CN111217958A - Water-soluble acrylic acid stabilizer and preparation method thereof - Google Patents
Water-soluble acrylic acid stabilizer and preparation method thereof Download PDFInfo
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- CN111217958A CN111217958A CN202010027320.1A CN202010027320A CN111217958A CN 111217958 A CN111217958 A CN 111217958A CN 202010027320 A CN202010027320 A CN 202010027320A CN 111217958 A CN111217958 A CN 111217958A
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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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/32—Polymerisation in water-in-oil emulsions
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- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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
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- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- 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
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- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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Abstract
The invention relates to the field of stabilizers and discloses a water-soluble acrylic acid stabilizer which comprises the following components in parts by weight: 10-30 parts of acrylic monomer, 2-8 parts of itaconic acid, 30-40 parts of acrylamide, 15-20 parts of neutralizer, 0.05-0.1 part of molecular weight regulator, 0.5-1.0 part of initiator and 140 parts of water. The preparation method of the stabilizer comprises the following steps: stirring water, acrylic monomers and itaconic acid, adding a neutralizer, keeping the temperature at no more than 40 ℃, and keeping the pH at 4.5-5.5; adding acrylamide and stirring; adding molecular weight regulator and water, and stirring to obtain mixed solution; taking out 20% of the mixed solution, heating to 60-70 ℃, adding an initiator, slowly dropwise adding the rest 80% of the mixed solution at 65-70 ℃ for 1-1.5 hours, and preserving heat for 30-40 minutes after polymerization to obtain the water-soluble stabilizer. The stabilizer prepared by the invention is used for preparing the thickening agent, can improve emulsion polymerization and distillation concentration, has good storage stability and use stability, and can reduce the using amount of a continuous phase solvent of the thickening agent and reduce the distillation burden.
Description
Technical Field
The invention relates to the technical field of thickening stabilizers, and particularly relates to a water-soluble acrylic acid stabilizer and a preparation method thereof.
Background
In recent decades, as the synthetic thickeners have the advantages of high color yield, good rheological property, convenient pulping, high paste forming speed and the like, domestic researchers have conducted intensive research on the synthetic thickeners, numerous synthetic thickener products appear on the market, and when the acrylate thickeners are prepared in an inverse emulsion polymerization mode, along with the requirements of the market on product transportation, use amount, environmental protection and the like, the whole acrylate thickener technology is promoted to be innovated.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, a first object of the present invention is to provide a water-soluble acrylic stabilizer which can improve emulsion polymerization and distillation concentration, has good storage stability and use stability, and can reduce the amount of a continuous phase solvent used as a thickener to reduce the distillation load.
The second purpose of the invention is to provide a preparation method of the water-soluble acrylic acid stabilizer, which is simple and easy to implement, has strong operability and is beneficial to improving the polymerization stability and the storage stability of the product.
In order to achieve the above purpose, the solution adopted by the invention is as follows:
a water-soluble acrylic acid stabilizer comprises the following components in parts by weight: 10-30 parts of acrylic monomer, 2-8 parts of itaconic acid, 30-40 parts of acrylamide, 15-20 parts of neutralizer, 0.05-0.1 part of molecular weight regulator, 0.5-1.0 part of initiator and 140 parts of water.
Further, the coating comprises the following components in parts by weight: 15-25 parts of acrylic monomer, 3-7 parts of itaconic acid, 35-40 parts of acrylamide, 16-20 parts of neutralizer, 0.06-0.1 part of molecular weight regulator, 0.6-1.0 part of initiator and 140 parts of water.
Further, the acrylic monomer is one or more of methacrylic acid, hydroxyethyl acrylate and methyl propyl hydroxyethyl.
Further, the neutralizing agent is 25-35% of liquid caustic soda.
Further, the molecular weight regulator is one or more of sodium formate, dodecyl mercaptan, and 2, 2, 4-dimethylpentanediol-1, 3-monoisobutyrate.
Further, the initiator is a persulfate system or an azo system.
Further, the initiator is one or more of potassium persulfate, ammonium persulfate and azodiisobutyl imidazole hydrochloride.
Further, the initiator is potassium persulfate.
A method of preparing a water soluble acrylic stabilizer comprising the steps of:
(1) adding 50 weight percent of water into a reactor, then adding acrylic acid monomer and itaconic acid, stirring uniformly, slowly adding a neutralizer dropwise, continuously stirring, keeping the neutralization temperature not more than 40 ℃, and controlling the neutralization pH value to be 4.5-5.5;
(2) adding acrylamide into the step (1), and stirring until the acrylamide is completely dissolved;
(3) adding a molecular weight regulator and 50 wt% of water into the step (2), and uniformly stirring to obtain a mixed solution;
(4) and (3) taking out 20% of the mixed solution in the step (3), heating the mixed solution to 60-70 ℃, adding an initiator, slowly dropwise adding the rest 80% of the mixed solution, controlling the polymerization temperature to be 65-70 ℃, controlling the dropwise adding time to be 1-1.5 hours, and after the polymerization is finished, preserving the heat for 30-40 minutes to obtain the water-soluble stabilizer.
Further, after the initiator is added in the step (4), after the temperature is raised to 70 ℃, the rest of the mixed solution is slowly dripped.
The invention has the beneficial effects that:
1. the water-soluble acrylic acid stabilizer is prepared by a free radical polymerization mode, acrylic acid is taken as a main monomer of the acrylic acid monomer, methyl, ethyl ester and other groups are introduced on an acrylic acid molecular chain, ester bonds, hydrogen bonds and the like can be formed on the molecular chain by introducing the groups, the hydrophobic end of the molecular chain tends to a continuous phase of the thickener in the polymerization of introducing the acrylic acid thickener, and the hydrophilic end of the molecular chain is combined in a water-in-oil water phase in a chemical bond mode in a water-in-oil phase, so that the whole water-in-oil emulsion particle is more stable and plays a role of the stabilizer, and the storage and the service performance of the thickener after being added into the thickener are greatly improved.
2. The water-soluble acrylic acid stabilizer can greatly improve the polymerization stability and the distillation stability of the thickening agent, and the inventor introduces sodium formate or dodecyl mercaptan and the like as molecular weight regulators to control the molecular weight of a polymer, so that the polymerization effect of the thickening agent is ensured, and the polymerization of the thickening agent is not influenced.
3. After the stability of the water-soluble acrylic acid stabilizer is improved, the inventor improves the initial concentration of polymerization in the formula design of the stabilizer, so that the use of a continuous phase solvent is reduced, the thickening capacity of a thickening agent is improved, the use amount is reduced, and the transportation pressure is reduced; meanwhile, the introduction of the water-soluble acrylic polymer stabilizer hinders the migration efficiency of free radical ions during inverse emulsion polymerization, and finally, the quality and performance of the thickening agent can be greatly improved.
4. In the preparation method, the initiator is added after the temperature is raised, so that more free radicals can be released by the initiator, the initiation reaction is quicker, and the molecular weight distribution of the polymer after the reaction is more uniform.
5. The preparation method is similar to seed emulsion polymerization, adopts a semi-continuous polymerization mode, can effectively control the heat release condition of polymerization on one hand, is convenient for production operation, and reduces risks; on the other hand, in the reaction process, the free radicals are always in a hunger and thirsty state, and after the new monomer is added, the monomer can be quickly consumed, so that the retention and self-polymerization of the monomer are avoided, the aim of effectively controlling the molecular weight is fulfilled, and the particle size distribution of the stabilizer is uniform and the performance is stable.
6. The preparation method of the water-soluble acrylic acid stabilizer is simple and has strong operability.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of a water-soluble acrylic acid-based stabilizer and a method for preparing the same according to embodiments of the present invention.
A water-soluble acrylic acid stabilizer comprises the following components in parts by weight: 10-30 parts of acrylic monomer, 2-8 parts of itaconic acid, 30-40 parts of acrylamide, 15-20 parts of neutralizer, 0.05-0.1 part of molecular weight regulator, 0.5-1.0 part of initiator and 140 parts of water. It is noted that acrylamide sulfonate can also be selected as the acrylamide in the stabilizer component.
In this embodiment, the acrylic monomer is one or more of methacrylic acid, hydroxyethyl acrylate, and methyl hydroxyethyl acrylate.
In this example, the neutralizing agent is 25-35% caustic soda.
In this example, the molecular weight regulator is one or more of sodium formate, dodecyl mercaptan, and 2, 2, 4-dimethylpentanediol-1, 3-monoisobutyrate. In the stabilizer, one or more of sodium formate, dodecyl mercaptan and 2, 2, 4-dimethylpentanediol-1, 3-monoisobutyrate are creatively introduced as molecular weight regulators by the inventor to control the molecular weight of the polymer, so that the polymerization effect of the polymer stabilizer is ensured and the polymerization of the thickener is not influenced.
In this example, the initiator is a persulfate system or an azo system.
In this embodiment, the initiator is one or more of potassium persulfate, ammonium persulfate and azobisisobutylimidazole hydrochloride, and preferably the initiator is potassium persulfate, and the potassium persulfate is dissolved and then is a neutral solution.
A method of preparing a water soluble acrylic stabilizer comprising the steps of:
(1) adding 50 weight percent of water into a reactor, then adding acrylic acid monomer and itaconic acid, stirring uniformly, slowly adding a neutralizer dropwise, continuously stirring, keeping the neutralization temperature not more than 40 ℃, and controlling the neutralization pH value to be 4.5-5.5;
(2) adding acrylamide or acrylamide sulfonate into the step (1), and stirring until the acrylamide or acrylamide sulfonate is completely dissolved;
(3) adding a molecular weight regulator and 50 wt% of water into the step (2), and uniformly stirring to obtain a mixed solution;
(4) and (3) taking out 20% of the mixed solution in the step (3), heating the mixed solution to 60-70 ℃, adding an initiator, heating, adding the initiator, wherein the initiator releases more free radicals, so that the initiation reaction is quicker, the molecular weight distribution of the polymer is more uniform after the reaction, slowly dripping the rest 80% of the mixed solution after the mixed solution is heated to 70 ℃, controlling the polymerization temperature to be 65-70 ℃, controlling the dripping time to be 1-1.5 hours, and preserving the heat for 30-40 minutes after the polymerization is finished to obtain the water-soluble stabilizer. The step is similar to seed emulsion polymerization, and adopts a semi-continuous polymerization mode, so that on one hand, the exothermic condition of polymerization can be effectively controlled, the production operation is convenient, and the risk is reduced; on the other hand, in the reaction process, the free radicals are always in a hunger and thirsty state, and after the new monomer is added, the monomer can be quickly consumed, so that the retention and self-polymerization of the monomer are avoided, the aim of effectively controlling the molecular weight is fulfilled, and the particle size distribution of the stabilizer is uniform and the performance is stable.
The water-soluble acrylic acid stabilizer is prepared by a free radical polymerization mode, acrylic acid is taken as a main monomer of the acrylic acid monomer, methyl, ethyl ester and other groups are introduced on an acrylic acid molecular chain, ester bonds, hydrogen bonds and the like can be formed on the molecular chain by introducing the groups, the hydrophobic end of the molecular chain tends to a continuous phase of the thickener in the polymerization of introducing the acrylic acid thickener, and the hydrophilic end of the molecular chain is combined in a water-in-oil water phase in a chemical bond mode in a water-in-oil phase, so that the whole water-in-oil emulsion particle is more stable and plays a role of the stabilizer, and the storage and the service performance of the thickener after being added into the thickener are greatly improved.
Example 1
A water-soluble acrylic acid stabilizer comprises the following components in parts by weight: 10 parts of methacrylic acid, 2 parts of itaconic acid, 40 parts of acrylamide, 15 parts of 25% liquid caustic soda, 0.05 part of sodium formate, 0.5 part of potassium persulfate and 120 parts of water. It is noted that acrylamide sulfonate can also be selected as the acrylamide in the stabilizer component.
A method of preparing a water soluble acrylic stabilizer comprising the steps of:
(1) adding 60 parts of water into a reactor, adding methacrylic acid and itaconic acid, stirring uniformly, slowly adding 25% liquid caustic soda dropwise, continuously stirring, keeping the neutralization temperature at 30 ℃, and controlling the neutralization pH value at 4.5;
(2) adding acrylamide or acrylamide sulfonate into the step (1), and stirring until the acrylamide or acrylamide sulfonate is completely dissolved;
(3) adding sodium formate and 60 parts of water into the step (2) and uniformly stirring to obtain a mixed solution;
(4) and (3) taking out 20% of the mixed solution in the step (3), heating the mixed solution to 60 ℃, adding potassium persulfate, observing the heat release condition, slowly dropwise adding the remaining 80% of the mixed solution after the mixed solution is heated to the highest temperature, controlling the polymerization temperature to be 65 ℃, controlling the dropwise adding time to be 1 hour, and preserving the temperature for 30 minutes after the polymerization is finished to obtain the water-soluble stabilizer.
Example 2
A water-soluble acrylic acid stabilizer comprises the following components in parts by weight: 30 parts of methacrylic acid, 8 parts of itaconic acid, 30 parts of acrylamide, 20 parts of 25% liquid caustic soda, 0.1 part of sodium formate, 1.0 part of potassium persulfate and 140 parts of water. It is noted that acrylamide sulfonate can also be selected as the acrylamide in the stabilizer component.
A method of preparing a water soluble acrylic stabilizer comprising the steps of:
(1) adding 70 parts of water into a reactor, adding methacrylic acid and itaconic acid, stirring uniformly, slowly adding a neutralizing agent dropwise, continuously stirring, keeping the neutralizing temperature at 35 ℃, and controlling the neutralizing pH value at 5.5;
(2) adding acrylamide or acrylamide sulfonate into the step (1), and stirring until the acrylamide or acrylamide sulfonate is completely dissolved;
(3) adding sodium formate and 70 parts of water into the step (2), and uniformly stirring to obtain a mixed solution;
(4) and (3) taking out 20% of the mixed solution in the step (3), heating to 70 ℃, adding potassium persulfate, observing the heat release condition, slowly dropwise adding the remaining 80% of the mixed solution after the mixed solution is heated to the highest temperature, controlling the polymerization temperature to be 70 ℃, controlling the dropwise adding time to be 1.5 hours, and preserving the temperature for 40 minutes after the polymerization is finished to obtain the water-soluble stabilizer.
Example 3
A water-soluble acrylic acid stabilizer comprises the following components in parts by weight: 20 parts of methacrylic acid, 5 parts of itaconic acid, 35 parts of acrylamide, 17 parts of 30% liquid caustic soda, 0.07 part of sodium formate, 0.8 part of potassium persulfate and 130 parts of water. It is noted that acrylamide sulfonate can also be selected as the acrylamide in the stabilizer component.
A method of preparing a water soluble acrylic stabilizer comprising the steps of:
(1) adding 65 parts of water into a reactor, adding methacrylic acid and itaconic acid, stirring uniformly, slowly adding 30% liquid alkali dropwise, continuously stirring, keeping the neutralization temperature at 30 ℃, and controlling the neutralization pH value at 5;
(2) adding acrylamide or acrylamide sulfonate into the step (1), and stirring until the acrylamide or acrylamide sulfonate is completely dissolved;
(3) adding sodium formate and 65 parts of water into the step (2) and uniformly stirring to obtain a mixed solution;
(4) and (3) taking out 20% of the mixed solution in the step (3), heating to 65 ℃, adding potassium persulfate, observing the heat release condition, slowly dropwise adding the remaining 80% of the mixed solution after the mixed solution is heated to the highest temperature, controlling the polymerization temperature to be 67 ℃, controlling the dropwise adding time to be 1 hour, and preserving the temperature for 35 minutes after the polymerization is finished to obtain the water-soluble stabilizer.
Example 4
A water-soluble acrylic acid stabilizer comprises the following components in parts by weight: 10 parts of hydroxyethyl acrylate, 2 parts of itaconic acid, 40 parts of acrylamide, 15 parts of 25% liquid caustic soda, 0.05 part of dodecyl mercaptan, 0.5 part of potassium persulfate and 120 parts of water. It is noted that acrylamide sulfonate can also be selected as the acrylamide in the stabilizer component.
A method of preparing a water soluble acrylic stabilizer comprising the steps of:
(1) adding 60 parts of water into a reactor, adding hydroxyethyl acrylate and itaconic acid, stirring uniformly, slowly adding 25% liquid alkali dropwise, continuously stirring, keeping the neutralization temperature at 30 ℃, and controlling the neutralization pH value at 4.5;
(2) adding acrylamide or acrylamide sulfonate into the step (1), and stirring until the acrylamide or acrylamide sulfonate is completely dissolved;
(3) adding dodecyl mercaptan and 60 parts of water into the step (2) and uniformly stirring to obtain a mixed solution;
(4) and (3) taking out 20% of the mixed solution in the step (3), heating the mixed solution to 60 ℃, adding potassium persulfate, observing the heat release condition, slowly dropwise adding the remaining 80% of the mixed solution after the mixed solution is heated to the highest temperature, controlling the polymerization temperature to be 65 ℃, controlling the dropwise adding time to be 1 hour, and preserving the temperature for 30 minutes after the polymerization is finished to obtain the water-soluble stabilizer.
Example 5
A water-soluble acrylic acid stabilizer comprises the following components in parts by weight: 30 parts of hydroxyethyl acrylate, 8 parts of itaconic acid, 30 parts of acrylamide, 20 parts of 35% liquid caustic soda, 0.1 part of dodecyl mercaptan, 1.0 part of potassium persulfate and 140 parts of water. It is noted that acrylamide sulfonate can also be selected as the acrylamide in the stabilizer component.
A method of preparing a water soluble acrylic stabilizer comprising the steps of:
(1) adding 70 parts of water into a reactor, adding hydroxyethyl acrylate and itaconic acid, stirring uniformly, slowly adding 35% liquid alkali dropwise, continuously stirring, keeping the neutralization temperature at 35 ℃, and controlling the neutralization pH value at 5.5;
(2) adding acrylamide or acrylamide sulfonate into the step (1), and stirring until the acrylamide or acrylamide sulfonate is completely dissolved;
(3) adding dodecyl mercaptan and 70 parts of water into the step (2) and uniformly stirring to obtain a mixed solution;
(4) and (3) taking out 20% of the mixed solution in the step (3), heating to 70 ℃, adding potassium persulfate, observing the heat release condition, slowly dropwise adding the rest 80% of the mixed solution after the mixed solution is heated to the highest temperature, controlling the polymerization temperature to be 70 ℃, controlling the dropwise adding time to be 1.5 hours, and preserving the temperature for 40 minutes after the polymerization is finished to obtain the water-soluble stabilizer.
Example 6
A water-soluble acrylic acid stabilizer comprises the following components in parts by weight: 20 parts of hydroxyethyl acrylate, 5 parts of itaconic acid, 35 parts of acrylamide, 17 parts of 30% caustic soda liquid, 0.08 part of dodecyl mercaptan, 0.7 part of potassium persulfate and 130 parts of water. It is noted that acrylamide sulfonate can also be selected as the acrylamide in the stabilizer component.
A method of preparing a water soluble acrylic stabilizer comprising the steps of:
(1) adding 65 parts of water into a reactor, adding hydroxyethyl acrylate and itaconic acid, stirring uniformly, slowly adding 30% liquid alkali dropwise, continuously stirring, keeping the neutralization temperature at 30 ℃, and controlling the neutralization pH value at 5;
(2) adding acrylamide or acrylamide sulfonate into the step (1), and stirring until the acrylamide or acrylamide sulfonate is completely dissolved;
(3) adding dodecyl mercaptan and 65 parts of water into the step (2) and uniformly stirring to obtain a mixed solution;
(4) and (3) taking out 20% of the mixed solution in the step (3), heating to 65 ℃, adding potassium persulfate, observing the heat release condition, slowly dropwise adding the rest 80% of the mixed solution after the mixed solution is heated to the highest temperature, controlling the polymerization temperature to be 65 ℃, controlling the dropwise adding time to be 1 hour, and preserving the temperature for 35 minutes after the polymerization is finished to obtain the water-soluble stabilizer.
Comparative example 1
A water-soluble acrylic acid stabilizer comprises the following components in parts by weight: 20 parts of methacrylic acid, 5 parts of itaconic acid, 17 parts of 30% liquid alkali, 0.07 part of sodium formate, 0.8 part of potassium persulfate and 130 parts of water.
A method of preparing a water soluble acrylic stabilizer comprising the steps of:
(1) adding 65 parts of water into a reactor, adding methacrylic acid and itaconic acid, stirring uniformly, slowly adding a neutralizing agent dropwise, continuously stirring, keeping the neutralizing temperature at 30 ℃, and controlling the neutralizing pH value at 5;
(2) adding sodium formate and 65 parts of water into the step (1) and uniformly stirring to obtain a mixed solution;
(3) and (3) taking out 20% of the mixed solution in the step (2), heating to 65 ℃, adding potassium persulfate, observing the heat release condition, slowly dropwise adding the remaining 80% of the mixed solution after the mixed solution is heated to the highest temperature, controlling the polymerization temperature to be 67 ℃, controlling the dropwise adding time to be 1 hour, and preserving the temperature for 35 minutes after the polymerization is finished to obtain the water-soluble stabilizer.
Comparative example 2
A water-soluble acrylic acid stabilizer comprises the following components in parts by weight: 20 parts of methacrylic acid, 5 parts of itaconic acid, 35 parts of acrylamide, 17 parts of 30% liquid caustic soda, 0.8 part of potassium persulfate and 130 parts of water.
A method of preparing a water soluble acrylic stabilizer comprising the steps of:
(1) adding 65 parts of water into a reactor, adding methacrylic acid and itaconic acid, stirring uniformly, slowly adding 30% liquid alkali dropwise, continuously stirring, keeping the neutralization temperature at 30 ℃, and controlling the neutralization pH value at 5;
(2) adding acrylamide or acrylamide sulfonate and 65 parts of water into the step (1), and stirring until the acrylamide or acrylamide sulfonate and the 65 parts of water are completely dissolved to obtain a mixed solution;
(3) and (3) taking out 20% of the mixed solution in the step (2), heating to 65 ℃, adding potassium persulfate, observing the heat release condition, slowly dropwise adding the remaining 80% of the mixed solution after the mixed solution is heated to the highest temperature, controlling the polymerization temperature to be 67 ℃, controlling the dropwise adding time to be 1 hour, and preserving the temperature for 35 minutes after the polymerization is finished to obtain the water-soluble stabilizer.
Example 1
The experimental method comprises the following steps: the stabilizers prepared in examples 1 to 6 and comparative examples 1 to 2 were added to the thickeners, respectively, and the thickeners were prepared in the proportions shown in Table 1, and the thickeners prepared in group 8 were numbered in experimental groups 1 to 8.
Table 1: conventional acrylic thickener formulations
Experimental example 2
The experimental method comprises the following steps: the thickeners prepared in experimental groups 1 to 6 and experimental group 8 in experimental example 1 and a blank control group (namely, no stabilizer is added in the thickener formula) are tested, and the benefit of the water-soluble acrylic acid stabilizer on the thickener is judged by observing the slag discharge condition and the distillation slag discharge condition of each thickener after the stabilizer is added and polymerized. Wherein, the distillation adopts a Shenshu scientific R-201 rotary evaporator, and the distillation concentration is carried out for 4 hours at 150 ℃.
Table 2: polymerization stability and distillation stability of thickener
| Stability of polymerization | Stability of distillation | |
| Blank control group | More slag | Much slag |
| Experimental group 1 | Qualified | Basic qualification of |
| Experimental group 2 | Qualified | Qualified |
| Experimental group 3 | Qualified | Qualified |
| Experimental group 4 | Qualified | Qualified |
| Experimental group 5 | Qualified | Qualified |
| Experimental group 6 | Qualified | Qualified |
| Experimental group 8 | Qualified | Qualified |
It can be seen from the data in table 2 that, based on the same thickener formulation, the stabilizers of the present embodiment introduced into experimental groups 1-6 are better than those of the control group and experimental group 8, the molecular weight regulator of the present invention is not added into the experimental group 8, and the stabilizers prepared within the component proportion range provided by the embodiments of the present invention can greatly improve the polymerization stability and distillation stability of the thickener, the inventors control the molecular weight of the water-soluble acrylic polymer stabilizer, and by introducing sodium formate or dodecyl mercaptan as the molecular weight regulator, the molecular weight of the polymer can be controlled, so as to ensure the polymerization stabilizer effect without affecting the polymerization of the thickener.
Example 3
The experimental method comprises the following steps: the respective thickeners prepared in experimental groups 1 to 7 of experimental example 1 and the blank control group (i.e., the thickener formulation without the stabilizer added) were left to stand at room temperature for the same period of time to examine the storage stability and the use stability of the respective thickeners.
Table 3: storage stability and stability in use testing of thickeners
| Standing for 1 month | Standing for 3 months | Standing for 6 months | |
| Blank control group | Slightly delaminated and slightly precipitated | Obvious demixing and little precipitation | Large amount of separation and obvious precipitation |
| Experimental group 1 | No demixing and no precipitation | Little demixing and no precipitation | Little separation and little precipitation |
| Experimental group 2 | No demixing and no precipitation | Little demixing and no precipitation | Little separation and little precipitation |
| Experimental group 3 | No demixing and no precipitation | Little demixing and no precipitation | Little separation and little precipitation |
| Experimental group 4 | No demixing and no precipitation | Little demixing and no precipitation | Little separation and little precipitation |
| Experimental group 5 | No demixing and no precipitation | Little demixing and no precipitation | Little separation and little precipitation |
| Experimental group 6 | No demixing and no precipitation | Little demixing and no precipitation | Little separation and little precipitation |
| Experimental group 7 | Slightly delaminated without precipitation | Slight separation and slight precipitation | Obvious layering and littleMake precipitation |
As can be seen from the data in Table 3, on the basis of the same thickener formula, the stabilizer of the embodiment introduced into the experimental groups 1-6 is superior to that of the control group and the experimental group 7, the acrylamide or the acrylamide sulfonate in the invention is not added into the experimental group 7, and the storage stability and the use stability of the thickener can be greatly improved by comparing the experimental groups 1-6 with those of the control group and the experimental group 7 through the stabilizer prepared within the component proportion range provided by the embodiment of the invention. The water-soluble acrylic acid stabilizer is prepared by a free radical polymerization mode, acrylic acid is taken as a main monomer of the acrylic acid monomer, methyl, ethyl ester and other groups are introduced on an acrylic acid molecular chain, and ester bonds, hydrogen bonds and the like can be formed on the molecular chain by introducing the groups; and then the polymer is added into the polymerization of an acrylic thickener, the hydrophobic end of the polymer tends to a continuous phase and a water-in-oil phase, and the hydrophilic end is combined in the water-in-oil water phase in a chemical bond mode, so that the whole water-in-oil emulsion particle is better and more stable, plays the role of a stabilizer, and greatly improves the storage stability and the use stability.
Experimental example 4
The experimental method comprises the following steps: each thickener prepared in experimental groups 1-8 of experimental example 1 and a blank control group (i.e., no stabilizer added to the thickener formulation) were tested to examine the performance comparison of the addition of the stabilizer to the polymerization concentration and the amount of continuous phase.
Table 4: comparison of the Properties of the polymeric concentration of thickener and amount of continuous phase
| Concentration of polymerization | Continuous phase ratio | |
| Blank control group | 27％ | 30％ |
| Experimental group 1 | 35％ | 25％ |
| Experimental group 2 | 40％ | 21％ |
| Experimental group 3 | 40％ | 21％ |
| Experimental group 4 | 35％ | 25％ |
| Experimental group 5 | 40％ | 21％ |
| Experimental group 6 | 35％ | 25％ |
| Experimental group 7 | 30％ | 27％ |
| Experimental group 8 | 30％ | 27％ |
As can be seen from the data in Table 4, the stabilizers of the examples introduced into the experimental groups 1 to 6 are superior to those of the control group, the experimental group 7 and the experimental group 8 on the basis of the same thickener formulation, which indicates that the stabilizers prepared in the component proportion range provided by the examples of the present invention can greatly improve the polymer concentration of the thickener, reduce the dosage of the continuous phase, and have no influence on the product quality. Due to the improvement of the stability, the inventor reduces the use of the continuous phase solvent, improves the thickening capability of the thickening agent, reduces the use amount and reduces the transportation pressure by improving the initial concentration of polymerization in the formula design of the stabilizing agent. However, during inverse emulsion polymerization, free radical ions need to continuously penetrate through a water-in-oil interface, and the introduction of the water-soluble acrylic polymer stabilizer hinders the migration efficiency of the free radical ions, so that the quality and the performance of the thickener can be greatly improved finally.
In conclusion, the stabilizer prepared by the formula and the proportion range of the components provided by the embodiment of the invention is used for preparing the thickening agent, can improve emulsion polymerization and distillation concentration, has good storage stability and use stability, and can reduce the using amount of the continuous phase solvent of the thickening agent and reduce the distillation burden.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The water-soluble acrylic acid stabilizer is characterized by comprising the following components in parts by weight: 10-30 parts of acrylic monomer, 2-8 parts of itaconic acid, 30-40 parts of acrylamide, 15-20 parts of neutralizer, 0.05-0.1 part of molecular weight regulator, 0.5-1.0 part of initiator and 140 parts of water.
2. The water-soluble acrylic stabilizer according to claim 1, characterized by comprising the following components in parts by weight: 15-25 parts of acrylic monomer, 3-7 parts of itaconic acid, 35-40 parts of acrylamide, 16-20 parts of neutralizer, 0.06-0.1 part of molecular weight regulator, 0.6-1.0 part of initiator and 140 parts of water.
3. The water-soluble acrylic stabilizer according to claim 1 or 2, wherein the acrylic monomer is one or more of methacrylic acid, hydroxyethyl acrylate and methyl hydroxyethyl acrylate.
4. The water-soluble acrylic stabilizer according to claim 1 or 2, wherein the neutralizing agent is 25 to 35% of liquid alkali.
5. The water-soluble acrylic stabilizer according to claim 1 or 2, wherein the molecular weight regulator is one or more of sodium formate, dodecyl mercaptan, 2, 2, 4-dimethylpentanediol-1, 3-monoisobutyrate.
6. The water-soluble acrylic stabilizer according to claim 1 or 2, wherein the initiator is a persulfate system or an azo system.
7. The water-soluble acrylic stabilizer according to claim 6, wherein the initiator is one or more of potassium persulfate, ammonium persulfate and azobisisobutylimidazole hydrochloride.
8. The water-soluble acrylic stabilizer according to claim 7, wherein the initiator is potassium persulfate.
9. A method for preparing a water-soluble acrylic stabilizer according to any one of claims 1 to 8, comprising the steps of:
(1) adding 50 weight percent of water into a reactor, then adding acrylic acid monomer and itaconic acid, stirring uniformly, slowly adding a neutralizer dropwise, continuously stirring, keeping the neutralization temperature not more than 40 ℃, and controlling the neutralization pH value to be 4.5-5.5;
(2) adding acrylamide into the step (1), and stirring until the acrylamide is completely dissolved;
(3) adding a molecular weight regulator and 50 wt% of water into the step (2), and uniformly stirring to obtain a mixed solution;
(4) and (3) taking out 20% of the mixed solution in the step (3), heating the mixed solution to 60-70 ℃, adding an initiator, slowly dropwise adding the rest 80% of the mixed solution, controlling the polymerization temperature to be 65-70 ℃, controlling the dropwise adding time to be 1-1.5 hours, and after the polymerization is finished, preserving the heat for 30-40 minutes to obtain the water-soluble stabilizer.
10. The method for preparing a water-soluble acrylic stabilizer according to claim 9, wherein the remaining mixture is slowly added dropwise after the initiator is added in the step (4) and the temperature is raised to 70 ℃.
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| CN113637348A (en) * | 2021-08-26 | 2021-11-12 | 苏州弗克技术股份有限公司 | Sound-absorbing noise-reducing putty paste and preparation method thereof |
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| CN101619543A (en) * | 2009-07-27 | 2010-01-06 | 成都德美精英化工有限公司 | Thickening agent synthesized by acrylic ester and preparation method thereof |
| CN104530326A (en) * | 2014-12-30 | 2015-04-22 | 成都德美精英化工有限公司 | Synthetic method of inkjet printing thickener and thickener |
| CN106758392A (en) * | 2016-12-29 | 2017-05-31 | 四川省纺织科学研究院 | A kind of new dye stamp synthetic thickening agent and preparation method thereof, application |
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| CN101619543A (en) * | 2009-07-27 | 2010-01-06 | 成都德美精英化工有限公司 | Thickening agent synthesized by acrylic ester and preparation method thereof |
| CN104530326A (en) * | 2014-12-30 | 2015-04-22 | 成都德美精英化工有限公司 | Synthetic method of inkjet printing thickener and thickener |
| CN106758392A (en) * | 2016-12-29 | 2017-05-31 | 四川省纺织科学研究院 | A kind of new dye stamp synthetic thickening agent and preparation method thereof, application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113637348A (en) * | 2021-08-26 | 2021-11-12 | 苏州弗克技术股份有限公司 | Sound-absorbing noise-reducing putty paste and preparation method thereof |
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