Crosslinked polymer resin for contaminant adsorption from water

Patent metadata

Field	Value
Publication number	US-10889688-B2
Application number	US-201816001307-A
Country	US
Kind code	B2
Filing date	Jun 6, 2018
Priority date	Jun 6, 2018
Publication date	Jan 12, 2021
Grant date	Jan 12, 2021

Abstract

Cross-linked polymer resins and related salts, solvates, tautomers or stereoisomers are described herein. The cross-linked polymer resins may comprise monomer units of N,N-diallyl aminoalkylphosphonate, a hydrophobic pendant, a tetraallylpiperazinium cross-linker, and sulfur dioxide. A method for producing the cross-linked polymer resins is described. The cross-linked polymer resins may be used as adsorbent materials for the removal of heavy metal ions and contaminant dyes from aqueous solutions. Used cross-linked polymer resins may be removed from solution, cleaned, and reused while maintaining adsorption capacity.

First claim

The invention claimed is:

1. A cross-linked polymer resin of formula (I)

or a salt, solvate, tautomer, or stereoisomer thereof;
wherein each R 1 is —H, a positive counter ion, an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl;
wherein each R 2 , R 3 , R 4 , and R 5 is independently —H, an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl;
wherein R 6 is an optionally substituted arylalkyl;
wherein m and n are independently a whole number in the range of 1-10;
wherein x, y, and z are independently a whole number greater than zero; and
wherein Z − is a counter ion.

2. The cross-linked polymer resin of claim 1 , wherein a ratio of x toy is 5:1-10:1, and a ratio of z to y is 1:1-5:1.

3. The cross-linked polymer resin of claim 1 , wherein a compound of formula (I) is porous and has a specific surface area of 40-70 m 2 /g.

4. The cross-linked polymer resin of claim 1 , wherein a compound of formula (I) is porous and has an average pore diameter of 4-20 nm.

5. The cross-linked polymer resin of claim 1 , wherein a compound of formula (I) is

6. The cross-linked polymer resin of claim 1 , wherein a compound of formula (I) is

7. A method for producing the cross-linked polymer resin of claim 1 , comprising:
reacting an arylalkyl halide with a diallylamine to form a hydrophobic pendant monomer; and
cyclocopolymerizing the hydrophobic pendant monomer with a N,N-diallyl aminoalkylphosphonate monomer, a tetraallylpiperazinium cross-linking monomer, dissolved sulfur dioxide, and a free radical initiator in a solvent to form the cross-linked polymer resin.

8. The method of claim 7 , wherein the N,N-diallyl aminoalkylphosphonate monomer has a structure of formula (II)

or a salt, solvate, tautomer, or stereoisomer thereof;
wherein each R 1 is —H, a positive counter ion, an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl; and
m is a whole number in the range of 1-10.

9. The method of claim 8 , wherein the N,N-diallyl aminoalkylphosphonate monomer compound of formula (II) is

wherein m is 1 or 3.

10. The method of claim 7 , wherein the tetraallylpiperazinium cross-linking monomer has a structure of formula (III)

or a salt, solvate, tautomer or stereoisomer thereof;
wherein R 2 , R 3 , R 4 , and R 5 are independently —H, an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted aryl; and
Z − is a counter ion.

11. The method of claim 10 , wherein the tetraallylpiperazinium cross-linking monomer compound of formula (III) is

12. The method of claim 7 , wherein the hydrophobic pendant monomer has a structure of formula (IV)

or a salt, solvate, tautomer, or stereoisomer thereof,
wherein R 6 is an optionally substituted arylalkyl,
wherein n is a whole number in the range of 1-10, and
wherein Z − is a counter ion.

13. The method of claim 10 , wherein the hydrophobic pendant monomer compound of formula (IV) is

14. The method of claim 7 , further comprising contacting the cross-linked polymer resin with a base to form an expanded cross-linked polymer resin.

15. A method of reducing a contaminant concentration from an aqueous solution with the cross-linked polymer resin of claim 1 , comprising:
contacting the cross-linked polymer resin with an aqueous solution comprising the contaminant at a contaminant concentration of 0.5-100 mg/L,
wherein the cross-linked polymer resin reduces the contaminant concentration by adsorption.

16. The method of claim 15 , wherein the cross-linked polymer resin has a concentration of 0.1-5.0 g/L in the aqueous solution, and
wherein the aqueous solution has a pH of 3-7.

17. The method of claim 15 , wherein the contaminant is a heavy metal ion or a dye.

18. The method of claim 17 , wherein the contaminant is a heavy metal ion, and
wherein the cross-linked polymer resin has an adsorption capacity of 10-100 mg of contaminant per g of the cross-linked polymer resin.

19. The method of claim 17 , wherein at least 90% of the total mass of the heavy metal ion is removed from the aqueous solution in at least 9 minutes.

20. The method of claim 15 , further comprising:
separating the cross-linked polymer resin from the aqueous solution to produce a recovered cross-linked polymer resin;
mixing the recovered cross-linked polymer resin with an acidic solution;
removing the acidic solution to produce a cleaned cross-linked polymer resin; and
reusing the cleaned cross-linked polymer resin, which maintains an adsorption capacity for at least 5 purification cycles.

Assignees

• Univ King Fahd Pet & Minerals

Inventors

• Awadh Tawfik Abdo Saleh
• Ali Shaikh A
• Rachman Ihsan B

Classifications

• C08F283/00

  Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G · CPC title

• B01J20/267 Primary

  Cross-linked polymers · CPC title

• C02F2101/103

  Arsenic compounds · CPC title

• B01J20/28059

  being less than 100 m2/g · CPC title

• C02F2101/308

  Dyes; Colorants; Fluorescent agents · CPC title