Alkene stabilizers for 3-isothiazolone compounds

Abstract: A method of stabilizing a 3-isothiazolone compound against chemical decomposition, comprising introducing a sufficient amount of an alkene to stabilize said 3-isothiazolone compound is disclosed.

Description: This invention relates to the field of stabilization of 3-isothiazolone compounds. 3-Isothiazolone compounds are among the most successful commercial biocides but suffer from a problem regarding chemical instability. Many stabilizers and stabilization methods have been proposed and used, among which are those disclosed in patent applications assigned to Rohm and Haas Company. Metal nitrates (referred to in this field as "salts") have been used to stabilize isothiazolones, but salt stabilization has certain disadvantages. Salt free systems have been proposed by Amick, et al., U.S.-A-4,824,957, but require certain alcohol solvents. The Amick system has disadvantages in certain systems in which the biocide protects a hydrocarbon because the Amick glycols are not miscible in the hydrocarbon. It is an object of this invention to provide an improved stabilization method for 3-isothiazolone compounds, in particular in systems containing hydrocarbons. Accordingly the present invention provides in one aspect a composition containing less than 1% water and comprising at least one 3-isothiazolone compound of the formula wherein Y is hydrogen, an alkyl or substituted alkyl of 1 to 18 carbon atoms, an unsubstituted or halo-substituted alkenyl or alkynyl of 2 to 8 carbon atoms, a cycloalkyl or substituted cycloalkyl of 3 to 12 carbon atoms, an aralkyl or halo-, (C 1 -C 4 ) alkyl-, or (C 1 -C 4 ) alkoxy-substituted aralkyl of to 10 carbon atoms, or an aryl or halo-, (C 1 -C 4 ) alkyl-, or (C 1 -C 4 ) alkoxy-substituted aryl of up to 10 carbon atoms; and R and R 1 are each independently hydrogen, halogen, or a (C 1 -C 4 ) alkyl group, or alternatively may be joined to form a saturated, unsaturated or aromatic 5- or 6-membered fused carbocyclic ring; and an alkene comprising a (C 5 -C 7 ) cyclo- or (C 6 -C 14 ) bicycloalkene, optionally substituted with one or more of (C 1 -C 8 ) alkyl, (C 2 -C 8 ) alkenyl, (C 2 -C 8 ) alkynyl or (C 1 -C 4 ) alkoxy, in an amount effective to stabilise said 3-isothiazolone against chemical decomposition. Another aspect of the invention provides a method of stabilising a 3-isothiazolone as defined above against chemical decomposition, comprising incorporating therewith an effective amount of an alkene as defined in any preceding claim, the weight ratio of isothiazolone to alkene being preferably from 1:100 to 10:1, and more preferably from 1:1 to 5:1. The use of such alkenes to stabilize 3-isothiazolones is also considered part of the invention. A further aspect of the invention comprises a method of preventing or inhibiting the growth of bacteria, fungi, algae or yeast in a locus susceptible or subject to contamination thereby, comprising incorporating into or onto said locus, in an amount effective to adversely affect said growth, a composition as defined above. Suitable alkenes are those selected from (C 5 -C 7 ) cyclo- and (C 6 -C 14 ) bicycloalkenes, optionally substituted with one or more radicals selected from the group consisting of (C 1 -C 8 ) alkyl, (C 1 -C 8 ) alkenyl, (C 1 -C 8 ) alkynyl, and (C 1 -C 4 ) alkoxy. The preferred alkenes are norbornene, cyclohexene, and 1-tetradecene. Preferred weight ratios of 3-isothiazolone compound to alkene are about 1:100 to 10:1, and particularly from 1:1 to 5:1. Preferred compositions are "salt-free," i.e., free of metal salts. Solvents such as ethyl acetate or hydroxy compounds such isopropanol, 2-butanol, dipropylene glycol, and hydrocarbons are suitable. As hydrocarbons, kerosene, xylene and other aromatic hydrocarbons are useful. Preferred concentrations of 3-isothazolone in such solutions are about 0.1 to 20 %, more preferably about 1 to 10 % by weight. The alkenes can be incorporated by simple addition to the 3-isothiazolone biocide compound, or solutions thereof, in amounts sufficient to stabilize the isothiazolone biocide. 3-isothiazolone biocides are especially suitable for protecting systems having both an organic and a water phase, e.g fuel storage tanks, because the biocide is soluble in both phases. The alkenes used in this invention are soluble in the organic phase. An especially suitable locus is motor fuel. Suitable 3-isothiazolone compounds are those which function as biocidal compounds, generally of the formula wherein R, R 1 and Y are as defined above. In particular Y may be a (C 1 -C 18 )alkyl or (C 3 -C 12 )cycloalkyl each optionally substituted with one or more of hydroxy, halo, cyano, alkylamino, dialkylamino, arylamino, carboxy, carbalkoxy, alkoxy, aryloxy, alkylthio, arylthio, haloalkoxy, cycloalkylamino, carbamoxy, or isothiazolonyl; an unsubstituted or halo-substituted (C 2 -C 8 )alkenyl or alkynyl; a (C 7 -C 10 )aralkyl optionally substituted with one or more of halogen, (C 1 -C 4 )alkyl or (C 1 -C 4 )alkoxy; and a (C 6 -C 10 )aryl optionally substituted with one or more of halogen, nitro, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkyl-acylamino, carb(C 1 -C 4 )alkoxy or sulfamyl. Especially suitable 3-isothiazolones are 5-chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone, and 4,5-dichloro-2- n -octyl-3-isothiazolone. The following examples are presented to illustrate certain embodiments of the invention. Example 1 5-Chloro-2-methyl-3-isothiazolone + norbornene in 2-butanol Five samples were prepared by dissolving 5-chloro-2-methyl-3-isothiazolone + norbornene in 2-butanol (20:80) and adding different amounts of norbornene. The samples were put in a 55°C oven and analyzed periodically. Results are shown in Table 1. Stabilization of 5-chloro-2-methyl-3-isothiazolone by norbornene in 2-butanol Norbornene (%) % 5-Chloro-2-methyl-3-isothiazolone remaining after: 0 days 14 days 34 days 0 20.1 22.4 <0.1 4.2 19.0 19.2 20.1 7.9 18.1 18.9 19.9 11.3 17.5 17.8 17.8 16.0 15.8 17.6 22.8 Example 2 5-Chloro-2-methyl-3-isothiazolone + norbornene in 2-propanol Two samples were prepared by dissolving 5-chloro-2-methyl-3-isothiazolone in 2-propanol (20:80). One was used as a control and norbornene was added to the other. Both samples were then put in a 55 °C oven and analyzed periodically. It should be noted that the 2-propanol used has trace amounts of water. Stabilization of 5-chloro-2-methyl-3-isothiazolone by norbornene in 2-propanol Norbornene (%) 5-Chloro-2-methyl-3-isothiazolone remaining after: 0 days 14 days 34 days 0 19.4 19.5 <0.1 8.8 16.9 17.5 17.0 Example 3 Mixture of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone + norbornene in 2-propanol A solution of a mixture of 5-chloro-2-methyl-3-isothiazolone ("5-Chloro") and 2-methyl-3-isothiazolone ("2-Methyl") was prepared in 2-propanol (16.1g). This solution was distributed into 6 vials and varying amounts of norbornene added. They were then put in a 55 °C oven and analyzed periodically. Results are shown in Table 3. Stabilization of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone by norbornene in 2-propanol % Remaining After X Days Norbornene (%) % 2-Methyl % 5-Chloro 0 days 2 days 30 days 0 days 12 days 30 days 0 4.9 0.4 0.7 12.3 0.5 <0.1 3 4.7 4.4 3.9 11.8 12.4 12.8 6.3 4.5 4.3 4.0 11.6 11.6 11.4 11.8 4.2 4.0 3.9 10.7 10.9 10.9 16.7 4.0 3.9 3.7 10.1 10.4 10.3 21.0 3.9 3.8 3.7 9.9 10.2 10.1 Thus both 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3- isothiazolone are completely stabilized with norbornene. Example 4 (Comparative) Mixture of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone + norbornene in 2-propanol with 2% added water A solution of 5-chloro-2-methyl-3-isothiazolone ("5-Chloro") and 2-methyl-3-isothiazolone ("2-Methyl") (3.11 g) was prepared in 2-propanol (12.1g). This solution was distributed in 6 vials. Water (2%) and varying amounts of norbornene was then added. These were then put in a 55°C oven and analyzed periodically. The results are shown in Table 4. Norbornene as a Stabilizer for a mixture of 5-Chloro-2-methyl-3-isothiazolone and 2-Methyl-3-isothiazolone in a Norbornene + 2-Propanol + Water System Norbornene (%) 2-Methyl (%) 5-Chloro (%) 0 days 7 days 21 days 0 days 7 days 21 days 0 1.7 0.22 - 12.2 0.23 - 1.2 2.3 0.14 - 16.7 0.09 - 2.3 2.3 0.08 - 16.5 0.09 - 4.2 2.2 0.10 - 16.2 0.07 - 8.1 2.2 0.10 - 15.7 <0.1 - 14.1 2.0 0.97 0.1 14.7 13.5 <0.1 These results indicate that the presence of ∼2% water in the solution overwhelms the stabilization properties of norbornene. Some stability is realized when an approximately equivalent weight percent of norbornene to AI is used. Example 5 Stabilization of a mixture of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone with norbornene in dipropylene glycol containing 0.5 % water To 19.9 g of dipropylene glycol was added 0.1 g of water. To this was added 5-chloro-2-methyl-3-isothiazolone ("5-Chloro") and 2-methyl-3-isothiazolone ("2-Methyl"). This solution was distributed into 6 vials and varying amounts of norbornene was added. The vials were put in a 55°C oven and analyzed periodically. Results are shown in Table 5. Stabilization of a mixture of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone with norbornene in DPG (0.5 % water) Norbornene (%) 2-Methyl (%) 5-Chloro (%) 0 days 14 days 30 days 0 days 14 days 30 days 0 4.5 0.6 - 11.7 0 0 1.6 4.4 0.18 - 11.7 0 - 3.2 4.3 3.3 0.6 11.5 10.4 0.1 6.5 4.2 3.7 2.7 11.2 10.8 10.1 9.0 4.1 3.7 3.3 11.0 10.7 10.4 14.3 4.4 3.6 3.3 10.5 10.2 9.7 Example 6 Cyclohexene as a stabilizer for a mixture of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone. A solution of 5-chloro-2-methyl-3-isothiazolone ("5-Chloro") and 2-methyl-3-isothiazolone ("2-Methyl") (3.6 g) was dissolved in 17 g of dipropylene glycol. This solution was distributed into 6 vials (3 g each) and varying amounts of cyclohexene was added. The vials were then heated at 55 °C and analyzed periodically. Results are shown in Table 6. Stabilization of a mixture of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone by cyclohexene in DPG Cyclohexene (%) 2-Methyl (%) 5-Chloro (%) 0 days 13 days 30 days 0 days 13 days 30 days 0 5.0 0.49 - 11.4 <0.1 - 3.2 4.7 0.35 - 10.1 0.19 - 6.8 4.6 0.23 - 10.9 0.10 - 9.1 4.5 0.95 0.66 10.6 8.6 0.0 11.8 4.4 0.59 0.62 10.5 7.9 0.0 16.7 4.3 2.6 0.46 10.2 9.0 0.0 These results indicate that cyclohexene functions as a stabilizer. Since the isothiazolone batch used was already dark in colour (later analysis indicated 5% decomposition), the data may not reflect the results expected from a pure batch of starting material. Example 7 (Comparative) Attempted stabilization of a mixture of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone with 3,4-dihydro-2H-pyran (DHP) in 2-propanol. A solution of 5-chloro-2-methyl-3-isothiazolone ("5-Chloro") and 2-methyl-3-isothiazolone ("2-Methyl") (3.6 g) was prepared in 2 propanol (16.1 g) containing water as an impurity and distributed into 6 vials. Varying amounts of DHP was added and the vials put in a 55 °C oven. Active ingredient analysis was done periodically. As the following results (Table 7) indicate, DHP imparts no stability to isothiazolones in alcohol-water systems. It is expected that DHP would stabilize the isothiazolone in hydrocarbon systems such as fuel. 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone + DHP in 2-propanol. DHP (%) 2-Methyl (%) 5-Chloro (%) 0 days 12 days 0 days 12 days 0 5.3 0.4 11.6 0.4 3.5 5.1 0.7 11.1 0.1 6.3 5.0 0.6 10.8 0.1 11.8 4.2 0.7 10.2 0.6 16.7 4.4 0.7 9.7 0.5 21.1 4.2 0.6 9.2 0.4 Example 8 (Comparative) Other olefins that were tested but failed to show any stabilizing properties in 2-propanol/water systems were cyclooctene, dicylopentadiene and indene. It is expected that these alkenes would function to stabilize the biocide in non-aqueous systems, however. Example 9 In a formulation comprised of 3 parts by weight of a mixture of 5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone in a 3:1 ratio, 94 parts by weight of a mixture of kerosene (64 parts by weight) and diethylene glycol butyl ether (20 parts by weight), 3 parts by weight norbornene stabilizer was added. The control had no norbornene. After eight weeks at 55°C, the control had no 5-chloro-2-methyl-3-isothiazolone left, whereas the composition of the invention had 100% 5-chloro-2-methyl-3-isothiazolone remaining. Example 10 Example 9 was repeated except using 1 part by weight norbornene. No loss of 5-chloro-2-methyl-3-isothiazolone was observed after eight weeks at 55° C. Example 11 Example 9 was repeated except using 1-tetradecene as stabilizer resulting in 86% 5-chloro-2-methyl-3-isothiazolone remaining after four weeks at 55° C and complete loss by eight weeks. Although specific embodiments and examples have been described herein, these have been provided by way of explanation and are not intended to limit the scope of the claims.

Claims: Composition containing less than 1% water and comprising at least one 3-isothiazolone compound of the formula wherein Y is hydrogen, an alkyl or substituted alkyl of 1 to 18 carbon atoms, an unsubstituted or halo-substituted alkenyl or alkynyl of 2 to 8 carbon atoms, a cycloalkyl or substituted cycloalkyl of 3 to 12 carbon atoms, an aralkyl or halo-, (C 1 -C 4 ) alkyl-, or (C 1 -C 4 ) alkoxy-substituted aralkyl of to 10 carbon atoms, or an aryl or halo-, (C 1 -C 4 ) alkyl-, or (C 1 -C 4 ) alkoxy-substituted aryl of up to 10 carbon atoms; and R and R 1 are each independently hydrogen, halogen, or a (C 1 -C 4 ) alkyl group, or alternatively may be joined to form a saturated, unsaturated or aromatic 5- or 6-membered fused carbocyclic ring; and an alkene comprising a (C 5 -C 7 ) cyclo- or (C 6 -C 14 ) bicycloalkene, optionally substituted with one or more of (C 1 -C 8 ) alkyl, (C 2 -C 8 ) alkenyl, (C 2 -C 8 ) alkynyl or (C 1 -C 4 ) alkoxy, in an amount effective to stabilise said 3-isothiazolone against chemical decomposition. Composition according to claim 1 wherein the weight ratio of isothiazolone to alkene is from 1:100 to 10:1, preferably from 1:1 to 5:1. Composition according to claim 1 or 2 wherein the alkene is norbornene, cyclohexene, cyclohexadiene or tetradecene. Composition according to any preceding claim wherein said 3-isothiazolone is 5-chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone, or 4,5-dichloro-2- n -octyl-3-isothiazolone. Composition according to any preceding claim which is free of metal salts. Composition according to any preceding claim further comprising a solvent which does not interfere with the stabilizing action of said alkene, which solvent is preferably isopropanol, 2-butanol, dipropylene glycol, ethyl acetate, or a hydrocarbon, preferably kerosene, xylene or another aromatic hydrocarbon. Method of stabilising a 3-isothiazolone as defined in any preceding claim against chemical decomposition in a composition comprising less than 1% water, comprising incorporating therewith an effective amount of an alkene as defined in any preceding claim, the weight ratio of isothiazolone to alkene being preferably from 1:100 to 10:1, and more preferably from 1:1 to 5:1. Method of preventing or inhibiting the growth of bacteria, fungi, algae or yeast in a locus susceptible or subject to contamination thereby, comprising incorporating into or onto said locus, in an amount effective to adversely affect said growth, a composition as defined in any of claims 1 to 6. Method according to claim 8 wherein said locus is an aqueous medium, a cosmetic formulation, fabric, leather, paper, or wood, a solid protective or decorative film, or a fuel composition which comprises water as impurity. Use of an alkene as defined in any of claims 1 to 3 to stabilize 3-isothiazolones against chemical decomposition in compositions comprising less than 1% water.

Inventors: GHOSH TIRTHANKAR, MATTOX JOHN ROBERT, GHOSH, TIRTHANKAR, MATTOX, JOHN ROBERT
Applicants: ROHM & HAAS, ROHM AND HAAS COMPANY
Application year: 1992
Main classification: C07D275
IPC codes: A01N43, A61K8, A01N25, D21H17, D06M13, D06M101