High exchange-capacity anion exchange resin with dual functional-groups and method of synthesis thereof

Patent metadata

Field	Value
Publication number	US-9950319-B2
Application number	US-201515511184-A
Country	US
Kind code	B2
Filing date	Jul 13, 2015
Priority date	Jul 15, 2014
Publication date	Apr 24, 2018
Grant date	Apr 24, 2018

Abstract

The present disclosed are a high exchange-capacity anion exchange resin with dual functional-groups and method of synthesis thereof. The invention relates to the field of environmental function material synthesis and application. The resin is based on chloromethylated polystyrene-divinylbenzene polymer as matrix, and by primary amination and quaternization, yields an anion exchange resin with dual functional-groups having both a weak base anionic group and a strong base anionic group. The anion exchange resin not only has high adsorption capacity for water-born nitrate ions, but also can effectively squelch natural organic acids such as phytic acid in water, thus simultaneously removing nitrate ions and phytic acid organic matter from water. Therefore, the resin has a broad application potential in the fields of drinking water treatment, groundwater remediation, and advanced urban sewage treatment.

First claim

What is claimed is:

1. A high exchange-capacity anion exchange resin with dual functional-groups, comprising:
a matrix of chloromethylated polystyrene-divinylbenzene polymer;
a weak base anion exchange group formed by grafting a primary amine onto the matrix;
a strong base anion exchange group formed by grafting 3-chloro-2-hydroxypropyltrimethylammonium chloride onto the primary amine, wherein the resin is of formula I:

wherein m represents a degree of polymerization and is within the range of 3000 to 5000.

2. The high exchange-capacity anion exchange resin with dual functional-groups according to claim 1 , wherein a total exchange capacity of the anion exchange resin is 6.3-7.9 mmol/g, wherein a strong base exchange capacity is 3.8-4.7 mmol/g, a weak base exchange capacity is 2.5-3.2 mmol/g, and the average particle diameter of the resin is 550-650 μm.

3. A method for synthesizing a high exchange-capacity anion exchange resin with dual functional-groups according to claim 1 , comprising:
(1) carrying out a primary amination reaction, which comprises dissolving chloromethylated polystyrene-divinylbenzene polymer to swell in a mixed solution of absolute ethanol and choroform, adding hexamethylenetetramine, stirring the reaction mixture at 35-45° C. for 6-7 hours; filtering out the polymer, washing the polymer with ethanol, and placing the polymer into a mixed acid solution of concentrated hydrochloric acid-absolute ethanol at a ratio of chloromethylated polystyrene-divinylbenzene polymer (g):mixed acid solution (ml)=1:4-5, reacting at 35-45° C. for 2-3 hours, filtering out the polymerized product, washing with water, transitioning in a NaOH solution for 2-3 hours washing with water, and filtering to obtain poly(divinylbenzene-vinylbenzyl amine) polymers; and
(2) carrying out a quaternization reaction, which comprises adding the poly(divinylbenzene-vinylbenzyl amine) polymers from step (1) to a mixed solution formulation of 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solution and NaOH at a ratio of poly(divinylbenzene-vinylbenzyl amine) polymers (g):the mixed solution formulation (ml)=1-2:50, stirring the reaction mixture at 70-80° C. for 2-3 hours, washing the product with 10-30% HCl solution and deionized water, drying in vacuum at 40-60° C. to obtain the high exchange-capacity anion exchange resin with dual functional-groups.

4. The method for synthesizing the high exchange-capacity anion exchange resin with dual functional-groups according to claim 3 , wherein, in step (1), chloromethylated polystyrene-divinylbenzene polymer is dissolved to swell in the mixed solution of absolute ethanol and chloroform at 20-25° C. for 3-4 hours at a ratio of chloromethylated polystyrene-divinylbenzene polymer (g):absolute ethanol (ml):chloroform (ml):hexamethylenetetramine (g) of 5:15-20:2-4:4-5.

5. The method for synthesizing the high exchange-capacity anion exchange resin with dual functional-groups according to claim 3 , wherein the mixed acid solution of concentrated hydrochloric acid-absolute ethanol in the step (1) is a mixed acid solution formulation of 37.5% (mass %) concentrated HCl mixed with absolute ethanol at a ration of concentrated HCl (m1):absolute ethanol (ml) in the range of 1:2-3.

6. The method for synthesizing the high exchange-capacity anion exchange resin with dual functional-groups according to claim 3 , wherein the NaOH solution for transitioning has a concentration of 1% (mass %).

7. The method for synthesizing the high exchange-capacity anion exchange resin with dual functional-groups according to claim 3 , wherein the 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solution in the step (2) is 60% (mass %), the NaOH solution is 40% (mass %), and the ratio between the 3-chloro-2-hydroxypropyltrimethylammonium chloride aqueous solution and the NaOH solution is 8-10:1 in volume.

8. The method for synthesizing the high exchange-capacity anion exchange resin with dual functional-groups according to claim 3 , wherein the vacuum drying step is performed under the pressure of −0.09 to -0.08 MPa for 12-24 hours.

Assignees

• Nanjing University Of Technology
• Nanjing Univ Yancheng Environmental Protection Tech And Engineering Research Inst
• Nanjing Univ Yancheng Environmental Protection Technology And Engineering Research Institute

Inventors

• Wang Jinnan
• Wang Yi
• Yang Xin
• Cheng Cheng
• Chen Chen

Classifications

• C08F212/36

  Divinylbenzene · CPC title

• B01J41/13 Primary

  obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds · CPC title

• C08F8/44

  Preparation of metal salts or ammonium salts · CPC title

• C08F8/32

  by reaction with amines · CPC title

• B01J41/05

  in the strongly basic form · CPC title