Drug – bio-affecting and body treating compositions – Preparations characterized by special physical form – Biocides; animal or insect repellents or attractants
Reexamination Certificate
1994-09-22
2001-09-25
Venkat, Jyothsna (Department: 1615)
Drug, bio-affecting and body treating compositions
Preparations characterized by special physical form
Biocides; animal or insect repellents or attractants
C525S326800, C525S328200, C525S328600, C525S333200, C525S333300, C525S333600
Reexamination Certificate
active
06294185
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to biocidal polymers for disinfection of halogen-sensitive organisms and the precursor polymers and monomers from which the biocidal polymers can be prepared. In particular, biocidal polymers of cyclic N-halamines and their precursor cyclic amine monomers and polymers are provided. Additionally provided are methods of making such monomers and polymers. The biocidal cyclic N-halamine polymers are useful for disinfection of habitats such as air and gas streams, water such as in potable water supplies, swimming pools, industrial water systems and air conditioning systems, organic fluids, hard surfaces, and elastomeric, plastic and fabric materials.
2. Background Art
Current disinfectants which are in use for purposes such as disinfecting water, as can be used in potable water supplies, swimming pools, hot tubs, industrial water systems, cooling towers, spacecraft, waste water treatment plants, air conditioning systems, military field units, camping expeditions, and in other sanitizing applications, as well as of organic fluids such as oils, paints, coatings, and preservatives, and in various medicinal applications all have serious limitations. Sources of the most commonly used disinfectant free halogen (chlorine, bromine, or iodine) are effective disinfectants, but free halogen is corrosive toward materials, toxic to marine life, reactive with organic contaminants to produce toxic trihalomethanes, irritating to the skin and eyes of humans, and relatively unstable in water, particularly in the presence of sunlight or heat. Ozone and chlorine dioxide are also effective disinfectants, but they are not persistent in water such that they have to be replenished frequently; they also may react with organic contaminants to produce products having unknown health risks. Combined halogen compounds such as the commercially employed hydantoins and cyanurates as well as the recently discovered oxazolidinones (Kaminski et al., U.S. Pat. Nos. 4,000,293 and 3,931,213) and imidazolidinones (Worley et al., U.S. Pat. Nos. 4,681,948; 4,767,542; 5,057,612; 5,126,057) are much more stable in water than are free halogen, ozone, and chlorine dioxide, but in general they require longer contact times to inactivate microorganisms than do the less stable compounds mentioned.
A characteristic which all of the aforementioned disinfectants have in common is that they are soluble to some extent in water. Thus humans or animals drinking or contacting the water are exposed to the compounds and products of their reactions with contaminants which could cause health risks in some situations.
Polymeric quaternary ammonium anionic-exchange resins have been known for many years (see for example U.S. Pat. Nos. 2,595,225; 2,923,701; 2,980,657; 2,980,634; 3,147,218; 3,288,770; 3,316,173; 3,425,790; 3,462,363; 3,554,905; 3,539,684; 3,817,860; 3,923,665; 4,187,183; 4,349,646; 4,420,590). The “polyquats” have important limitations. Most are soluble in water which means that they could pose a threat to humans or animals drinking or contacting water containing them. The insoluble polyquats tend to release fairly high concentrations of free halogen, and the most effective of these release the triiodide ion, which is undesirable with respect to dietary intake for certain groups of the population (U.S. Pat. No. 4,349,646). Such compounds are also generally expensive to manufacture.
Functionally modified poly(styrene-divinylbenzene) compounds containing N-chlorinated sulfonamide moieties have been prepared and shown to have biocidal properties (see for example Emerson et al.,
Ind. Eng. Chem. Prod. Res. Dev.,
17:269 (1978);
Ind. Eng. Chem. Res.,
29:448 (1990);
Ind. Eng. Chem. Res.,
30:2426 (1991)). However, these N-halamines do not contain the N—Cl or N—Br moieties in a cyclic ring and are hence not expected to be as stable toward release of free halogen as those to be described herein. In fact, they are known to release greater than 1 milligram per liter of free chlorine when the pH of water flowing through them is greater than 7.0.
Therefore, there is a great need for insoluble broad-spectrum disinfectants which kill microorganisms upon contact, but which do not leach undesirable organic contaminants into the medium to be disinfected, and which maintain a very low concentration of free halogen (less than 1 milligram per liter) in such medium. There is also a need for methods to treat many various habitats in which halogen-sensitive microorganisms dwell.
This invention solves this need by providing precursor cyclic amine polymers and precursor cyclic amine monomers, and methods for preparing them, for use in preparing biocidal polymers and copolymers such as cyclic N-halamine polymers. Also provided are methods of preparing cyclic N-halamine biocidal polymers.
SUMMARY OF THE INVENTION
The present invention relates to a cyclic amine polymer comprising a monomeric repeating unit of the structure:
wherein R
1
is selected from the group consisting of hydrogen and from C
1
to C
4
alkyl; n is at least 2; R
10
is a bond or parasubstituted phenyl; and R
11
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 R
10
is attached to a linkage carbon of R
11
, wherein said linkage carbon of R
11
is a carbon located on the ring of R
11
and is substituted with a substituent selected from the group consisting of C
1
-C
4
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 C
1
-C
4
alkyl, phenyl, alkyl-substituted phenyl, benzyl, alkyl-substituted benzyl, pentamethylene in spirosubstituted form and tetramethylene in spirosubstituted form;
or the monomeric repeating unit is of the structure:
wherein R
1
is selected from the group consisting of hydrogen and C
1
to C
4
alkyl; and n is at least 2.
The invention additionally provides a cyclic amine monomer comprising a single mononomeric unit of the structure:
wherein R
1
is selected from the group consisting of hydrogen and from C
1
to C
4
alkyl; R
10
is a bond or parasubstituted phenyl; and R
11
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 R
10
is attached to a linkage carbon of R
11
, wherein said linkage carbon of R
11
is a carbon located on the ring of R
11
and is substituted with a substituent selected from the group consisting of C
1
-C
4
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 C
1
-C
4
alkyl, phenyl, alkyl-substituted phenyl, benzyl, alkyl-substituted benzyl, pentamethylene in spirosubstituted form and tetramethylene in spirosubstituted form. The nitrogen heteroatoms in these monomers can be halogenated.
The instant invention further provides a biocidal polymer comprising a monomeric repeating unit of the structure:
wherein R
1
is selected from the group consisting of hydrogen and from C
1
to C
4
alkyl; n is at least 2; R
10
is a bond or parasubstituted phenyl; and R
11
is a cyclic N-halamine 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 R
10
is attached to a linkage carbon of R
11
, wherein said linkage carbon of R
11
is a carbon located on the ring of R
11
and is substituted with a substituent selected from the group consisting of C
1
-C
4
alkyl, benzyl, a
Chen Tay-Yuan
Sun Gang
Sun Wanying
Worley Shelby D.
Auburn University
Christensen O'Connor Johnson & Kindness PLLC
Venkat Jyothsna
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