CN112321756A - Preparation method of highly sulfonated polystyrene resin - Google Patents
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Abstract
The invention provides a preparation method of highly sulfonated polystyrene resin, wherein the used unmodified resin is polystyrene resin microspheres with large particle size, the anion monomer for modification is sodium styrene sulfonate, the polystyrene resin microspheres are firstly swelled by dichloromethane, then washed and filtered by tetrahydrofuran, ultrapure water, absolute ethyl alcohol and methanol for several times, and finally dried in vacuum; then, grafting an acylation reagent chloroacetyl chloride on the surface of the pretreated microsphere by utilizing a Friedel-crafts acylation reaction to obtain an acylated polystyrene resin macromolecular initiator; and finally, initiating the polymerization of the monomer sodium styrene sulfonate on the surface of the polystyrene resin by utilizing an atom transfer radical polymerization method and taking cuprous bromide as a catalyst and pentamethyldiethylenetriamine as a ligand. The invention solves the problems of small quantity of sulfonic acid groups, difficult control of reaction process, low strength of resin microspheres and high cost caused by steric hindrance effect when the surface of the existing large-particle-size polystyrene resin microspheres is sulfonated.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to functionalized modification of a polymer, in particular to a sulfonation modification method of polystyrene resin microspheres.
[ background of the invention ]
The polystyrene resin microspheres are rigid beads prepared by using styrene as a monomer and divinylbenzene as a crosslinking agent, and the diameters of the rigid beads are different from dozens of nanometers to hundreds of micrometers. The different sizes determine the different physical properties of the microspheres. The nano-scale polystyrene resin microspheres are usually used as a carrier of a catalyst because of their relatively small surface energy. The micron-level polystyrene resin microspheres have larger surface energy, and the reaction activation energy cannot be effectively reduced when the micron-level polystyrene resin microspheres are used as catalyst carriers, but the effect is better when the micron-level polystyrene resin microspheres are used as adsorbents. Compared with the pure solid resin microspheres, the resin microspheres with porous/vacuum structures have higher specific surface area and adsorption performance.
The unmodified polystyrene resin microspheres cannot meet the specific adsorption application requirements, and the modification of polystyrene resin to enable the polystyrene resin to meet the use under specific conditions is the key point and the main direction of the research and development of the current polystyrene resin microspheres. At present, there are two main methods for preparing sulfonated polystyrene resin microspheres, one is to add a monomer containing sulfonic acid groups and divinyl benzene for polymerization in the process of synthesizing polystyrene resin microspheres, for example, sodium styrene sulfonate is used as a functional monomer, and the monomer and the divinyl benzene are subjected to emulsion polymerization to prepare sulfonated polystyrene resin microspheres with particles of 80-90nm in particle size; the main defect is that the number of sulfonic groups on the surface of the microsphere is small, because in the copolymerization process of sulfonic styrene and divinyl benzene, the sulfonic groups are polymerized outwards from seeds to form the microsphere, so that a plurality of functional groups are polymerized in the microsphere, and although the sulfonation degree is higher, the utilization rate of the sulfonic groups on the surface is too low. The second method mainly adopts a reagent containing sulfur element as a sulfonation reagent, such as fuming concentrated sulfuric acid, gaseous or liquid sulfur trioxide and the like. The disadvantages are mainly two-fold. Firstly, the modified microspheres have low hardness and are fragile, and the thermal stability of sulfonic acid groups is poor; secondly, in these methods, the sulfonic acid groups are present as a single layer on the surface of the microspheres, resulting in too small a number of sulfonic acid groups on the surface of the resin microspheres.
The number of functional groups on the surface of the polystyrene resin microsphere can be increased by grafting the high molecular polymer on the surface of the polystyrene resin microsphere. The polystyrene crosslinking adsorption resin can be subjected to reactions such as sulfonation, halogenation, Friedel-crafts acylation and the like by utilizing the chemical activity of benzene rings on a high molecular chain of the polystyrene crosslinking adsorption resin, and then various functional groups are introduced, so that the polystyrene crosslinking adsorption resin is very suitable for preparing resin microspheres with high selectivity and high adsorbability. The high molecular polymer can be grafted on the Surface of the resin microsphere by Atom-mediated Atom transfer polymerization (ATRP) and Reversible addition-fragmentation chain transfer polymerization (RAFT). The ATRP method firstly prepares halogen acetylation polystyrene resin microspheres through Friedel-Crafts reaction, and then performs a series of atom transfer radical reactions with transition metal halogen atoms based on Kharash addition reaction. Compared with RAFT, the ATRP method does not need to load a reagent on the surface of the resin microsphere, has no side reaction, ensures that the grafted polymer molecules are uniformly distributed, easily controls the length of the polymer molecular chain and has higher monomer conversion rate.
The traditional polystyrene resin microsphere surface modification adopts the polystyrene resin with smaller grain diameter, and the modification is easier. The resin microspheres with larger size are more convenient to use in application, but the polystyrene resin microspheres with the size of hundreds of micrometers are difficult to chemically modify due to larger surface area. The existing polystyrene resin microsphere surface modification usually adopts monomer direct polymerization, and a steric hindrance effect exists in the polymerization process to influence the further polymerization of the monomer, so that the polymer on the resin microsphere surface is unevenly distributed and has low polymerization degree.
[ summary of the invention ]
The technical problem to be solved by the invention is to provide a preparation method of polystyrene resin with high sulfonic acid group content on the surface, which solves the problems of low surface sulfonic acid group content and uneven distribution, dangerous and difficult control in the sulfonation polymerization process, low resin microsphere strength and high cost caused by steric hindrance effect in the polymerization process of the existing large-particle-size sulfonated polystyrene resin microspheres.
The invention is realized by the following steps:
a method for preparing a highly sulfonated polystyrene resin, the method comprising the steps of:
step 1, pretreatment of unmodified polystyrene resin: weighing a certain amount of polystyrene resin microspheres, adding dichloromethane to swell for 5-15h, sequentially washing and filtering with tetrahydrofuran, ultrapure water, absolute ethyl alcohol and absolute methyl alcohol for 2-3 times respectively, and finally drying in vacuum at 20-30 ℃ to constant weight;
step 2, chloracetylating the polystyrene resin microspheres: weighing the polystyrene resin microspheres treated in the step 1, adding dichloromethane into a high-pressure reaction bottle to swell for 5-10h, then adding aluminum chloride and chloroacetyl chloride into a reaction system, carrying out high-pressure closed reaction for 1-5h at 25-50 ℃, finally filtering out a reaction reagent, washing and filtering with tetrahydrofuran, water, 3% mass fraction diluted hydrochloric acid, absolute ethyl alcohol and methanol for 2-3 times respectively, and carrying out vacuum drying at 20-30 ℃ to constant weight to obtain chloroacetylated polystyrene resin microspheres;
step 3, sulfonation modification of polystyrene resin microspheres: swelling the chloroacetylated polystyrene resin microspheres treated in the step 2 in an ultrapure water solution for 5-10h, dissolving sodium styrene sulfonate in the ultrapure water and mixing with the swelled chloroacetylated polystyrene resin microspheres, adjusting the pH to 4-6 by using a sodium hydroxide solution, adding ligand pentamethyldiethylenetriamine and catalyst cuprous bromide treated by glacial acetic acid, removing oxygen in the solution by a bubbling method, placing in a water bath shaking table at 60-85 ℃, and reacting at the rotating speed of 140 rpm; after the reaction is finished, washing and filtering the mixture for 2 to 3 times respectively by using tetrahydrofuran, water, 3 percent of dilute hydrochloric acid and methanol; finally drying the mixture in vacuum at the temperature of 20-30 ℃ to constant weight.
Further, the polystyrene resin microspheres adopted in the step 1 are large-particle size polystyrene resin microspheres with the particle size of 300-500 μm.
Further, the weight parts of each reactant in the step 2 are as follows: 5 parts of polystyrene resin microspheres, 60-80 parts of dichloromethane, 2-10 parts of chloroacetyl chloride and 4-12 parts of aluminum chloride.
Further, the weight parts of each reactant in the step 3 are as follows: 5 parts of chloracetyl polystyrene resin microspheres, 100-180 parts of ultrapure water, 15-25 parts of anionic monomer sodium styrene sulfonate, 3-9 parts of cuprous bromide serving as a catalyst, 40-60 parts of ligand pentamethyldiethylenetriamine and 2-8 parts of sodium hydroxide.
The method of the invention has the following advantages:
when the method is used for sulfonating and modifying the polystyrene resin microspheres, the large-particle-size polystyrene resin microspheres with uniformly distributed surfaces and high anionic sulfonic acid group content are prepared by changing chloroacetylation and sulfonation modification processes, the influence of oxygen and steric hindrance effect on reaction is effectively eliminated in a polymerization process, the sulfonic acid groups are covered on the surfaces of the microspheres by a single-layer mesh polymer, and the method has the advantages of large particle size and high content of surface sulfonic acid groups which are not easy to break, and solves the problems of small quantity of surface sulfonic acid groups, difficult control and danger in a sulfonation process, low strength of the resin microspheres and high cost in the traditional sulfonation method.
The sulfonated polystyrene resin microspheres prepared by the invention can be used for wastewater treatment, ion exchange, sugar separation and carriers of certain catalysts, and are functional polystyrene resin microspheres with excellent performance.
[ description of the drawings ]
The invention will now be further described with reference to the following examples.
FIG. 1 is an infrared spectroscopic analysis chart of polystyrene resin microspheres having a high-density sulfonic acid group on the surface thereof prepared in example 1 of the present invention.
[ detailed description ] embodiments
The invention discloses a preparation method of highly sulfonated polystyrene resin, which comprises the following steps:
step 1, pretreatment of unmodified polystyrene resin: weighing a certain amount of polystyrene resin microspheres, adding dichloromethane to swell for 5-15h, sequentially washing and filtering with tetrahydrofuran, ultrapure water, absolute ethyl alcohol and absolute methyl alcohol for 2-3 times respectively, and finally drying in vacuum at 20-30 ℃ to constant weight;
step 2, chloracetylating the polystyrene resin microspheres: weighing the polystyrene resin microspheres treated in the step 1, adding dichloromethane into a high-pressure reaction bottle to swell for 5-10h, then adding aluminum chloride and chloroacetyl chloride into a reaction system, carrying out high-pressure closed reaction for 1-5h at 25-50 ℃, finally filtering out a reaction reagent, washing and filtering with tetrahydrofuran, water, 3% mass fraction diluted hydrochloric acid, absolute ethyl alcohol and methanol for 2-3 times respectively, and carrying out vacuum drying at 20-30 ℃ to constant weight to obtain chloroacetylated polystyrene resin microspheres;
step 3, sulfonation modification of polystyrene resin microspheres: swelling the chloroacetylated polystyrene resin microspheres treated in the step 2 in an ultrapure water solution for 5-10h, dissolving sodium styrene sulfonate in the ultrapure water and mixing with the swelled chloroacetylated polystyrene resin microspheres, adjusting the pH to 4-6 by using a sodium hydroxide solution, adding ligand pentamethyldiethylenetriamine and catalyst cuprous bromide treated by glacial acetic acid, removing oxygen in the solution by a bubbling method, placing in a water bath shaking table at 60-85 ℃, and reacting at the rotating speed of 140 rpm; after the reaction is finished, washing and filtering the mixture for 2 to 3 times respectively by using tetrahydrofuran, water, 3 percent of dilute hydrochloric acid and methanol; finally drying the mixture in vacuum at the temperature of 20-30 ℃ to constant weight.
The polystyrene resin microspheres adopted in the step 1 are large-particle-size polystyrene resin microspheres with the particle size of 300-500 mu m.
The weight parts of the reactants in the step 2 are as follows: 5 parts of polystyrene resin microspheres, 60-80 parts of dichloromethane, 2-10 parts of chloroacetyl chloride and 4-12 parts of aluminum chloride.
The weight parts of the reactants in the step 3 are as follows: 5 parts of chloracetyl polystyrene resin microspheres, 100-180 parts of ultrapure water, 15-25 parts of anionic monomer sodium styrene sulfonate, 3-9 parts of cuprous bromide serving as a catalyst, 40-60 parts of ligand pentamethyldiethylenetriamine and 2-8 parts of sodium hydroxide.
Referring to fig. 1, the technical solution of the present invention will be described clearly and completely with reference to the accompanying drawings and the detailed description. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. 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.
Example 1: weighing 0.5g of polystyrene resin microspheres, adding dichloromethane to swell for 5h, washing and filtering the polystyrene resin microspheres in a sand core funnel by tetrahydrofuran, ultrapure water, absolute ethyl alcohol and absolute methyl alcohol for three times respectively, and finally drying the polystyrene resin microspheres in vacuum at 20 ℃ to constant weight.
Acylation of polystyrene resin microspheres: weighing 0.3g of pretreated polystyrene resin white balls, putting the white balls into a high-pressure reaction bottle, swelling the white balls for 5 hours by using 20ml of dichloromethane, adding 0.28g of catalyst aluminum chloride and 100 mu l of acetylation reagent chloroacetyl chloride, and carrying out shaking table reaction for 5 hours in a water bath in the high-pressure reaction bottle at 50 ℃. Cooling to room temperature, washing and filtering with tetrahydrofuran, 3% dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and methanol twice respectively, and finally drying in vacuum at 30 ℃ to constant weight to obtain the chloracetyl polystyrene resin microspheres.
Sulfonation modification of polystyrene resin microspheres: and (2) putting 0.3g of the chloroacetylated polystyrene resin microspheres treated in the step (2) into a beaker, swelling the chloroacetylated polystyrene resin microspheres for 5 hours by using 5ml of ultrapure water, dissolving 2g of sodium styrene sulfonate into 4ml of ultrapure water, mixing the solution with the swelled chloroacetylated polystyrene resin microspheres, adjusting the pH of the solution to 5.5 by using 40% sodium hydroxide solution, adding 0.4g of cuprous bromide serving as a glacial acetic acid treated catalyst and 1.3ml of pentamethyldiethylenetriamine serving as a ligand, and bubbling the solution in a conical flask for 30min to remove oxygen in a reaction system. Finally, the reaction is carried out for 10 hours at the temperature of 65 ℃ on a water bath shaker and at the speed of 10 rpm. After the reaction is finished, tetrahydrofuran, 3 percent of dilute hydrochloric acid, ultrapure water and methanol are respectively used for washing and filtering twice, and finally, the sulfonated polystyrene resin microspheres are obtained by vacuum drying at the temperature of 20 ℃ until the weight is constant. The weight gain was 64.29%, and the grafting rate was 9.16%.
Example 2: weighing 0.5g of polystyrene resin microspheres, adding dichloromethane to swell for 10h, washing and filtering the polystyrene resin microspheres in a sand core funnel by tetrahydrofuran, ultrapure water, absolute ethyl alcohol and absolute methyl alcohol for three times respectively, and finally drying the polystyrene resin microspheres in vacuum at 30 ℃ to constant weight.
Acylation of polystyrene resin microspheres: weighing 0.3g of pretreated polystyrene resin white balls, putting the white balls into a high-pressure reaction bottle, swelling the white balls by using 20ml of dichloromethane for 10 hours, adding 0.59g of catalyst aluminum chloride and 300 mu l of acetylation reagent chloroacetyl chloride, and carrying out shaking table reaction in the high-pressure reaction bottle at 50 ℃ for 5 hours in a water bath. Cooling to room temperature, washing and filtering with tetrahydrofuran, 3% dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and methanol twice respectively, and finally drying in vacuum at 30 ℃ to constant weight to obtain the chloracetyl polystyrene resin microspheres.
Anionization modification of polystyrene resin microspheres: and (2) putting 0.3g of the chloroacetylated polystyrene resin microspheres treated in the step (2) into a beaker, swelling the chloroacetylated polystyrene resin microspheres for 5 hours by using 5ml of ultrapure water, dissolving 2g of sodium styrene sulfonate into 10ml of ultrapure water, mixing the solution with the swelled chloroacetylated polystyrene resin microspheres, adjusting the pH of the solution to 5.0 by using 40% sodium hydroxide solution, adding 0.4g of cuprous bromide serving as a glacial acetic acid treated catalyst and 1.3ml of pentamethyldiethylenetriamine serving as a ligand, and bubbling the solution in a conical flask for 30min to remove oxygen in a reaction system. Finally, the reaction is carried out for 12h under the conditions of a water bath shaker at 85 ℃ and 140 rpm. After the reaction is finished, tetrahydrofuran, 3 percent of dilute hydrochloric acid, ultrapure water and methanol are respectively used for washing and filtering twice, and finally, the sulfonated polystyrene resin microspheres are obtained by vacuum drying at the temperature of 30 ℃ until the weight is constant. The weight gain was 72.37%, and the grafting yield was 11.9%.
Example 3: weighing 0.5g of polystyrene resin microspheres, adding dichloromethane to swell for 15h, washing and filtering the polystyrene resin microspheres in a sand core funnel by tetrahydrofuran, ultrapure water, absolute ethyl alcohol and absolute methyl alcohol for three times respectively, and finally drying the polystyrene resin microspheres in vacuum at 30 ℃ to constant weight.
Acylation of polystyrene resin microspheres: weighing 0.3g of pretreated polystyrene resin white balls, putting the white balls into a high-pressure reaction bottle, swelling the white balls by using 20ml of dichloromethane for 10 hours, adding 0.28g of catalyst aluminum chloride and 200 mu l of acetylation reagent chloroacetyl chloride, and carrying out shaking table reaction in the high-pressure reaction bottle at the temperature of 40 ℃ for 5 hours in a water bath. Cooling to room temperature, washing and filtering with tetrahydrofuran, 3% dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and methanol twice respectively, and finally drying in vacuum at 30 ℃ to constant weight to obtain the chloracetyl polystyrene resin microspheres.
Anionization modification of polystyrene resin microspheres: and (2) putting 0.3g of the chloroacetylated polystyrene resin microspheres treated in the step (2) into a beaker, swelling the chloroacetylated polystyrene resin microspheres for 10 hours by using 5ml of ultrapure water, dissolving 2g of sodium styrene sulfonate into 10ml of ultrapure water, mixing the solution with the swelled chloroacetylated polystyrene resin microspheres, adjusting the pH of the sodium styrene sulfonate solution to 6.0 by using 40% sodium hydroxide solution, adding 0.4g of cuprous bromide serving as a catalyst treated by glacial acetic acid and 1.5ml of pentamethyldiethylenetriamine serving as a ligand, and bubbling the solution in a conical flask for 30min to remove oxygen in a reaction system. Finally, the reaction is carried out for 10h at the temperature of 80 ℃ on a water bath shaker and at the speed of 140 rpm. After the reaction is finished, tetrahydrofuran, 3 percent of dilute hydrochloric acid, ultrapure water and methanol are respectively used for washing and filtering twice, and finally, the sulfonated polystyrene resin microspheres are obtained by vacuum drying at the temperature of 30 ℃ until the weight is constant. The weight gain rate is 70.31 percent, and the grafting rate is 10.5 percent.
FIG. 1 is a graph showing the IR spectrum analysis of chloroacetylated polystyrene resin microspheres and anionic sulfonated polystyrene resin microspheres prepared according to example 1. As can be seen from FIG. 1, the length of the groove is 1686cm-1At the absorption wavelength, the acetylated microspheres have an absorption peak compared with white spheres, the absorption peak is the absorption peak of carbonyl, and the carbonyl is from chloroacetyl chloride, which indicates successful chloroacetylation; the sulfonated PS curve shows characteristic absorption peaks of sulfonic acid groups at 1116 and 1180, wherein 1116 is an absorption peak of S ═ O bond in the sulfonic acid group; 1180 is the absorption peak of the S-O bond in the sulfonic acid group, which indicates that the styrene sodium sulfonate graft polymerization is successful.
The results of the three examples and the attached figures show that the polystyrene resin microspheres can be successfully subjected to high sulfonation modification by utilizing Friedel-crafts acylation and atom transfer radical polymerization.
Although specific embodiments of the invention have been described above, it will be understood by those skilled in the art that the specific embodiments described are illustrative only and are not limiting upon the scope of the invention, and that equivalent modifications and variations can be made by those skilled in the art without departing from the spirit of the invention, which is to be limited only by the appended claims.
Claims (4)
1. A preparation method of highly sulfonated polystyrene resin is characterized by comprising the following steps: the method comprises the following steps:
step 1, pretreatment of unmodified polystyrene resin: weighing a certain amount of polystyrene resin microspheres, adding dichloromethane to swell for 5-15h, sequentially washing and filtering with tetrahydrofuran, ultrapure water, absolute ethyl alcohol and absolute methyl alcohol for 2-3 times respectively, and finally drying in vacuum at 20-30 ℃ to constant weight;
step 2, chloracetylating the polystyrene resin microspheres: weighing the polystyrene resin microspheres treated in the step 1, adding dichloromethane into a high-pressure reaction bottle to swell for 5-10h, then adding aluminum chloride and chloroacetyl chloride into a reaction system, carrying out high-pressure closed reaction for 1-5h at 25-50 ℃, finally filtering out a reaction reagent, washing and filtering with tetrahydrofuran, water, 3% mass fraction diluted hydrochloric acid, absolute ethyl alcohol and methanol for 2-3 times respectively, and carrying out vacuum drying at 20-30 ℃ to constant weight to obtain chloroacetylated polystyrene resin microspheres;
step 3, sulfonation modification of polystyrene resin microspheres: swelling the chloroacetylated polystyrene resin microspheres treated in the step 2 in an ultrapure water solution for 5-10h, dissolving sodium styrene sulfonate in the ultrapure water and mixing with the swelled chloroacetylated polystyrene resin microspheres, adjusting the pH to 4-6 by using a sodium hydroxide solution, adding ligand pentamethyldiethylenetriamine and catalyst cuprous bromide treated by glacial acetic acid, removing oxygen in the solution by a bubbling method, placing in a water bath shaking table at 60-85 ℃, and reacting at the rotating speed of 140 rpm; after the reaction is finished, washing and filtering the mixture for 2 to 3 times respectively by using tetrahydrofuran, water, 3 percent of dilute hydrochloric acid and methanol; finally drying the mixture in vacuum at the temperature of 20-30 ℃ to constant weight.
2. The method for preparing an anionic sulfonated polystyrene resin as claimed in claim 1, wherein: the polystyrene resin microspheres adopted in the step 1 are large-particle-size polystyrene resin microspheres with the particle size of 300-500 mu m.
3. The method for preparing an anionic sulfonated polystyrene resin as claimed in claim 1, wherein: the weight parts of the reactants in the step 2 are as follows: 5 parts of polystyrene resin microspheres, 60-80 parts of dichloromethane, 2-10 parts of chloroacetyl chloride and 4-12 parts of aluminum chloride.
4. The method for preparing an anionic sulfonated polystyrene resin as claimed in claim 1, wherein: the weight parts of the reactants in the step 3 are as follows: 5 parts of chloracetyl polystyrene resin microspheres, 100-180 parts of ultrapure water, 15-25 parts of anionic monomer sodium styrene sulfonate, 3-9 parts of cuprous bromide serving as a catalyst, 40-60 parts of ligand pentamethyldiethylenetriamine and 2-8 parts of sodium hydroxide.
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