CN115888852A - Preparation process of acrylate weak acid cation exchange resin - Google Patents
Preparation process of acrylate weak acid cation exchange resin Download PDFInfo
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Abstract
The invention belongs to the technical field of cation exchange resin, and particularly relates to a preparation process of acrylate weak acid cation exchange resin. The preparation process comprises the following steps: (1) polymerization: dissolving the composite dispersing agent in water at room temperature, heating, adding a methine blue solution, a composite initiator, a pore-forming agent, a reaction monomer and a cross-linking agent for reaction, then cooling, filtering, washing materials, distilling to remove the pore-forming agent, washing with water, drying and screening to obtain white balls with the particle size of 0.315-0.8 mm; (2) hydrolysis: and mixing the white balls with liquid alkali at room temperature, and heating for reaction to obtain the acrylate weak acid cation exchange resin. The acrylate weak acid cation exchange resin prepared by the invention is milky white or white in appearance, and has weak polarity and higher volume total exchange capacity; the preparation process is simple and convenient to operate and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of cation exchange resin, and particularly relates to a preparation process of acrylate weak acid cation exchange resin.
Background
At present, strong resin is generally adopted as an adsorbing material to remove low-concentration salt in water, so that the water is partially or completely desalted to meet the production and living requirements. The strong resin can be added with a regenerant after being out of service to be recovered to an initial state, and the resin can be reused almost without limit.
However, when the strong resin is regenerated, the following disadvantages are present: regeneration of cation resins with strong acids, only H + Ion action, when anion resin is regenerated with strong base, only OH - The ions perform a displacement reaction, and the rest components in the regenerant are not utilized, so that the salt content in the regenerant is doubled. And, the strong resin pair H + Ions and OH - The affinity of ions is very small, and the strong resin can be completely regenerated only by adding a regenerant which is 100-200% higher than the stoichiometric quantity, so that a large amount of acid or alkali used as chemical raw materials is consumed, and the salinization of the water environment is aggravated.
Therefore, there is a need to develop a less polar weak acid carboxyl cation resin which is more suitable for the absorption of complex organic basic salts and generates only less acidic water. In addition, the appearance of the current commercially available weak acid acrylic resin is mostly light yellow, which also greatly limits the application of the weak acid acrylic resin in the food industry and the pharmaceutical industry, and the preparation process needs to be improved to improve the appearance of the weak acid acrylic resin.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation process of the acrylate weak acid cation exchange resin is provided, the prepared cation exchange resin is milky white in appearance, has weak polarity and higher volume total exchange capacity, and is suitable for industrial production.
The preparation process of the acrylate weak acid cation exchange resin comprises the following steps:
(1) Polymerization: dissolving a composite dispersing agent in water at room temperature, heating to 50-60 ℃, adding a methine blue solution, uniformly stirring, adding a mixture of a composite initiator, a pore-forming agent, a reaction monomer and a cross-linking agent, keeping the temperature at 65-75 ℃ for 3-6h, keeping the temperature at 85-90 ℃ for 2-5h, keeping the temperature at 95-98 ℃ for 4-6h, then cooling, filtering, washing, distilling to remove the pore-forming agent, washing with water, drying, and screening to obtain white balls with the particle size of 0.315-0.8 mm;
(2) Hydrolysis: mixing the white balls and the liquid caustic soda at room temperature, heating to 90-100 ℃, preserving heat for 5-10h, then cooling to below 50 ℃, and washing with water to be neutral to obtain the acrylate weak acid cation exchange resin.
In the invention, the composite dispersant consists of a dispersant A and a dispersant B in a mass ratio of 1 (30-170); the dispersant A is one or more of gelatin, carrageenan, guar gum, hydroxyethyl cellulose and polyvinyl alcohol; the dispersant B is one or more of sodium chloride, potassium chloride, calcium chloride and ammonium chloride.
The dispersant A can reduce the surface tension of water to enable monomers to be easily dispersed into small liquid beads, and can be adsorbed on the surfaces of the liquid beads in the polymerization process to prevent the liquid beads from merging and adhering in the collision process; the dispersant B is mainly an electrolyte and is used for increasing the interfacial tension between water and the monomers, reducing the solubility of the polymerized monomers in water, further avoiding the adhesion of the monomers and simultaneously reducing the temperature of the polymerization reaction.
In the present invention, the concentration of the methine blue solution is 0.1wt.%. The methylene blue is used as a water-soluble polymerization inhibitor, so that emulsion polymerization of the monomer in a water phase can be prevented, dissolved oxygen in water can be eliminated, the induction period of polymerization reaction is shortened, the reaction process is shortened, and the yield of the monomer is improved.
In the invention, the composite initiator consists of an initiator A and an initiator B with the mass ratio of 1 (0.1-0.3); the initiator A is one or two of benzoyl peroxide and lauroyl peroxide; the initiator B is one or more of azobisisobutyronitrile, azobisisoheptonitrile and azobisisovaleronitrile.
The polymerization mechanism of the invention is free radical polymerization, according to the properties of monomers used in raw materials, the polymerization needs to be initiated at low temperature, so that the azo initiator with lower initiation temperature and the organic peroxy initiator with high stability are adopted for composite initiation, stable reaction can be carried out after the polymerization reaction releases heat and is heated, the phenomenon of implosion and the condition of polymerization termination when the reaction conversion rate is lower can not occur, the reaction is carried out at a more uniform speed, and the uniformity of a white ball structure is promoted; in addition, the two initiators can initiate the chain termination of the free radical polymerization in different ways, so that the white sphere structure can be more uniform.
In the invention, the pore-foaming agent is one or more of n-butyl alcohol, isobutyl alcohol, toluene and n-heptane.
In the invention, the reaction monomer is one or two of acrylic acid and methacrylic acid, or one or two of acrylic acid and methacrylic acid is mixed with one or more of acrylonitrile, methyl acrylate, butyl acrylate, methyl methacrylate and butyl methacrylate.
In the invention, the crosslinking agent is one or more of triallyl cyanurate, triallyl isocyanurate and divinylbenzene.
Wherein, the reaction monomer forms the skeleton of the polymer, the cross linker and the reaction monomer are copolymerized, the macromolecular chains are in a network structure which is mutually cross-linked and intertwined, the specific surface area of the copolymer is increased, and the exchange performance of the ion exchange resin is improved.
In the step (1), the dosage of each raw material is as follows by mass:
350-500 parts of water, namely,
55-115 parts of a composite dispersant,
1-2 parts of methylene blue solution,
1.5-3 parts of a composite initiator,
20-75 parts of a pore-foaming agent,
100-130 parts of a reaction monomer,
15-40 parts of a cross-linking agent.
The white spheres obtained by adopting the raw material system have uniform granularity, no irregular particles, mild polymerization reaction process and better resin index after hydrolysis.
In the step (1) of the present invention, it is preferable to wash the material with hot water of 80 ℃ or higher.
In the step (1) of the present invention, the drying is preferably performed at a temperature of 60 to 80 ℃.
In step (2) of the present invention, the liquid alkali is preferably a sodium hydroxide solution with a concentration of 10-30wt.%, and the addition amount is 4-6 times of the mass of the white balls. Ester bonds are broken under the alkaline and heating conditions to generate sodium carboxylate, and the resin is converted into H type when in use, namely weak acid cation resin containing carboxylic acid groups.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the polymerization process, the composite initiator is adopted, and the polymerization rate between monomer phases is reduced by utilizing the coordination effect of different initiators, so that the white sphere structure is more uniform;
(2) According to the invention, the electrolyte is added into the conventional dispersing agent as a composite dispersing agent, wherein the conventional dispersing agent can reduce the surface tension of water, so that a monomer can be easily dispersed into small liquid beads, and meanwhile, the dispersing agent is adsorbed on the surface of the liquid beads in the polymerization process, so that the liquid beads are prevented from merging and adhering in the collision process, the electrolyte can increase the interfacial tension between water and the monomer, the solubility of the polymerized monomer in water is reduced, and the adhesion of the monomer is further avoided;
(3) In the invention, acrylic acid or methacrylic acid monomer with carboxylic acid group is added in the polymerization process, so that the hydrolysis reaction condition is relatively mild, an organic solvent is not required to be added to promote the hydrolysis reaction, and the obtained resin body has higher volume total exchange capacity;
(4) The acrylate weak acid cation exchange resin prepared by the invention is milk white in appearance, the resin main body has higher volume total exchange capacity and higher mechanical strength, and is suitable for absorption of complex organic basic salt.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto, and modifications of the technical solutions of the present invention by those skilled in the art should be within the scope of the present invention.
The starting materials used in the examples are, unless otherwise specified, commercially available conventional starting materials; the processes used in the examples, unless otherwise specified, are conventional in the art.
Example 1
The acrylate-based weak acid cation exchange resin was prepared as follows:
(1) Polymerization: adding 500mL of water and 0.8g of hydroxyethyl cellulose into a 1000mL glass three-necked bottle at room temperature, stirring for 10min, adding 0.8g of gelatin and 55g of sodium chloride, heating to 50 ℃, adding 2mL of a 0.1wt.% methylene blue solution, uniformly stirring, adding a mixture containing 24g of divinylbenzene, 15g of triallyl cyanurate, 101g of methacrylic acid, 40g of toluene, 2g of benzoyl peroxide and 0.6g of azobisisobutyronitrile, adjusting the particle size of liquid drops to be between 0.3 and 1.0mm, keeping the temperature at 70 ℃ for 4h, keeping the temperature at 85 ℃ for 2h and keeping the temperature at 95 ℃ for 6h, then cooling, filtering, washing the material with hot water at the temperature of more than 80 ℃, distilling to remove a pore-forming agent, washing with water, drying the balls at the temperature of 80 ℃, and screening white balls with the particle size of 0.315 to 0.8 mm;
(2) Hydrolysis: at room temperature, 100g of white balls and 600mL of 10wt.% sodium hydroxide solution are added into a 1000mL glass three-necked bottle, the temperature is raised to 100 ℃, the temperature is kept for 8h, then the temperature is lowered to below 50 ℃, and the mixture is washed to be neutral, so that the acrylate weak acid cation exchange resin is obtained and is milk white.
Example 2
The acrylate-based weak acid cation exchange resin was prepared as follows:
(1) Polymerization: adding 500mL of water and 1.0g of polyvinyl alcohol into a 1000mL glass three-necked bottle at room temperature, stirring for 10min, adding 0.5g of guar gum and 75g of potassium chloride, heating to 50 ℃, adding 2mL of a methylene blue solution with the concentration of 0.1 wt%, uniformly stirring, adding a mixture containing 22.6g of divinylbenzene, 8g of acrylonitrile, 100.4g of methacrylic acid, 20g of n-butyl alcohol, 2.4g of benzoyl peroxide and 0.3g of azobisisoheptonitrile, adjusting the particle size of liquid drops to be between 0.3 and 1.0mm, keeping the temperature at 65 ℃ for 3h, keeping the temperature at 85 ℃ for 3h, keeping the temperature at 95 ℃ for 6h, then cooling, filtering, washing the material with hot water at the temperature of more than 80 ℃, distilling to remove a pore-forming agent, washing with water, drying the balls at the temperature of 60 ℃, and screening white balls with the particle size of 0.315-0.8 mm;
(2) Hydrolysis: at room temperature, 100g of white balls and 500mL of 20wt.% sodium hydroxide solution are added into a 1000mL glass three-necked bottle, the temperature is increased to 90 ℃, the temperature is kept for 10h, then the temperature is reduced to below 50 ℃, and the mixture is washed to be neutral, so that the acrylate weak acid cation exchange resin is obtained and is milk white.
Example 3
The acrylate-based weak acid cation exchange resin was prepared as follows:
(1) Polymerization: adding 400mL of water and 1.2g of hydroxyethyl cellulose into a 1000mL glass three-necked bottle at room temperature, stirring for 10min, adding 80g of calcium chloride, heating to 50 ℃, adding 1.5mL of 0.1wt.% methylene blue solution, uniformly stirring, adding a mixture containing 20g of divinylbenzene, 3.2g of triallyl cyanurate, 7g of acrylic acid, 100g of methyl acrylate, 10g of methyl methacrylate, 25g of isobutanol, 2.5g of lauroyl peroxide and 0.4g of azobisisovaleronitrile, adjusting the particle size of liquid drops to be 0.3-1.0mm, preserving heat at 67 ℃ for 4h, preserving heat at 88 ℃ for 4h, preserving heat at 97 ℃ for 4h, cooling, filtering, washing the material with hot water at the temperature of more than 80 ℃, distilling to remove a pore-forming agent, washing with water, drying balls at the temperature of 60 ℃, and screening white balls with the particle size of 0.315-0.8 mm;
(2) Hydrolysis: at room temperature, 100g of white balls and 500mL of 20wt.% sodium hydroxide solution are added into a 1000mL glass three-necked bottle, the temperature is raised to 95 ℃, the temperature is kept for 8h, then the temperature is lowered to below 50 ℃, and the mixture is washed to be neutral, so that the acrylate weak acid cation exchange resin is obtained and is milk white.
Example 4
The acrylate-based weak acid cation exchange resin was prepared as follows:
(1) Polymerization: adding 360mL of water and 0.6g of hydroxyethyl cellulose into a 1000mL glass three-necked bottle at room temperature, stirring for 10min, adding 100g of ammonium chloride, heating to 55 ℃, adding 1mL of a 0.1wt.% methylene blue solution, uniformly stirring, adding a mixture containing 15g of divinylbenzene, 5g of triallyl isocyanurate, 10g of acrylic acid, 103g of methyl acrylate, 15g of n-heptane, 20g of toluene, 2.5g of benzoyl peroxide and 0.5g of azobisisobutyronitrile, adjusting the particle size of liquid drops to be between 0.3 and 1.0mm, keeping the temperature at 67 ℃ for 3h, keeping temperature at 85 ℃ for 3h, keeping temperature at 98 ℃ for 4h, then cooling, filtering, washing the material with hot water at the temperature of more than 80 ℃, distilling to remove a pore-forming agent, washing with water, drying the ball at the temperature of 60 ℃, and screening white balls with the particle size of 0.315 to 0.8 mm;
(2) Hydrolysis: at room temperature, 100g of white balls and 400mL of 30wt.% sodium hydroxide solution are added into a 1000mL glass three-necked bottle, the temperature is raised to 100 ℃, the temperature is kept for 10h, then the temperature is lowered to below 50 ℃, and the mixture is washed to be neutral, so that the acrylate weak acid cation exchange resin is obtained and is milk white.
Example 5
The acrylate-based weak acid cation exchange resin was prepared as follows:
(1) Polymerization: at room temperature, adding 350mL of water and 0.63g of hydroxyethyl cellulose into a 1000mL glass three-necked bottle, stirring for 10min, adding 90g of sodium chloride, heating to 55 ℃, adding 1mL of a 0.1wt.% methine blue solution, uniformly stirring, adding a mixture containing 18g of divinylbenzene, 45g of acrylic acid, 14g of methyl acrylate, 63g of methyl methacrylate, 30g of n-heptane, 40g of toluene, 2.0g of lauroyl peroxide and 0.5g of azobisisobutyronitrile, regulating a speed regulator to be 250r/min, regulating the particle size of liquid drops to be 0.3-1.0mm, keeping the temperature at 65 ℃ for 6h, keeping the temperature at 85 ℃ for 5h, keeping the temperature at 98 ℃ for 5h, then cooling, filtering, washing the material with hot water at the temperature of more than 80 ℃, distilling off a pore-forming agent, washing, drying the ball at the temperature of 60 ℃, and screening white balls with the particle size of 0.315-0.8 mm;
(2) Hydrolysis: at room temperature, 100g of white balls and 400mL of 30wt.% sodium hydroxide solution are added into a 1000mL glass three-necked bottle, the temperature is raised to 100 ℃, the temperature is kept for 10h, then the temperature is lowered to below 50 ℃, and the mixture is washed to be neutral, so that the acrylate weak acid cation exchange resin is obtained and is milk white.
Example 6
The acrylate-based weak acid cation exchange resin was prepared as follows:
(1) Polymerization: adding 350mL of water and 1.2g of hydroxyethyl cellulose into a 1000mL glass three-necked bottle at room temperature, stirring for 10min, adding 110g of calcium chloride, heating to 60 ℃, adding a mixture of 1mL of 0.1wt.% methylene blue solution, uniformly stirring, adding a liquid drop with the particle size of 0.3-1.0mm, keeping the temperature at 75 ℃ for 5h, keeping the temperature at 90 ℃ for 2h, keeping the temperature at 98 ℃ for 5h, then cooling, filtering, washing the material with hot water at more than 80 ℃, distilling to remove a pore-forming agent, washing with water, drying the ball at 60 ℃, and screening white balls with the particle size of 0.315-0.8 mm;
(2) Hydrolysis: at room temperature, 100g of white balls and 400mL of 30wt.% sodium hydroxide solution are added into a 1000mL glass three-necked bottle, the temperature is raised to 100 ℃, the temperature is kept for 10h, then the temperature is lowered to below 50 ℃, and the mixture is washed to be neutral, so that the acrylate weak acid cation exchange resin is obtained and is milk white.
Comparative example 1
This comparative example examines the effect of a single dispersant on the product properties and compared to example 1, differs only in that no sodium chloride is added, as follows:
polymerization: at room temperature, 500mL of water and 0.8g of hydroxyethyl cellulose are added into a 1000mL glass three-necked bottle, the mixture is stirred for 10min, 0.8g of gelatin is added, the temperature is raised to 50 ℃, 2mL of methylene blue solution with the concentration of 0.1wt.% is added, after the mixture is uniformly stirred, a mixture containing 24g of divinylbenzene, 15g of triallyl cyanurate, 101g of methyl acrylate, 40g of toluene, 2g of benzoyl peroxide and 0.6g of azobisisobutyronitrile is added, a speed regulator is used for 180r/min, the particle size of liquid drops is adjusted to be 0.3-1.0mm, the temperature is kept at 70 ℃ for 4h and 85 ℃ for 2h, a severe adhesion phenomenon occurs in the temperature keeping process at 85 ℃, polymer white balls with proper particle size are not obtained, and the next hydrolysis process cannot be carried out.
Comparative example 2
This comparative example examines the effect of a single initiator on the product properties and compared to example 3, differs only in that no azobisisovaleronitrile is added, by the following steps:
(1) Polymerization: adding 400mL of water and 1.2g of hydroxyethyl cellulose into a 1000mL glass three-necked bottle at room temperature, stirring for 10min, adding 80g of calcium chloride, heating to 50 ℃, adding 1.5mL of methylene blue solution with the concentration of 0.1 wt%, uniformly stirring, adding a mixture containing 20g of divinylbenzene, 3.2g of triallyl cyanurate, 7g of acrylic acid, 100g of methyl acrylate, 10g of methyl methacrylate, 25g of isobutanol and 2.5g of lauroyl peroxide, adjusting the particle size of liquid drops to be between 0.3 and 1.0mm, keeping the temperature at 67 ℃ for 4h, keeping the temperature at 88 ℃ for 4h and keeping the temperature at 97 ℃ for 4h, then cooling, filtering, washing the material with hot water at the temperature of more than 80 ℃, distilling to remove a pore-forming agent, washing with water, drying the balls at the temperature of 60 ℃, and screening white balls with the particle size of 0.315 to 0.8 mm;
(2) Hydrolysis: at room temperature, 100g of white balls and 500mL of 20wt.% sodium hydroxide solution are added into a 1000mL glass three-necked bottle, the temperature is raised to 95 ℃, the temperature is kept for 8h, then the temperature is lowered to below 50 ℃, and the mixture is washed to be neutral, so that the acrylate weak acid cation exchange resin is obtained and is light yellow.
Comparative example 3
This comparative example examines the effect of the polymerized monomers on the product properties and compared to example 5, differs only in that acrylic acid is replaced by equal mass of methyl acrylate, as follows:
(1) Polymerization: at room temperature, adding 350mL of water and 0.63g of hydroxyethyl cellulose into a 1000mL glass three-necked bottle, stirring for 10min, adding 90g of sodium chloride, heating to 55 ℃, adding a mixture of 1mL of 0.1wt.% methylene blue solution, uniformly stirring, adding a liquid drop with the particle size of 0.3-1.0mm, keeping the temperature at 65 ℃ for 6h, keeping the temperature at 85 ℃ for 5h, keeping the temperature at 98 ℃ for 5h, then cooling, filtering, washing the material with hot water at more than 80 ℃, distilling to remove a pore-forming agent, washing with water, drying the ball at 60 ℃, and screening white balls with the particle size of 0.315-0.8 mm;
(2) Hydrolysis: at room temperature, 100g of white balls and 400mL of 30wt.% sodium hydroxide solution are added into a 1000mL glass three-necked bottle, the temperature is raised to 100 ℃, the temperature is kept for 10h, then the temperature is lowered to below 50 ℃, and the mixture is washed to be neutral, so that the acrylate weak acid cation exchange resin is obtained and is milk white.
Comparative example 4
This comparative example examines the effect of the polymerized monomers and hydrolysis process on the product properties and compared to example 5, it is only different in that acrylic acid is replaced by equal mass of methyl acrylate and methanol is added in the hydrolysis process, as follows:
(1) Polymerization: at room temperature, adding 350mL of water and 0.63g of hydroxyethyl cellulose into a 1000mL glass three-necked bottle, stirring for 10min, adding 90g of sodium chloride, heating to 55 ℃, adding 1mL of a 0.1wt.% methine blue solution, uniformly stirring, adding a mixture containing 18g of divinylbenzene, 59g of methyl acrylate, 63g of methyl methacrylate, 30g of n-heptane, 40g of toluene, 2.0g of lauroyl peroxide and 0.5g of azobisisobutyronitrile, regulating a speed regulator to be 250r/min, regulating the particle size of liquid drops to be between 0.3 and 1.0mm, keeping the temperature at 65 ℃ for 6h, keeping the temperature at 85 ℃ for 5h, keeping the temperature at 98 ℃ for 5h, then cooling, filtering, washing the material with hot water at more than 80 ℃, distilling to remove a pore-forming agent, washing with water, drying the balls at 60 ℃, and screening white balls with the particle size of 0.315-0.8 mm;
(2) Hydrolysis: at room temperature, 100g of white balls, 50mL of methanol and 400mL of 30wt.% sodium hydroxide solution are added into a 1000mL glass three-necked bottle, a reflux device is installed on the bottle, the temperature is slowly increased to 95 ℃, the temperature is kept for 10h, then the temperature is increased to 150 ℃, the temperature is kept for 12h, then the temperature is reduced to below 50 ℃, and the solution is washed to be neutral, so that the acrylate weak acid cation exchange resin is obtained and is milky.
The acrylate weak acid cation exchange resins prepared in the examples and comparative examples are subjected to performance tests, wherein the water content is tested according to the standard GB/T5757-2008, the mass total exchange capacity and the volume total exchange capacity are tested according to the standard GB/T8144-2008, the osmosizing is tested according to the standard GB/T12598-2001, the wet vision is tested according to the standard GB/T8331-2008, the wet true is tested according to the standard GB/T8330-2008, and the transformation expansion rate is tested according to the standard GB/T11991-2008. The test results are shown in table 1.
Table 1 results of performance testing
As can be seen from the preparation processes of the examples and the comparative examples and the table 1, the acrylate ester weak acid cation exchange resin prepared by adopting the composite dispersant, the composite initiator and the acrylic acid and/or methacrylic acid polymerization monomer with carboxylic acid groups has milky appearance, high volume full exchange capacity of the resin main body and moderate transformation expansion rate, and is suitable for absorbing complex organic basic salt. Comparative example 1 adopts a single dispersant, a serious adhesion phenomenon is easy to occur in the heat preservation process, polymer white balls with proper granularity are not obtained, and the next hydrolysis process cannot be carried out; comparative example 2 adopts a single initiator, the uniformity of the white ball structure obtained by the polymerization process is poor, the infiltration and grinding round ball rate is far lower than that of examples 1-6, and the volume total exchange capacity of the resin main body is also low; the polymeric monomers of comparative examples 3-4, in which no acrylic acid and/or methacrylic acid polymeric monomer with carboxylic acid group is added, have a reduced volumetric total exchange capacity of the resin bulk, and in which comparative example 4, in which an organic solvent is added in the hydrolysis process, although its attrition sphericity is higher, will result in a further reduction in volumetric total exchange capacity of the resin bulk.
Claims (9)
1. A preparation process of acrylate weak acid cation exchange resin is characterized by comprising the following steps: the method comprises the following steps:
(1) Polymerization: dissolving a composite dispersing agent in water at room temperature, heating to 50-60 ℃, adding a methine blue solution, uniformly stirring, adding a mixture of a composite initiator, a pore-forming agent, a reaction monomer and a cross-linking agent, keeping the temperature at 65-75 ℃ for 3-6h, keeping the temperature at 85-90 ℃ for 2-5h, keeping the temperature at 95-98 ℃ for 4-6h, then cooling, filtering, washing, distilling to remove the pore-forming agent, washing with water, drying, and screening to obtain white balls with the particle size of 0.315-0.8 mm;
(2) Hydrolysis: mixing the white balls and the liquid caustic soda at room temperature, heating to 90-100 ℃, preserving heat for 5-10h, then cooling to below 50 ℃, and washing with water to be neutral to obtain the acrylate weak acid cation exchange resin.
2. The process for preparing an acrylate-based weak acid cation exchange resin according to claim 1, wherein: the composite dispersant consists of a dispersant A and a dispersant B in a mass ratio of 1 (30-170); the dispersant A is one or more of gelatin, carrageenan, guar gum, hydroxyethyl cellulose and polyvinyl alcohol; the dispersant B is one or more of sodium chloride, potassium chloride, calcium chloride and ammonium chloride.
3. The process according to claim 1, wherein the acrylic ester weak acid cation exchange resin comprises: the concentration of the methylene blue solution was 0.1wt.%.
4. The process according to claim 1, wherein the acrylic ester weak acid cation exchange resin comprises: the composite initiator consists of an initiator A and an initiator B with the mass ratio of 1 (0.1-0.3); the initiator A is one or two of benzoyl peroxide and lauroyl peroxide; the initiator B is one or more of azobisisobutyronitrile, azobisisoheptonitrile and azobisisovaleronitrile.
5. The process for preparing an acrylate-based weak acid cation exchange resin according to claim 1, wherein: the pore-foaming agent is one or more of n-butyl alcohol, isobutyl alcohol, toluene and n-heptane.
6. The process according to claim 1, wherein the acrylic ester weak acid cation exchange resin comprises: the reaction monomer is one or two of acrylic acid and methacrylic acid, or one or two of acrylic acid and methacrylic acid and one or more of acrylonitrile, methyl acrylate, butyl acrylate, methyl methacrylate and butyl methacrylate.
7. The process according to claim 1, wherein the acrylic ester weak acid cation exchange resin comprises: the cross-linking agent is one or more of triallyl cyanurate, triallyl isocyanurate and divinylbenzene.
8. The process according to claim 1, wherein the acrylic ester weak acid cation exchange resin comprises: in the step (1), the dosage of each raw material is as follows by mass:
350-500 parts of water, namely,
55-115 parts of a composite dispersant,
1-2 parts of methylene blue solution,
1.5 to 3 portions of composite initiator,
20-75 parts of a pore-foaming agent,
100-130 parts of a reaction monomer,
15-40 parts of a cross-linking agent.
9. The process according to claim 1, wherein the acrylic ester weak acid cation exchange resin comprises: in the step (2), the liquid alkali is a sodium hydroxide solution with the concentration of 10-30wt.%, and the addition amount is 4-6 times of the mass of the white balls.
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| CN117024654A (en) * | 2023-09-05 | 2023-11-10 | 河北利江生物科技有限公司 | Synthesis method of low-conversion-expansion-rate acrylic weak-acid cation exchange resin |
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| CN105884967A (en) * | 2015-08-26 | 2016-08-24 | 同济大学 | Contamination-resistant large-capacity macroporous weak-acid resin synthesis method |
| CN107814862A (en) * | 2017-11-14 | 2018-03-20 | 李博 | A kind of Macroporous weak acid cation exchange resin suitable for one-step method |
| CN108219087A (en) * | 2018-01-12 | 2018-06-29 | 南京大学 | A kind of acidproof high mechanical properties weak acid cation exchange microballoon resin of magnetic acrylic acid series and preparation method thereof |
| CN113058661A (en) * | 2021-02-25 | 2021-07-02 | 宁波争光树脂有限公司 | Preparation method of macroporous acrylic acid weak acid cation exchange resin |
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2023
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| CN102190753A (en) * | 2010-03-19 | 2011-09-21 | 周家付 | Preparation method for macroporous weak-acidic cation exchange resin |
| CN103951780A (en) * | 2014-05-13 | 2014-07-30 | 安徽三星树脂科技有限公司 | Preparation method of macroporous weak-acidity cation exchange resin |
| CN105884967A (en) * | 2015-08-26 | 2016-08-24 | 同济大学 | Contamination-resistant large-capacity macroporous weak-acid resin synthesis method |
| CN107814862A (en) * | 2017-11-14 | 2018-03-20 | 李博 | A kind of Macroporous weak acid cation exchange resin suitable for one-step method |
| CN108219087A (en) * | 2018-01-12 | 2018-06-29 | 南京大学 | A kind of acidproof high mechanical properties weak acid cation exchange microballoon resin of magnetic acrylic acid series and preparation method thereof |
| CN113058661A (en) * | 2021-02-25 | 2021-07-02 | 宁波争光树脂有限公司 | Preparation method of macroporous acrylic acid weak acid cation exchange resin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117024654A (en) * | 2023-09-05 | 2023-11-10 | 河北利江生物科技有限公司 | Synthesis method of low-conversion-expansion-rate acrylic weak-acid cation exchange resin |
| CN117024654B (en) * | 2023-09-05 | 2024-05-28 | 河北利江生物科技有限公司 | Synthesis method of low-conversion-expansion-rate acrylic weak-acid cation exchange resin |
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