CN109833854B - Macroporous adsorption resin and preparation method thereof - Google Patents
Macroporous adsorption resin and preparation method thereof Download PDFInfo
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Abstract
The invention provides a macroporous adsorption resin which is prepared from the following raw materials: water, gelatin, styrene, divinylbenzene, white oil, an initiator, a pore-foaming agent, solvent oil, 1, 2-dichloroethane, zinc chloride and chloromethyl ether. The wax-free polyurethane foam is prepared by the steps of white ball polymerization, white ball drying and screening, wax extraction, wax ball drying and screening, chlorination, chlorine ball drying and post-crosslinking reaction. The prepared resin has large specific surface area and porosity, good mechanical strength, high temperature resistance, simple preparation process and easy industrial production.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to macroporous adsorption resin and a preparation method thereof.
Background
The adsorption resin refers to a high molecular polymer, and can be used for removing organic matters in wastewater, decoloring sugar liquor, separating and refining natural products and biochemical products and the like. The adsorption resin has a plurality of varieties, and the change of the monomer and the change of the functional group on the monomer can endow the resin with various special properties. High molecular weight polymers such as polystyrene resins and polyacrylate resins are commonly used. The adsorption resin is a resin adsorbent which has the characteristic of adsorption and has a porous three-dimensional structure. It is a new porous resin developed in the field of polymer in recent years, and is made up by using monomers of styrene and divinylbenzene, etc. and adopting suspension copolymerization process in the presence of organic solvent of toluene, etc. It is widely used for wastewater treatment, medicament separation and purification, as a carrier of chemical reaction catalysts, and as a filler of molecular weight fractionation columns of gas chromatography and gel permeation chromatography. Its advantages are easy regeneration and repeated use.
The adsorption resin is manufactured by a plurality of manufacturers and a plurality of varieties at home and abroad. With the increasing demands of China on the types and the quantity of the products, more and more manufacturers improve the products.
Chinese patent CN101070400A discloses a preparation method of imidazole modified styrene macroporous adsorption resin, and provides a preparation method of imidazole modified styrene macroporous adsorption resin. The preparation method comprises two steps, firstly, the salt forming reaction of imidazole is carried out, a specific functional group is introduced on the 1 position to realize the functionalization of imidazole, and then the imidazole is reacted with the styrene type macroporous adsorption resin which has been subjected to chlorination reaction to realize the imidazole modification of the styrene type macroporous adsorption resin. The invention introduces the functionalized imidazole ions into the styrene type macroporous adsorption resin, and utilizes the unique physical and chemical properties of the imidazole ions and the controllability of the physicochemical properties of the imidazole ions, thereby not only increasing the polarity and the hydrophilicity of the resin, but also widening the separation and purification range of the styrene type macroporous adsorption resin in the fields of food, medicine and the like. However, the product of the invention is small in pore size, and is difficult to achieve effective adsorption on some separation and purification objects with large molecular weight, so that the application of the product is limited.
Chinese patent application CN107163176A discloses a preparation method of macroporous adsorption resin, which is characterized by comprising the following steps: preparing a monomer: putting the diethylbenzene, the methyl acrylate and the dibenzoyl peroxide into a reaction kettle according to the formula, stirring for 25-30 minutes at room temperature, putting the pore-foaming agent cyclohexane, stirring for 25-30 minutes at room temperature, and preparing a water phase: adding a proper amount of water into a reaction kettle, then adding the powdery salt, and stirring to make the salt water uniform. Adding gelatin and methylene blue, stirring, heating to 55-60 deg.C, turning off stirring, pumping the prepared monomer into reaction kettle, stirring for 10-15 min without heating, wherein the water phase is 55-60 deg.C at first, and the temperature in the reaction kettle is 40-45 deg.C after adding monomer. After stirring for 10-15 minutes, slowly heating to 68-70 ℃. Starting heat preservation timing, after preserving heat for 4-5 hours, heating by steam to 70-75 ℃, preserving heat for 6-7 hours, and keeping stirring. However, the invention has small specific surface area and small pore volume, so the adsorption capacity is low.
Chinese patent application CN102190751A discloses a method for preparing a medium-polarity macroporous adsorbent resin. Taking 1-50 parts of styrene, 2-10 parts of hydroxyethyl acrylate and 50-100 parts of divinylbenzene with the weight percentage of 80% as monomers according to the weight ratio; taking toluene accounting for 50-200 percent of the total weight of the monomers and carbon alcohol accounting for 33-135 percent of the total weight of the monomers as mixed pore-foaming agents, taking benzoyl peroxide accounting for 0.1-2 percent of the total weight of the monomers and azobisisobutyronitrile accounting for 0.1-2 percent of the total weight of the monomers as initiators, and mixing to obtain an oil phase; dissolving 0.2-1 part of polyvinyl alcohol, 0.5-1 part of gelatin and 5-10 parts of sodium chloride in 100 parts of deionized water according to the weight ratio to prepare a water phase; adding the oil phase into the water phase, heating, reacting, filtering, extracting with acetone, leaching with ethanol until the washing liquid is clear; obtaining the macroporous cation resin. The method solves the problem of low purity of the extract obtained by the traditional resin extraction and separation method, but has small porosity and poor mechanical strength, and limits the development and application of the extract in the industry.
At present, no macroporous adsorption resin exists, the specific surface area and the porosity are large, the mechanical strength is good, the high temperature resistance is high, the preparation process is simple, and the industrial production is easy to realize.
Disclosure of Invention
In order to solve the problems, the invention provides a macroporous adsorption resin which is prepared from the following raw materials: water, gelatin, styrene, divinylbenzene, white oil, an initiator, a pore-foaming agent, solvent oil, 1, 2-dichloroethane, zinc chloride and chloromethyl ether.
Further, the initiator is azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide and cyclohexanone peroxide; the pore-foaming agent is toluene.
Further, the resin comprises, by weight, 300 parts of water, 5-10 parts of gelatin, 10-20 parts of styrene, 20-50 parts of divinylbenzene, 10-30 parts of white oil, 2-5 parts of an initiator, 2-5 parts of a pore-foaming agent, 50-100 parts of solvent oil, 5-10 parts of 1, 2-dichloroethane, 5-10 parts of zinc chloride and 200 parts of 150-part of chloromethyl ether.
The invention also provides a preparation method of the macroporous adsorption resin, which comprises the following steps:
(1) white ball polymerization: heating water, adding gelatin, stirring, adding styrene, divinylbenzene, white oil, pore-forming agent and initiator, heating for shaping, keeping the temperature after shaping, heating again, keeping the temperature for the second time, and washing to obtain white balls;
(2) drying and screening white balls: drying the white balls until the weight loss rate is less than 8.0%, and sieving to obtain qualified white balls;
(3) wax extraction: adding qualified white balls into solvent oil, stirring, heating, keeping the temperature, pumping out the solvent oil, repeating the above operations for 5-6 times, and washing to obtain wax balls;
(4) drying and screening wax balls: drying the wax balls until the weight loss rate is not more than 3%, and sieving to obtain qualified wax balls;
(5) chlorination: adding qualified wax balls into chloromethyl ether, heating, preserving heat, cooling, adding zinc chloride twice, then heating for the second time, preserving heat for the second time, cooling for the second time, performing solid-liquid separation, and washing a solid phase to obtain chlorine balls;
(6) drying the chlorine balls: drying the chlorine ball with the weight loss rate of 1.5-9.5% to obtain the qualified chlorine ball;
(7) post-crosslinking reaction: mixing 1, 2-dichloroethane with qualified chlorine balls, stirring, heating, keeping the temperature, adding zinc chloride, heating for the second time, keeping the temperature for the second time, heating for the third time, keeping the temperature for the third time, cooling to obtain finished balls, performing solid-liquid separation on the finished balls and the 1, 2-dichloroethane, washing the finished balls, and filtering to obtain the macroporous adsorption resin.
Further, in the step (1), water is heated to 50-60 ℃; heating to 70-85 deg.C; the temperature is raised for the second time to 85-92 ℃.
Further, in the step (1), gelatin is added and stirred for 1-2 h.
Further, in the step (1), after shaping, the temperature is kept for 2-3h, the temperature is kept for 6-9h for the second time, and the mixture is washed by water at 60 ℃.
Further, in the step (1), the washing is performed 5 times with water at 60 ℃.
Further, in the step (2), the drying temperature is not higher than 80 ℃, and white balls with the grain size of 0.5mm-1.0mm are obtained by sieving.
Further, in the step (3), the temperature is raised to 35-60 ℃, the temperature is kept for 0.5-2h, and the solvent oil is No. 120 solvent oil.
Further, in the step (4), the drying temperature is not higher than 80 ℃, and white balls with the grain size of 0.5mm-1.0mm are obtained by sieving.
Further, in the step (5), adding qualified wax balls into chloromethyl ether, heating to 30-40 ℃, preserving heat for 2-5h, cooling to below 30 ℃, adding zinc chloride twice, then heating to 35-45 ℃ for the second time, preserving heat for 60-100h, cooling to below 30 ℃ for the second time, carrying out solid-liquid separation, and washing the solid phase with ethanol for 5 times to obtain the chlorine balls.
Further, in the step (6), the drying temperature is 80-90 ℃.
Further, in the step (7), the temperature is raised to 35-50 ℃, and the temperature is kept for 2-5 h; heating to 85-100 ℃ for the second time, and preserving heat for 0.2-2h for the second time; the temperature is raised to 105-150 ℃ for the third time, and the temperature is kept for 8-20h for the third time.
Further, in the step (7), the temperature is reduced to below 40 ℃.
Further, in the step (7), the washing process comprises washing with ethanol for 5 times, and then washing with water for 5 times.
Further, the amount of zinc chloride added in the step (5) and the step (7) is the same.
The principle of the white ball reaction is as follows:
the invention has the advantages that: the macroporous adsorption resin produced by the invention creatively determines the preparation raw materials and the proportion thereof, and the obtained product has larger specific surface area and porosity, better mechanical strength and high temperature resistance through reasonable temperature rise and reduction procedures, and the preparation process is simple and easy for industrial production.
Detailed Description
The invention will be further described with reference to specific embodiments, the advantages and features of which will become apparent from the description, but which are given by way of illustration only and are not intended to limit the scope of the invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Example 1
The raw materials comprise: 200 parts of water, 10 parts of gelatin, 10 parts of styrene, 50 parts of divinylbenzene, 10 parts of white oil, 5 parts of azobisisobutyronitrile, 2 parts of toluene, 100 parts of No. 120 solvent oil, 5 parts of 1, 2-dichloroethane, 10 parts of zinc chloride and 150 parts of chloromethyl ether.
The preparation method comprises the following steps:
(1) white ball polymerization: heating water to 50 ℃, adding gelatin, stirring for 1h, adding styrene, divinylbenzene, white oil, toluene and azodiisobutyronitrile, heating to 70 ℃, shaping, then preserving heat for 2h, then heating to 85 ℃ for the second time, preserving heat for 6h for the second time, washing with 60 ℃ water for 5 times after heat preservation, and obtaining white balls;
(2) drying and screening white balls: drying the white balls at a drying temperature of not more than 80 ℃ until the weight loss rate is less than 8.0%, and sieving the dried white balls to obtain white balls with the particle size of 0.5-1.0 mm, thereby obtaining qualified white balls;
(3) wax extraction: adding qualified white balls into No. 120 solvent oil, stirring, heating to 35 deg.C, maintaining the temperature for 0.5h, removing solvent oil, repeating the above operation for 6 times, and washing with water to obtain wax balls;
(4) drying and screening wax balls: drying the wax balls at a drying temperature of no more than 80 ℃ until the weight loss rate is no more than 3%, and sieving the dried wax balls to obtain wax balls with the particle size of 0.5mm-1.0mm, thereby obtaining qualified wax balls;
(5) chlorination: adding qualified wax balls into chloromethyl ether, heating to 30 ℃, preserving heat for 2 hours, cooling to below 30 ℃, adding 5 parts of zinc chloride twice, then heating to 35 ℃, preserving heat for 60 hours, cooling to below 30 ℃, carrying out solid-liquid separation, and washing a solid phase with ethanol for 5 times to obtain chlorine balls;
(6) drying the chlorine balls: drying the chlorine ball at the drying temperature of 80 ℃ and the weight loss rate of 1.5-9.5 percent to obtain the qualified chlorine ball;
(7) post-crosslinking reaction: mixing 1, 2-dichloroethane with qualified chlorine balls, stirring, heating to 35 ℃, keeping the temperature for 2 hours, adding 5 parts of zinc chloride, heating to 85 ℃ for the second time, keeping the temperature for 0.2 hour for the second time, heating to 105 ℃ for the third time, keeping the temperature for 8 hours for the third time, cooling to 40 ℃ to obtain finished balls, performing solid-liquid separation on the finished balls and the 1, 2-dichloroethane, washing the finished balls by using ethanol, washing for five times by using deionized water, and draining to obtain the macroporous adsorption resin.
Example 2
The raw materials comprise: 300 parts of water, 5 parts of gelatin, 20 parts of styrene, 20 parts of divinylbenzene, 10 parts of white oil, 2 parts of initiator, 5 parts of pore-foaming agent, 50 parts of solvent oil, 10 parts of 1, 2-dichloroethane, 5 parts of zinc chloride and 200 parts of chloromethyl ether.
The preparation method comprises the following steps:
(1) white ball polymerization: heating water to 60 ℃, adding gelatin, stirring for 2h, adding styrene, divinylbenzene, white oil, toluene and azodiisovaleronitrile, heating to 85 ℃, shaping, then preserving heat for 3h, heating to 92 ℃ for the second time, preserving heat for 9h, washing with 60 ℃ water for 6 times after heat preservation, and obtaining white balls;
(2) drying and screening white balls: drying the white balls at a drying temperature of not more than 80 ℃ until the weight loss rate is less than 8.0%, and sieving the dried white balls to obtain white balls with the particle size of 0.5-1.0 mm, thereby obtaining qualified white balls;
(3) wax extraction: adding qualified white balls into No. 120 solvent oil, stirring, heating to 60 ℃, keeping the temperature for 2h, pumping out the solvent oil, repeating the operation for 6 times, and washing to obtain wax balls;
(4) drying and screening wax balls: drying the wax balls at a drying temperature of no more than 80 ℃ until the weight loss rate is no more than 3%, and sieving the dried wax balls to obtain wax balls with the particle size of 0.5mm-1.0mm, thereby obtaining qualified wax balls;
(5) chlorination: adding qualified wax balls into chloromethyl ether, heating to 40 ℃, preserving heat for 5 hours, cooling to below 30 ℃, adding 2.5 parts of zinc chloride twice, then heating to 45 ℃, preserving heat for 100 hours, cooling to below 30 ℃, carrying out solid-liquid separation, and washing a solid phase with ethanol for 5 times to obtain chlorine balls;
(6) drying the chlorine balls: drying the chlorine ball at the drying temperature of 80 ℃ and the weight loss rate of 1.5-9.5 percent to obtain the qualified chlorine ball;
(7) post-crosslinking reaction: mixing 1, 2-dichloroethane with qualified chlorine balls, stirring, heating to 50 ℃, preserving heat for 5 hours, adding 2.5 parts of zinc chloride, heating to 100 ℃ for the second time, preserving heat for 2 hours for the second time, heating to 150 ℃ for the third time, preserving heat for 20 hours for the third time, cooling to 40 ℃ to obtain finished balls, performing solid-liquid separation on the finished balls and the 1, 2-dichloroethane, washing the finished balls by using ethanol, washing for five times by using deionized water, and draining to obtain the macroporous adsorption resin.
Example 3
The raw materials comprise: 250 parts of water, 8 parts of gelatin, 15 parts of styrene, 35 parts of divinylbenzene, 20 parts of white oil, 4 parts of benzoyl peroxide, 3 parts of pore-forming agent, 80 parts of solvent oil, 7 parts of 1, 2-dichloroethane, 8 parts of zinc chloride and 170 parts of chloromethyl ether.
The preparation method comprises the following steps:
(1) white ball polymerization: heating water to 55 ℃, adding gelatin, stirring for 2h, adding styrene, divinylbenzene, white oil, toluene and benzoyl peroxide, heating to 80 ℃ for shaping, keeping the temperature for 3h after shaping, then heating to 90 ℃ for the second time, keeping the temperature for 7h for the second time, and washing with 60 ℃ water for 6 times after keeping the temperature to obtain white balls;
(2) drying and screening white balls: drying the white balls at a drying temperature of not more than 80 ℃ until the weight loss rate is less than 8.0%, and sieving the dried white balls to obtain white balls with the particle size of 0.5-1.0 mm, thereby obtaining qualified white balls;
(3) wax extraction: adding qualified white balls into No. 120 solvent oil, stirring, heating to 60 ℃, keeping the temperature for 2h, pumping out the solvent oil, repeating the operation for 6 times, and washing to obtain wax balls;
(4) drying and screening wax balls: drying the wax balls at a drying temperature of no more than 80 ℃ until the weight loss rate is no more than 3%, and sieving the dried wax balls to obtain wax balls with the particle size of 0.5mm-1.0mm, thereby obtaining qualified wax balls;
(5) chlorination: adding qualified wax balls into chloromethyl ether, heating to 35 ℃, preserving heat for 4 hours, cooling to below 30 ℃, adding 4 parts of zinc chloride twice, then heating to 40 ℃, preserving heat for 80 hours, cooling to below 30 ℃, carrying out solid-liquid separation, and washing a solid phase with ethanol for 5 times to obtain chlorine balls;
(6) drying the chlorine balls: drying the chlorine ball at the drying temperature of 80 ℃ and the weight loss rate of 1.5-9.5 percent to obtain the qualified chlorine ball;
(7) post-crosslinking reaction: mixing 1, 2-dichloroethane with qualified chlorine balls, stirring, heating to 50 ℃, preserving heat for 5 hours, adding 4 parts of zinc chloride, heating to 90 ℃ for the second time, preserving heat for 2 hours for the second time, heating to 120 ℃ for the third time, preserving heat for 10 hours for the third time, cooling to 40 ℃ to obtain finished balls, performing solid-liquid separation on the finished balls and the 1, 2-dichloroethane, washing the finished balls by using ethanol, washing for five times by using deionized water, and draining to obtain the macroporous adsorption resin.
Comparative example 1 compared to example 1, the composition of the raw materials alone was different and no white oil was contained.
Comparative example 2 is different from example 1 only in the composition of the raw materials in parts by weight.
The raw materials comprise: 200 parts of water, 10 parts of gelatin, 70 parts of styrene, 80 parts of divinylbenzene, 10 parts of white oil, 1 part of azobisisobutyronitrile, 2 parts of toluene, 20 parts of No. 120 solvent oil, 5 parts of 1, 2-dichloroethane, 10 parts of zinc chloride and 150 parts of chloromethyl ether.
Compared with the example 1, the temperature of the steps (1) and (7) is increased in one step without a heat preservation process in the comparative example 3.
The raw materials comprise: 200 parts of water, 10 parts of gelatin, 10 parts of styrene, 50 parts of divinylbenzene, 10 parts of white oil, 5 parts of azobisisobutyronitrile, 2 parts of toluene, 100 parts of No. 120 solvent oil, 5 parts of 1, 2-dichloroethane, 10 parts of zinc chloride and 150 parts of chloromethyl ether.
The preparation method comprises the following steps:
(1) white ball polymerization: heating water to 50 ℃, adding gelatin, stirring for 1h, adding styrene, divinylbenzene, white oil, toluene and azobisisobutyronitrile, heating to 85 ℃ for shaping, and then washing with 60 ℃ water for 5 times to obtain white spheres;
(2) drying and screening white balls: drying the white balls at a drying temperature of not more than 80 ℃ until the weight loss rate is less than 8.0%, and sieving the dried white balls to obtain white balls with the particle size of 0.5-1.0 mm, thereby obtaining qualified white balls;
(3) wax extraction: adding qualified white balls into No. 120 solvent oil, stirring, heating to 35 deg.C, maintaining the temperature for 0.5h, removing the solvent oil, repeating the above operation for 6 times, and washing to obtain wax balls;
(4) drying and screening wax balls: drying the wax balls at a drying temperature of no more than 80 ℃ until the weight loss rate is no more than 3%, and sieving the dried wax balls to obtain wax balls with the particle size of 0.5mm-1.0mm, thereby obtaining qualified wax balls;
(5) chlorination: adding qualified wax balls into chloromethyl ether, heating to 35 ℃, preserving heat for 4 hours, cooling to below 30 ℃, adding 4 parts of zinc chloride twice, then heating to 40 ℃, preserving heat for 80 hours, cooling to below 30 ℃, carrying out solid-liquid separation, and washing a solid phase with ethanol for 5 times to obtain chlorine balls;
(6) drying the chlorine balls: drying the chlorine ball at the drying temperature of 80 ℃ and the weight loss rate of 1.5-9.5 percent to obtain the qualified chlorine ball;
(7) post-crosslinking reaction: mixing 1, 2-dichloroethane with qualified chlorine spheres, adding 4 parts of zinc chloride, stirring, heating to 105 ℃, cooling to 40 ℃ to obtain finished spheres, performing solid-liquid separation on the finished spheres and the 1, 2-dichloroethane, washing the finished spheres with ethanol for five times, washing with deionized water for five times, and filtering to obtain the macroporous adsorption resin.
Comparative example 4 the drying temperatures of steps (2), (4) and (6) were different from those of example 1.
The raw materials comprise: 200 parts of water, 10 parts of gelatin, 10 parts of styrene, 50 parts of divinylbenzene, 10 parts of white oil, 5 parts of azobisisobutyronitrile, 2 parts of toluene, 100 parts of No. 120 solvent oil, 5 parts of 1, 2-dichloroethane, 10 parts of zinc chloride and 150 parts of chloromethyl ether.
The preparation method comprises the following steps:
(1) white ball polymerization: heating water to 50 ℃, adding gelatin, stirring for 1h, adding styrene, divinylbenzene, white oil, toluene and azodiisobutyronitrile, heating to 70 ℃, shaping, then preserving heat for 2h, then heating to 85 ℃ for the second time, preserving heat for 6h for the second time, washing with 60 ℃ water for 5 times after heat preservation, and obtaining white balls;
(2) drying and screening white balls: drying the white balls at 85 ℃ until the weight loss rate is less than 8.0%, and sieving the dried white balls to obtain white balls with the particle size of 0.5-1.0 mm, thereby obtaining qualified white balls;
(3) wax extraction: adding qualified white balls into No. 120 solvent oil, stirring, heating to 35 deg.C, maintaining the temperature for 0.5h, removing the solvent oil, repeating the above operation for 6 times, and washing to obtain wax balls;
(4) drying and screening wax balls: drying the wax balls at the drying temperature of 90 ℃ until the weight loss rate is not more than 3%, and sieving the dried wax balls to obtain the wax balls with the grain size of 0.5mm-1.0mm, thereby obtaining qualified wax balls;
(5) chlorination: adding qualified wax balls into chloromethyl ether, heating to 30 ℃, preserving heat for 2 hours, cooling to below 30 ℃, adding 5 parts of zinc chloride twice, then heating to 35 ℃, preserving heat for 60 hours, cooling to below 30 ℃, carrying out solid-liquid separation, and washing a solid phase with ethanol for 5 times to obtain chlorine balls;
(6) drying the chlorine balls: drying the chlorine ball at 70 ℃ with the weight loss rate of 1.5-9.5 percent to obtain the qualified chlorine ball;
(7) post-crosslinking reaction: mixing 1, 2-dichloroethane with qualified chlorine balls, stirring, heating to 35 ℃, keeping the temperature for 2 hours, adding 5 parts of zinc chloride, heating to 85 ℃ for the second time, keeping the temperature for 0.2 hour for the second time, heating to 105 ℃ for the third time, keeping the temperature for 8 hours for the third time, cooling to 40 ℃ to obtain finished balls, performing solid-liquid separation on the finished balls and the 1, 2-dichloroethane, washing the finished balls by using ethanol, washing for five times by using deionized water, and draining to obtain the macroporous adsorption resin.
Experimental example 1 measurement of specific surface area and porosity
The specific surface area and porosity of the product were determined using BTE.
The samples were weighed, degassed by heating and evacuation, and then weighed. After cooling under vacuum at room temperature for 30min, the sample was placed on a BET for analysis, and the following results were obtained:
experimental example 2 measurement of mechanical Strength-sphericity ratio after grinding
The method for measuring the sphericity after grinding is described in GB/T11992-2008, 8.2. The experimental results are as follows:
experimental example 3
And measuring the glass transition temperature of the product by using a thermogravimetric analyzer.
Weighing a sample, putting the sample into an instrument, and measuring the glass transition temperature of the sample.
The experimental results are as follows:
compared with the prior art, the product obtained by the invention has the advantages of large specific surface area and porosity, good mechanical strength, high temperature resistance, simple preparation process and easy industrial production.
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed above, and the technical means also comprises the technical scheme formed by any combination of the technical features. While the foregoing is directed to embodiments of the present invention, it is noted that various changes and modifications may be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. The macroporous adsorption resin is characterized by comprising the following raw materials in parts by weight: 300 parts of 200-wall-changing water, 5-10 parts of gelatin, 10-20 parts of styrene, 20-50 parts of divinylbenzene, 10-30 parts of white oil, 2-5 parts of initiator, 2-5 parts of pore-foaming agent, 50-100 parts of solvent oil, 5-10 parts of 1, 2-dichloroethane, 5-10 parts of zinc chloride and 200 parts of 150-wall-changing chloromethyl ether;
wherein the initiator is one or more of azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide and cyclohexanone peroxide; the pore-foaming agent is toluene;
the preparation method of the resin comprises the following steps:
(1) white ball polymerization: heating water, adding gelatin, stirring, adding styrene, divinylbenzene, white oil, pore-forming agent and initiator, heating for shaping, keeping the temperature after shaping, heating again, keeping the temperature for the second time, and washing to obtain white balls;
(2) drying and screening white balls: drying the white balls until the weight loss rate is less than 8.0%, and sieving to obtain qualified white balls;
(3) wax extraction: adding qualified white balls into solvent oil, stirring, heating, keeping the temperature, pumping out the solvent oil, repeating the above operations for 5-6 times, and washing to obtain wax balls;
(4) drying and screening wax balls: drying the wax balls until the weight loss rate is not more than 3%, and sieving to obtain qualified wax balls;
(5) chlorination: adding qualified wax balls into chloromethyl ether, heating, preserving heat, cooling, adding zinc chloride twice, then heating for the second time, preserving heat for the second time, cooling for the second time, performing solid-liquid separation, and washing a solid phase to obtain chlorine balls;
(6) drying the chlorine balls: drying the chlorine ball with the weight loss rate of 1.5-9.5% to obtain the qualified chlorine ball;
(7) post-crosslinking reaction: mixing 1, 2-dichloroethane with qualified chlorine balls, stirring, heating, preserving heat, adding zinc chloride, heating for the second time, preserving heat for the second time, heating for the third time, preserving heat for the third time, cooling to obtain finished balls, performing solid-liquid separation on the finished balls and the 1, 2-dichloroethane, washing the finished balls, and filtering to obtain macroporous adsorption resin;
in the step (1), water is heated to 50-60 ℃; heating to 70-85 deg.C; the temperature is increased to 85-92 ℃ for the second time;
the drying temperature in the step (2) is not higher than 80 ℃;
the drying temperature in the step (4) is not higher than 80 ℃;
the drying temperature in the step (6) is 80-90 ℃;
in the step (7), the temperature is raised to 35-50 ℃, and the temperature is kept for 2-5 h; heating to 85-100 ℃ for the second time, and preserving heat for 0.2-2h for the second time; the temperature is raised to 105-150 ℃ for the third time, and the temperature is kept for 8-20h for the third time.
2. The method for preparing the resin according to claim 1, comprising the steps of:
(1) white ball polymerization: heating water, adding gelatin, stirring, adding styrene, divinylbenzene, white oil, pore-forming agent and initiator, heating for shaping, keeping the temperature after shaping, heating again, keeping the temperature for the second time, and washing to obtain white balls;
(2) drying and screening white balls: drying the white balls until the weight loss rate is less than 8.0%, and sieving to obtain qualified white balls;
(3) wax extraction: adding qualified white balls into solvent oil, stirring, heating, keeping the temperature, pumping out the solvent oil, repeating the above operations for 5-6 times, and washing to obtain wax balls;
(4) drying and screening wax balls: drying the wax balls until the weight loss rate is not more than 3%, and sieving to obtain qualified wax balls;
(5) chlorination: adding qualified wax balls into chloromethyl ether, heating, preserving heat, cooling, adding zinc chloride twice, then heating for the second time, preserving heat for the second time, cooling for the second time, performing solid-liquid separation, and washing a solid phase to obtain chlorine balls;
(6) drying the chlorine balls: drying the chlorine ball with the weight loss rate of 1.5-9.5% to obtain the qualified chlorine ball;
(7) post-crosslinking reaction: mixing 1, 2-dichloroethane with qualified chlorine balls, stirring, heating, keeping the temperature, adding zinc chloride, heating for the second time, keeping the temperature for the second time, heating for the third time, keeping the temperature for the third time, cooling to obtain finished balls, performing solid-liquid separation on the finished balls and the 1, 2-dichloroethane, washing the finished balls, and filtering to obtain the macroporous adsorption resin.
3. The preparation method according to claim 2, wherein in the step (2), white balls with the grain size of 0.5mm-1.0mm are obtained by sieving; and (4) screening to obtain white balls with the particle size of 0.5mm-1.0 mm.
4. The preparation method according to claim 2, wherein in the step (3), the temperature is raised to 35-60 ℃, the temperature is kept for 0.5-2h, and the solvent oil is No. 120 solvent oil.
5. The preparation method according to claim 2, wherein in the step (5), the qualified wax balls are added into chloromethyl ether, the temperature is raised to 30-40 ℃, the temperature is kept for 2-5h, the temperature is lowered to below 30 ℃, zinc chloride is added in two times, then the temperature is raised to 35-45 ℃ for the second time, the temperature is kept for 60-100h for the second time, the temperature is lowered to below 30 ℃ for the second time, solid-liquid separation is carried out, and the solid phase is washed by ethanol, so that the chlorine balls are obtained.
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