Cross-linked diallyl quaternary ammonium salt tetrapolymers and methods thereof

Patent metadata

Field	Value
Publication number	US-9790296-B2
Application number	US-201514644822-A
Country	US
Kind code	B2
Filing date	Mar 11, 2015
Priority date	Mar 11, 2015
Publication date	Oct 17, 2017
Grant date	Oct 17, 2017

Abstract

Cross-linked tetrapolymers made up of different diallyl zwitterionic diallyl quaternary ammonium salt monomers, with one of them functioning as a cross-linking monomer. The cross-linked terpolymers include a repeating unit with multiple ligand centers that different metal ions can bind to. The cross-linked tetrapolymers are cationic, zwitterionic and anionic, and can be in either an acidic form or a basic form. A method of removing metal ions from an aqueous solution with these cross-linked tetrapolymers is also described.

First claim

The invention claimed is:

1. A cross-linked tetrapolymer comprising a repeating unit of four zwitterionic diallyl quaternary ammonium salt monomers having one of the following Formulas 1 or 2:

wherein X is F, Cl, Br, I, NO 3 or other suitable anion; M is Li, Na, K or other suitable cation; R1, R2 and R3 are independently substituted or unsubstituted alkyl or aryl groups having 1-6 carbon atoms;
wherein the four monomers are present in the tetrapolymer at a molar ratio of x 1 :x 2 :x 3 :y; x 1 , x 2 and x 3 are each 30-32, y is 4-10 and
wherein the repeating unit comprises a plurality of ligand centers and one of the four monomers is a cross-linking monomer.

2. The cross-linked tetrapolymer of claim 1 , wherein the tetrapolymer is one of cationic, zwitterionic and anionic.

3. The cross-linked tetrapolymer of claim 1 , wherein the tetrapolymer is in an acidic form or a basic form.

4. The cross-linked tetrapolymer of claim 1 , wherein the repeating unit comprises at least 7 ligand centers.

5. The cross-linked tetrapolymer of claim 1 , wherein the four monomers are present in the tetrapolymer at a molar ratio of 31:31:31:7;
wherein the monomer having the lower number of moles is the cross-linking monomer.

6. The cross-linked tetrapolymer of claim 1 , wherein the four monomers are:
4-(diallylammonio)butanoate;
N-allyl-N-(3-phosphonopropyl)prop-2-en-1-aminum chloride;
methylene 3-(diallylammonio)propane-1-sulfinate; and
1,1,4,4-tetrallylpiperazine-1,4-dium chloride;
wherein 1,1,4,4-tetrallylpiperazine-1,4-dium chloride is the cross-linking monomer.

7. The cross-linked tetrapolymer of claim 1 , wherein the tetrapolymer is prepared by heating a solution comprising the four zwitterionic diallyl quaternary ammonium salt monomers at a molar ratio of x 1 :x 2 :x 3 :y and ammonium persulfate to 80-100° C. under an inert atmosphere;
wherein x 1 , x 2 and x 3 are each 30-32, y is 4-10 and the monomer having the lower number of moles is the cross-linking monomer.

8. A method of removing Cr(III) ions from an aqueous solution, comprising:
contacting the aqueous solution with an adsorbent comprising the cross-linked tetrapolymer of claim 1 .

9. The method of claim 8 , wherein the Cr(III) ions have an initial concentration range of 5-500 ppm.

10. The method of claim 8 , wherein the cross-linked tetrapolymer is present in a concentration range of 0.02-0.1 g L −1 per total volume of the aqueous solution.

11. The method of claim 8 , wherein the contacting is carried out at a temperature of 20-65° C.

12. The method of claim 8 , wherein the contacting is carried out at pH 4-7.

13. The method of claim 8 , wherein the contacting is carried out for 10-120 min.

14. The method of claim 8 , wherein the cross-linked tetrapolymer has a Cr(III) maximum adsorption capacity of 45-55 mg g −1 based on the total weight of the cross-linked tetrapolymer.

15. The method of claim 8 , wherein the contacting removes at least 85% of the Cr(III) ions present in the aqueous solution.

16. The method of claim 8 , wherein after contacting, one or more Cr(III) ions are coordinated to the ligand centers of the cross-linked tetrapolymer.

17. The method of claim 8 , wherein the method is in a batch mode.

18. The method of claim 8 , further comprising: desorbing the Cr(III) from the adsorbent to regenerate the adsorbent for Cr(III) removal.

Assignees

• Univ King Fahd Pet & Minerals

Inventors

• Haladu Shamsuddeen Abdullahi
• Ali Shaikh Asrof
• Saleh Tawfik Abdo

Classifications

• C02F1/285

  using synthetic organic sorbents · CPC title

• C08F26/06 Primary

  by a heterocyclic ring containing nitrogen · CPC title

• C02F2101/22

  Chromium or chromium compounds, e.g. chromates · CPC title