US 12,221,503 B2
Quaternary ammonium group-grafted cation resin and preparation method thereof
Xueming Chen, Hangzhou (CN); and Xuejiao Zhang, Hangzhou (CN)
Assigned to ZHEJIANG UNIVERSITY, Hangzhou (CN)
Appl. No. 17/642,966
Filed by ZHEJIANG UNIVERSITY, Hangzhou (CN)
PCT Filed Mar. 1, 2021, PCT No. PCT/CN2021/078380
§ 371(c)(1), (2) Date Mar. 15, 2022,
PCT Pub. No. WO2021/238315, PCT Pub. Date Dec. 2, 2021.
Claims priority of application No. 202010447925.6 (CN), filed on May 25, 2020.
Prior Publication US 2022/0332873 A1, Oct. 20, 2022
Int. Cl. C08F 8/30 (2006.01); B01J 39/20 (2006.01); B01J 49/30 (2017.01); C02F 1/469 (2023.01); C08F 8/32 (2006.01); C08F 8/34 (2006.01); C08F 8/36 (2006.01); C08F 257/02 (2006.01); C02F 101/20 (2006.01)
CPC C08F 257/02 (2013.01) [B01J 39/20 (2013.01); B01J 49/30 (2017.01); C02F 1/4695 (2013.01); C02F 2101/20 (2013.01)] 6 Claims
 
1. A preparation method of a quaternary ammonium group-grafted cation resin, comprising the following steps:
1) introducing a quaternary ammonium group into a chloromethylated cross-linked polystyrene (PS) resin comprising:
1.1) adding a chloromethylated cross-linked PS resin and trimethylamine hydrochloride successively to a reaction vessel;
1.2) adding a 20% sodium hydroxide aqueous solution dropwise to the reaction vessel within 1 hour, keeping a first temperature at 30° C. to 40° C., and continuously stirring to allow a first reaction for 2 hours;
1.3) after the first reaction is completed, filtering a first reaction solution to obtain a first intermediate resin, and washing the first intermediate resin with a 5% sodium hydroxide aqueous solution, a 5% hydrochloric acid aqueous solution, and deionized water successively until a first effluent has a pH of 7 to obtain a first washed resin; and
1.4) drying the first washed resin at 60° C. to obtain a quaternary ammonium group-grafted chloromethylated cross-linked PS resin;
and
2) sulfonating the quaternary ammonium group-grafted chloromethylated cross-linked PS resin comprising:
2.1) adding the quaternary ammonium group-grafted chloromethylated cross-linked PS resin obtained in step 1.4), 1,2-dichloroethane, silver sulfate, concentrated sulfuric acid, and fuming sulfuric acid successively to the reaction vessel;
2.2) keeping a second temperature at 50° C. to 60° C., and continuously stirring to allow a second reaction for 1 hour;
2.3) raising the second temperature to 70° C. to 80° C., and continuously stirring to allow the second reaction for 1 hour;
2.4) raising the second temperature to 115° C. to 125° C., and continuously stirring to allow the second reaction for 5 hours;
2.5) after the second reaction is completed, cooling a second reaction solution to room temperature, and diluting and filtering the second reaction solution to obtain a second intermediate resin; and washing the second intermediate resin with deionized water to obtain a second washed resin, converting the second washed resin with a 5% hydrochloric acid aqueous solution to obtain a converted resin, and washing the converted resin with deionized water until a second effluent has a pH of 7; and
2.6) drying the converted resin at 60° C. to obtain the quaternary ammonium group-grafted cation resin;
wherein the method features the following relative amounts of raw materials in parts by weight:
10 to 20 parts of chloromethylated cross-linked PS resin,
40 to 80 parts of 1,2-dichloroethane,
5 to 20 parts of trimethylamine hydrochloride,
20 to 80 parts of 20% sodium hydroxide aqueous solution,
500 to 1,000 parts of 5% sodium hydroxide aqueous solution,
1,000 to 2,000 parts total of 5% hydrochloric acid aqueous solution,
0.5 to 1 part of silver sulfate,
15 to 30 parts of concentrated sulfuric acid,
15 to 30 parts of fuming sulfuric acid, and
9,000 to 18,000 parts total of deionized water.
 
6. A quaternary ammonium group-grafted cation resin prepared by the preparation method according to claim 1.