Antimicrobial solution of formaldehyde substituted hydantoin and process for preparation

• US 5,616,722 A
• Filed: 12/05/1995
• Issued: 04/01/1997
• Est. Priority Date: 12/05/1995
• Status: Expired due to Term

• Current Assignee: Rhodia Operations (Solvac SA)
• Original Assignee: Mcintyre Group, Ltd. (Solvac SA)
• Inventors: Zehner, Darrell J., Otterson, Richard J., Schoenberg, Thomas G.
• Primary Examiner(s): Higel, Floyd D.
• Application Number:
  US08/567,150
• Time in Patent Office: 483 Days
• Field of Search: 548/319.1, 514/389
• US Class Current: 548/319.1
• CPC Class Codes: A01N 2300/00 Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
• CPC Class Codes: A01N 25/02 containing liquids as carriers, diluents or solvents
• CPC Class Codes: A01N 31/04 Oxygen or sulfur attached to an aliphatic side-chain of a carbocyclic ring system
• CPC Class Codes: A01N 37/40 having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
• CPC Class Codes: A01N 39/00 Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or , e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
• CPC Class Codes: A01N 43/50 1,3-Diazoles; Hydrogenated 1,3-diazoles
• CPC Class Codes: A61K 31/4166 having oxo groups directly attached to the heterocyclic ring, e.g. phenytoin
• CPC Class Codes: C07D 233/74 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to other ring members

Abstract

A method of preparing a formaldehyde substituted hydantoin in the form of a liquid antimicrobial preservative solution is disclosed. The inventive solution prepared by the disclosed method comprises a condensation product of a 5,5-disubstituted hydantoin and formaldehyde prepared in the presence of an antimicrobial liquid phenylic or benzylic alcohol. The inventive solution inhibits or retards microbial growth when an effective microbial inhibiting amount is subsequently added to a medium capable of supporting undesirable microbial growth. Preferably the inventive solution contains 1,3-dimethylol-5,5-dimethyl hydantoin prepared in the presence of phenoxyethanol and including an effective antimicrobial amount of at least one paraben preservative prepared by an embodiment of the disclosed method.

Claims

1. A method for preparing an antimicrobial solution of a formaldehyde substituted hydantoin comprising the steps of sequentially:

(a) dissolving a formaldehyde selected from the group consisting or paraformaldehyde and formalin in at least one liquid aromatic alcohol having the formula;

##STR2## where R is selected from the group consisting of --CH₂ OH, --OCH₂ --OH, --OCH₂ CH₂ OH, --CH₂ CH₂ OH, --OC₃ H₆ OH, and --C₃ H₆ OH to provide a liquid medium containing at least about 2 weight percent 100 weight percent total formaldehyde on a calculated liquid medium basis;

(b) heating said liquid medium to a temperature in the range of about 35°

to about 55°

C. to provide a heated liquid medium;

(c) admixing into said heated liquid medium, a 5,5-disubstituted hydantoin wherein each such substituent is independently selected from the class consisting of phenyl and lower alkyl groups containing less than 7 carbon atoms per group to provide a reaction mixture, the amount of said hydantoin so admixed being sufficient to produce in said reaction mixture an initial calculated mole ratio of formaldehyde to said hydantoin of about 1;

1 to about 3;

1;

(d) further heating under autogenous conditions said reaction mixture to a temperature in the range of about 80°

to about 110°

C. and maintaining said temperature until the reaction between said paraformaldehdye and said hydantoin is substantially complete, thereby to attach methylol functional groups to at least one of the two nitrogen atoms of the ring of said hydantoin, the amount of free formaldehyde present in said resulting reaction mixture being below about 2 weight percent based on the total weight of said resulting reaction mixture; and

(e) thereafter cooling said resulting reaction mixture to provide said antimicrobial solution, said antimicrobial solution being characterized by;

(1) containing a condensation product of said paraformaldehyde and said hydantoin wherein methylol functional groups are attached to at least one of the two nitrogen atoms of the ring of said hydantoin; and

(2) having the capacity to inhibit and/or retard the growth of microorganisms when an effective antimicrobial amount of said antimicrobial solution is subsequently included in a medium capable of supporting growth of said microorganisms.

2. The process of claim 1 wherein said antimicrobial solution additionally contains about 1 to about 15 weight percent water based on total weight of said antimicrobial solution, said water having been added in at least one of said steps (a) through (e).

3. The process of claim 1 wherein said antimicrobial solution additionally contains from greater than 0 to about 25 weight percent of at least one dissolved paraben ester, said paraben ester having been added in at least one of said steps (a) through (e).

4. The process of claim 1 wherein said antimicrobial solution additionally contains from greater than 0 to about 25 weight percent of at least one dissolved paraben ester, said paraben ester having been added in at least one of said steps (a) through (e).

5. The process of claim 4 wherein said paraben ester is added in said step (3) by first cooling said reaction mixture to a temperature in the range of about 40°

to about 50°

C., then dissolving said paraben ester in said so partially cooled reaction mixture, and thereafter cooling said resulting reaction mixture to ambient temperature.

6. The process of claim 1 wherein said antimicrobial solution is filtered.

7. The process of claim 1 wherein said antimicrobial solution is adjusted by addition thereto of an aqueous acidifying or alkalizing agent in an amount sufficient to produce a dilution pH in the range of about 6 to about 8.5.

8. The process of claim 2 wherein:

(a) said liquid aromatic alcohol is phenoxyethanol;

(b) said 5,5-disubstituted hydantoin is 5,5-dimethyl hydantoin; and

(c) said calculated mole ratio of said formaldehyde to said hydantoin is such that said condensation product comprises at least about 10 weight percent 1,3-dimethylol-5,5-dimethyl hydantoin.

9. The process of claim 8 wherein said antimicrobial solution additionally contains about 3 to about 15 weight percent of dissolved paraben esters.

10. The antimicrobial solution produced by the process of claim 1, and wherein on a 100 weight percent solution basis:

(a) the amount of said aromatic alcohol is in the range of about 30 to about 80 weight percent; and

(b) the amount of said methylol substituted 5,5-disubstituted hydantoin is in the range of about 30 to about 80 weight percent.

11. The antimicrobial solution produced by the process of claim 4, and wherein on a 100 weight percent solution basis:

(a) the amount of said aromatic alcohol is in the range of about 40 to about 60 weight percent;

(b) the amount of said methylol substituted 5,5-disubstituted hydantoin is in the range of about 20 to about 50 weight percent;

(c) the amount of said water is in range of about 2 to about 15 weight percent; and

(d) the amount of said paraben ester is in the range of about 2 to about 20 weight percent.

12. The antimicrobial solution produced by the process of claim 9 and wherein on a 100 weight percent solution basis:

(a) the amount of said phenoxyethanol is in the range of about 45 to about 55 weight percent;

(b) the total amount of said dimethylol substituted 5,5-dimethyl hydantoin is in the range of about 25 to about 35 weight percent, and the formaldehyde condensate therewith contains a mole ratio of formaldehyde to 5,5-dimethyl hydantoin in the range of about 1.5;

1 to about 2.1;

1 and a content of 1,3-dimethylol-5,5-dimethyl hydantoin of at least about 10 weight percent; and

(c) the amount of said water is in the range of about 6 to about 10 weight percent.

13. A method of inhibiting or retarding microbial growth in a medium capable of supporting microorganism growth, said method comprising incorporating into said medium an antimicrobially effective amount of said antimicrobial solution of claim 10.