Monomeric and polymeric cyclic amine and N-halamine compounds

• US 5,889,130 A
• Filed: 07/31/1997
• Issued: 03/30/1999
• Est. Priority Date: 03/12/1993
• Status: Expired due to Fees

• Current Assignee: Auburn University
• Original Assignee: Auburn University
• Inventors: Sun, Gang, Worley, Shelby D., Sun, Wanying, Chen, Tay-Yuan
• Primary Examiner(s): Smith, Jeffrey
• Assistant Examiner(s): Cheng, Wu C.
• Application Number:
  US08/903,861
• Time in Patent Office: 607 Days
• Field of Search: 525/326.8, 526/261, 526/262
• US Class Current: 526/261
• CPC Class Codes: A01N 59/00 Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
• CPC Class Codes: C07D 233/74 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to other ring members
• CPC Class Codes: C07D 251/20 with no nitrogen atoms directly attached to a ring carbon atom
• CPC Class Codes: C08F 12/26 Nitrogen
• CPC Class Codes: C08F 8/30 Introducing nitrogen atoms or nitrogen-containing groups
• CPC Class Codes: C08F 8/48 Isomerisation; Cyclisation
• CPC Class Codes: Y02W 10/37 using solar energy

Abstract

Cyclic amine monomers and polymers and N-halamine biocidal polymer compounds are provided. Methods of making and using the same wherein the functional groups unhalogenated or halogenated hydantoins, triazine diones, imidazolidinones, and pyrimidinones are substituted onto inexpensive polymer units such as polystyrene, polyethylene, and modified polymethacrylamide are provided. The cyclic amine monomers and polymers can be utilized to form the biocidal N-halamine polymers. These N-halamine polymers are stable, insoluble biocides which release only small amounts of free halogen and other impurities. They can be useful as disinfectants for potable water, swimming pools, hot tubs, industrial water systems, cooling towers, air-conditioning systems, gas streams, paints, oils, ointments, fabrics, rubber materials, sterile bandages, coatings, hard surfaces, liners of containers, and the like.

Claims

1. A method of preparing a cyclic amine polymer comprising the steps of

a) heating a poly-4-vinylacetophenone under vacuum to crack it into the corresponding monomer;

b) converting the aceto moiety on the monomer to a hydantoin or triazine-2,4-dione moiety to form a 4-vinylphenyl hydantoin or 4-vinylphenyl triazine-2,4-dione monomer; and

c) polymerizing the 4-vinylphenyl hydantoin or 4-vinylphenyl triazine-2,4-dione monomer to form a cyclic amine polymer.

2. The method of claim 1, wherein the 4-vinylphenyl hydantoin or 4-vinylphenyl triazine-2,4-dione monomer is copolymerized with at least one other type monomer to form a copolymer.

3. A method of preparing a biocidal cyclic N-halarnine polymer comprising the step of halogenating the polymer produced by the method of claim 1 with at least one halogen selected from the group consisting of chlorine and bromine.

4. A method of preparing a biocidal cyclic N-halamine polymer comprising the step of halogenating the copolymer produced by the method of claim 2 with at least one halogen selected from the group consisting of chlorine and bromine.

5. A method of preparing a biocidal cyclic N-halamine polymer comprising the step of halogenating the copolymer produced by the method of claim 4 with at least one halogen selected from the group consisting of chlorine and bromine.

6. The method of claim 1, wherein the poly-4-vinylacetophenone is unsubstituted at the vinyl carbon linked to the acetophenone.

7. The method of claim 1, wherein the poly-4-vinylacetophenone is substituted at the vinyl carbon linked to the acetophenone with from C₁ to C₄ alkyl.

8. The method of claim 1, wherein the poly-4-vinylacetophenone is substituted with a methyl group.

9. The method of claim 2, wherein the other type monomer is selected from the group consisting of acrylonitrile, styrene, acrylamide, methacrylamide, methyl methacrylate, ethylene, propylene, butylenes, butadiene and a cyclic amine monomer comprising a single monomeric unit of the structure:

##STR12## wherein R¹ is selected from the group consisting of hydrogen and from C₁ to C₄ alkyl;

R¹⁰ is a bond or parasubstituted phenyl; and

R¹¹ is a cyclic amine unit of a 5- to 6-membered heterocyclic ring in which the members of the ring are all selected from the group consisting of at least 3 carbon atoms, from 1 to 3 nitrogen heteroatoms, and from 0 to 1 oxygen heteroatom;

wherein R¹⁰ is attached to a linkage carbon of R¹¹, wherein said linkage carbon of R¹¹ is a carbon located on the ring of R¹¹ and is substituted with a substituent selected from the group consisting of C₁ -C₄ alkyl, benzyl, and alkyl-substituted benzyl;

wherein from 0 to 2 non-linkage carbon members are a carbonyl group;

wherein from 0 to 1 non-linkage carbon member is substituted with a moiety selected from the group consisting of C₁ -C₄ alkyl, phenyl, alkyl-substituted phenyl, benzyl, alkyl-substituted benzyl, pentamethylene in spirosubstituted form and tetramethylene in spirosubstituted form.