate, 0.70 g of pentaerythritol triallyl ether and 0.60 g of polyether polyol are sequentially added into a four-mouth reaction bottle, nitrogen is introduced, and the mixture is stirred and heated. When the temperature of the system reached 65 ℃, a solution of 0.20 g of initiator lauroyl peroxide dissolved in 60 ml of ethyl acetate was added dropwise to the reaction system over 1 hour, and the reaction system became cloudy after about 20 minutes. After the initiator is added dropwise, keeping the temperature of 65 ℃ for reaction for 4 hours, stopping heating, reducing the temperature to 41 ℃, concentrating under reduced pressure at 2000-5000 Pa, and recovering the solvent; when no solvent can be recovered, increasing the vacuum degree to 0-300 Pa, and continuously drying the materials at 50-80 ℃ for 4 hours to obtain white powdery solid. A0.2% aqueous solution was prepared, neutralized to pH6.77 with triethanolamine, and had a viscosity of 35200 Pa.s and a light transmittance of 92.9% as measured by an NDJ-5S viscometer.
Example 8
A thermometer, a mechanical stirring paddle, a reflux condenser tube and a constant-pressure dropping funnel are sequentially arranged on a 1000 ml four-mouth glass bottle, nitrogen is led into a reaction bottle from the upper end of the funnel, and is led out from the upper end of the reflux condenser tube to enter a bubbler. 75 g of acrylic acid, 5.00 g of lauryl acrylate, 0.90 g of dodecyl-dimethyl-2-phenoxy-ethyl ammonium bromide, 400 g of cyclohexane, 200 g of ethyl acetate, 0.80 g of pentaerythritol triallyl ether and 0.60 g of polyoxyethylene sorbitan fatty acid ester are sequentially added into a four-mouth reaction bottle, nitrogen is introduced, stirring is carried out, and the temperature is raised. When the temperature of the system reached 65 ℃, a solution of 0.20 g of initiator lauroyl peroxide dissolved in 60 ml of ethyl acetate was added dropwise to the reaction system over 1 hour, and the reaction system became cloudy after about 20 minutes. After the initiator is added dropwise, keeping the reaction at 63 ℃ for 4 hours, stopping heating, reducing the temperature to 41 ℃, concentrating under reduced pressure at 2000-5000 Pa, and recovering the solvent; when no solvent can be recovered, increasing the vacuum degree to 0-300 Pa, and continuously drying the materials at 50-80 ℃ for 4 hours to obtain white powdery solid. A0.2% aqueous solution was prepared, neutralized to pH6.35 with triethanolamine, and had a viscosity of 36800 Pa.s and a light transmittance of 93.5% as measured by an NDJ-5S viscometer.
Example 9
A thermometer, a mechanical stirring paddle, a reflux condenser tube and a constant-pressure dropping funnel are sequentially arranged on a 1000 ml four-mouth glass bottle, nitrogen is led into a reaction bottle from the upper end of the funnel, and is led out from the upper end of the reflux condenser tube to enter a bubbler. 80 g of acrylic acid, 5g of hexadecyl acrylate, 1.0 g of lauryl pyridinium chloride, 400 g of cyclohexane, 200 g of ethyl acetate, 0.50 g of pentaerythritol triallyl ether, 0.3 g of polyethylene glycol diacrylate and 0.60 g of polyether polyol are sequentially added into a four-mouth reaction bottle, nitrogen is introduced, stirring is carried out, and the temperature is increased. When the temperature of the system reached 65 ℃, a solution of 0.20 g of initiator lauroyl peroxide dissolved in 60 ml of ethyl acetate was added dropwise to the reaction system over 1 hour, and the reaction system became cloudy after about 20 minutes. After the initiator is added dropwise, keeping the reaction at 64 ℃ for 4 hours, stopping heating, reducing the temperature to 43 ℃, concentrating under reduced pressure at 2000-5000 Pa, and recovering the solvent; when no solvent can be recovered, increasing the vacuum degree to 0-300 Pa, and continuously drying the materials at 50-80 ℃ for 5 hours to obtain white powdery solid. A0.2% aqueous solution was prepared, neutralized to pH6.81 with triethanolamine, and measured to have a viscosity of 35600 Pa.s and a light transmittance of 93.7% using an NDJ-5S viscometer.
Example 10
A thermometer, a mechanical stirring paddle, a reflux condenser tube and a constant-pressure dropping funnel are sequentially arranged on a 1000 ml four-mouth glass bottle, nitrogen is led into a reaction bottle from the upper end of the funnel, and is led out from the upper end of the reflux condenser tube to enter a bubbler. 80 g of acrylic acid, 5g of lauryl acrylate, 1.0 g of lauryl dimethyl ammonium oxide, 400 g of cyclohexane, 200 g of ethyl acetate, 0.80 g of pentaerythritol triallyl ether and 0.60 g of sorbitan fatty acid ester are sequentially added into a four-mouth reaction bottle, nitrogen is introduced, and the mixture is stirred and heated. When the temperature of the system reached 65 ℃, a solution of 0.20 g of initiator lauroyl peroxide dissolved in 60 ml of ethyl acetate was added dropwise to the reaction system over 1 hour, and the reaction system became cloudy after about 20 minutes. After the initiator is added dropwise, keeping the temperature of 65 ℃ for reaction for 4 hours, stopping heating, reducing the temperature to 43 ℃, concentrating under reduced pressure at 2000-5000 Pa, and recovering the solvent; when no solvent can be recovered, increasing the vacuum degree to 0-300 Pa, and continuously drying the materials at 50-80 ℃ for 5 hours to obtain white powdery solid. A0.2% aqueous solution was prepared, neutralized to pH6.83 with triethanolamine, and measured to have a viscosity of 32800 Pa.s and a light transmittance of 92.9% using an NDJ-5S viscometer.
Comparative example
A thermometer, a mechanical stirring paddle, a reflux condenser tube and a constant-pressure dropping funnel are sequentially arranged on a 1000 ml four-mouth glass bottle, nitrogen is led into a reaction bottle from the upper end of the funnel, and is led out from the upper end of the reflux condenser tube to enter a bubbler. 80 g of acrylic acid, 420 g of cyclohexane, 200 g of ethyl acetate, 0.81 g of pentaerythritol triallyl ether and 0.80 g of Hypermer B-246 were sequentially added into a four-neck reaction flask, nitrogen gas was introduced, stirring was carried out, and the temperature was increased. When the temperature of the system reached 65 ℃, a solution of 0.20 g of initiator lauroyl peroxide dissolved in 20 ml of ethyl acetate was added dropwise to the reaction system over 1 hour, and the reaction system became cloudy after about 20 minutes. After the initiator is added dropwise, the reaction is kept at 65 ℃ for 5 hours, the heating is stopped, when the temperature is reduced to 43 ℃, the pressure of 2000-5000 Pa is reduced and the concentration is carried out, the solvent is recovered to obtain the emulsion thickener, the thickener is prepared into 0.2 percent aqueous solution, the viscosity is 17600 mPa.s by using an NDJ-5S viscometer, and the light transmittance is 87.0 percent.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims, any of the claimed embodiments may be used in any combination.
Those of ordinary skill in the art will understand that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same, although the present application is described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: it is possible to modify the solutions described in the previous embodiments or to substitute some or all of the technical features thereof without departing from the scope of the claims.

Claims (10)

1. A preparation method of a polyacrylic acid thickener is characterized by comprising the following steps:
s1, mixing and dissolving acrylic acid, a comonomer, a dispersant, a cationic modifier and a crosslinking agent in an organic solvent under an inert atmosphere to obtain a mixed solution;
s2, stirring and heating the mixed solution, dropwise adding an initiator, carrying out heat preservation reaction, and then cooling to obtain a reaction crude product;
and S3, distilling the reaction crude product under reduced pressure, and drying in vacuum to obtain the polyacrylic acid thickening agent.
2. The method of claim 1, wherein the comonomer comprises one or more of maleic acid, fumaric acid, itaconic acid, lauryl acrylate, cetyl acrylate, and stearyl acrylate.
3. The method for preparing polyacrylic acid thickener according to claim 1, wherein the dispersant comprises one or more of sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyether polyol.
4. The method for preparing polyacrylic acid thickener according to claim 1, wherein the cross-linking agent comprises one or more of pentaerythritol triallyl ether, polyethylene glycol diacrylate, tripropylene glycol diacrylate, sucrose allyl ether, and sucrose allyl ester.
5. The method of claim 1, wherein the initiator comprises one or more of lauroyl peroxide, benzoyl peroxide, azobisisobutyronitrile, and azobisisoheptonitrile.
6. The method of claim 1, wherein the cationic modifier comprises one or more of ammonium salt, lactate salt, pyridinium salt.
7. The method of claim 4, wherein the ammonium salt comprises one or more of dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, hexadecyl trimethyl ammonium bromide, dodecyl-dimethyl-2-phenoxy-ethyl ammonium bromide, behenyl-2-hydroxypropyl trimethyl ammonium chloride, didecyl dimethyl ammonium chloride, methyl diethyl poly propoxy ammonium chloride, lauryl dimethyl ammonium oxide.
8. The method for preparing polyacrylic acid thickener according to claim 4, wherein the lactate comprises one or more of cocamidopropyl dimethylamine lactate and isostearamidopropyl morpholine lactate.
9. The method of claim 4, wherein the pyridinium salt is pyridinium lauryl chloride.
10. Use of a polyacrylic acid thickener prepared according to the preparation method of any one of claims 1 to 9 in a neutral aqueous solution, wherein the polyacrylic acid thickener is present in an amount of 0.1 to 0.2% by mass of the neutral aqueous solution.
CN202111643743.7A 2021-12-30 2021-12-30 Preparation method and application of polyacrylic acid thickening agent Pending CN114456299A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4800220A (en) * 1986-03-14 1989-01-24 Manufacture De Produits Chimiques Protex Crosslinked carboxylic copolymers usable as thickeners in aqueous media and preparation thereof
CN103183765A (en) * 2013-04-10 2013-07-03 中国日用化学工业研究院 Preparation method of powdery polyacrylic acid thickener
CN112876596A (en) * 2021-01-06 2021-06-01 广州市东雄化工有限公司 Solution type alcohol disinfection gel thickening agent and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4800220A (en) * 1986-03-14 1989-01-24 Manufacture De Produits Chimiques Protex Crosslinked carboxylic copolymers usable as thickeners in aqueous media and preparation thereof
CN103183765A (en) * 2013-04-10 2013-07-03 中国日用化学工业研究院 Preparation method of powdery polyacrylic acid thickener
CN112876596A (en) * 2021-01-06 2021-06-01 广州市东雄化工有限公司 Solution type alcohol disinfection gel thickening agent and preparation method thereof

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