Method for preparing bromourea

• US 9,133,109 B2
• Filed: 09/19/2011
• Issued: 09/15/2015
• Est. Priority Date: 09/21/2010
• Status: Active Grant

• Current Assignee: Bromine Compounds Limited (ICL Group Ltd.)
• Original Assignee: Bromine Compounds Limited (ICL Group Ltd.)
• Inventors: Antebi, Shomo, Feldman, David
• Primary Examiner(s): Zucker, Paul A
• Assistant Examiner(s): LUDERER, MARK R
• Application Number:
  US13/823,757
• Publication Number:
  US 20130178532A1
• Time in Patent Office: 1,457 Days
• Field of Search: 564/32, 514/588
• US Class Current: 1/1
• CPC Class Codes: A01N 33/08 containing oxygen or sulfur
• CPC Class Codes: A01N 47/28 Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< isoureas, isothioureas A01N47/42
• CPC Class Codes: A01N 59/00 Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
• CPC Class Codes: C07C 273/1863 from urea

Abstract

The invention provides a process for manufacturing biocidal compositions containing bromourea derivatives, including the reaction of salts or adducts of the urea derivatives with an oxidizer.

Claims

1. A method for manufacturing bromourea comprising

(i) providing an aqueous solution comprising a salt or adduct of urea of the general structure A-U, where A stands for an acid selected from HBr or HCl and U stands for urea,

(ii) providing an aqueous solution of an oxidizer, and

(iii) combining at least two liquid streams, one of which comprises the solution provided in step (i) and the other one comprises the solution provided in step (ii) whereby forming bromourea or chlorourea and adding to said streams a solution comprising bromide source if said acid is HCl,

thereby obtaining an acidic composition comprising said bromourea wherein said urea is in a molar excess over said acid, and the molar ratio of said acid to said oxidizer is at least 1.0, said solutions being stored as stable precursors and being optionally diluted before combining said streams in situ, and wherein the active bromine in the combined streams, measured as the total chlorine by iodometry is up to 5%.

2. The method according to claim 1, wherein said urea is in at least three fold molar excess over said acid and at least ten fold excess over said oxidizer.

3. The method according to claim 1, wherein said urea is in about fifteen fold molar excess over said acid, and wherein said molar ratio of said acid to said oxidizer is at least 2.0.

4. The method according to claim 1 where A stands for HCl, comprising

i) reacting said salt or adduct with NaOCl, thereby forming chlorourea, and

ii) adding to said chlorourea a solution comprising NaBr, thereby obtaining a composition comprising bromourea.

5. The method according to claim 1 where A stands for HBr or a mixture of HBr with HCl, comprising reacting said salt or adduct with NaOCl, thereby forming bromourea and obtaining a composition comprising bromourea.

6. The method according to claim 1, wherein said oxidizer is selected from NaOCl, LiOCl, Ca(OCl)₂, ClO₂, ozone, urea hydroperoxide, hydrogen peroxide, hydrogen peroxide precursors, percarbonates, perborates, peracetates or peroxycarboxylic acids, persulfates, and electrolytically prepared species.

7. The method according to claim 1, comprising combining at least two liquid streams, in any order, one of which comprises an aqueous solution of said oxidizer.

8. The method according to claim 1, comprising combining at least two liquid streams, in any order, one of which comprises an aqueous solution of urea hydrochloride or urea hydrobromide.

9. The method according to claim 1, comprising combining at least two liquid streams, in any order, one of which comprises chlorourea or NaOCl.

10. The method according to claim 1, comprising combining at least two liquid streams, in any order, one of which comprises an aqueous solution containing bromide anion.

11. The method according to claim 1, comprising

i) reacting a salt or adduct of urea of the general structure A-U, where A stands for HCl and U stands for urea with an oxidizer comprising NaOCl, while stirring a mixture comprising urea, HCl, and NaOCl, wherein said urea is in a molar excess over said HCl, and said HCl is in a molar excess over said NaOCl, thereby providing a mixture comprising chlorourea;

and

ii) reacting said mixture comprising chlorourea with a bromide source, thereby providing a mixture comprising bromourea.

12. The method according to claim 1, comprising

i) electrolytically treating a salt or adduct of urea of the general structure A-U, where A stands for HCl or HBr, and U stands for urea, thereby providing a mixture comprising chlorourea or bromourea;

and optionally

ii) reacting said mixture with a bromide source thereby converting said chlorourea to bromourea.

13. A biocidal and antibiofouling composition containing a bromourea manufactured according to claim 1, comprising urea partially in non-brominated form and partially in brominated form, wherein the non-brominated part of urea is in at least three fold molar excess over said brominated part of said urea.

14. The biocidal and antibiofouling composition according to claim 13, wherein said urea is in at least four fold molar excess over said acid and in at least ten fold molar excess over said oxidizer.

15. The biocidal and antibiofouling composition according to claim 13, obtained in a process comprising reacting a salt or adduct of urea of the general structure A-U, where A stands for acid selected from HCl or HBr, and U stands for urea, with an oxidizer comprising NaClO, in a mixture containing urea, said acid, and said oxidizer, wherein said urea is in at least ten fold molar excess over said acid and in at least twenty fold molar excess over said oxidizer.

16. The biocidal and antibiofouling composition according to claim 13, comprising an aqueous mixture of urea, brominated urea, and chloride, wherein said urea is in at least ten fold molar excess over said brominated urea, and in at least ten fold molar excess over said chloride.

17. The biocidal and antibiofouling composition according to claim 13, comprising an aqueous mixture of urea, bromourea, and chloride, wherein said urea is in at least fifteen fold molar excess over said bromourea, and in at least fifteen fold molar excess over said chloride.

18. The biocidal and antibiofouling composition according to claim 13 comprising bromourea obtained by reacting aqueous urea with a hydrohalic acid and sodium hypochlorite in a molar excess of urea over the acid of at least 10.

19. A method of cleaning industrial equipment, irrigation pipes, and agricultural equipment, comprising contacting the surfaces or volumes to be cleaned with a biocidal and antifouling composition according to claim 14.

20. The method according to claim 1 wherein the pH in the combined streams is from 1.15 to 2.3.