Polymeric quaternary ammonium trihalides useful as microbicides, sanitizers and disinfectants

Abstract: Polymeric quaternary ammonium trihalides, preferably triiodides, and use of polymeric quaternary ammonium trihalides to inhibit the growth of microorganisms in aquatic systems, to disinfect or sanitize surfaces and to disinfect the skin of animals, including humans.

Description: This invention encompasses polymeric quaternary ammonium trihalides, particularly triiodides, and their use as general microbicides, particularly as bactericides and fungicides, for aqueous systems, as surface, particularly hard surface, disinfectants or sanitizers, and as disinfectants for animal skin, including the skin of humans. Polymeric quaternary ammonium compounds (also known as ionene polymers or polymeric quats) containing chlorides and bromides as anions have been shown to be aquatic bactericides and algicides (U.S. Patent Nos. 3,874,870, 3,931,319, 4,027,202, and 4,581,058). In fact, Busan 77 polymer, an ionene chloride, is sold commercially as an algicide and bactericide for various aquatic systems, such as water cooling devices, swimming pools, and fresh water holding tanks. However, these polymeric quats could stand improvement. In particular, it would be significant to develop polymeric quats that are even better fungicides, and also are faster in killing bacteria. The present invention can constitute such an improvement and describes compounds which contain trihalide as the counter ion to the quaternary nitrogens in the polymer chain and which are useful as aquatic microbicides, disinfectants for human skin, and surface disinfectants or sanitizers. Representative trihalides useful in the present invention include Br₃-, I₃-, BrI₂-, C1I₂-, C1Br₂- and Br₂I-. I₃- is the preferred trihalide. U.S. Patent Nos. 3,778,476 and 3,989,336 describe the preparation of some of these compounds. The compounds of these two patents are proposed therein for use in coating substrates to provide an antibacterial layer for an application such as surgical sutures. The present invention is the method of using ionene trihalides to disinfect or sanitize surfaces and provide microorganism control in aquatic systems and also includes some novel trihalide compounds. The inventors have discovered a new method of inhibiting the growth of a microorganism in aquatic systems susceptible to the growth of such microorganisms, a new method of disinfecting or sanitizing surfaces and a new method of disinfecting skin. The methods use ionene trihalides, preferably ionene triiodides, which can prevent the proliferation of microorganisms, such as bacteria, fungi, and algae, in various systems which contain or move water. Thus one feature of the invention provides polymeric quaternary ammonium compounds having the formula wherein X₁, X₂ and X₃ are each a halogen atom and can all be the same halogen or different halogens and wherein R¹ and R², which can be the same or different, each represent an alkyl group having from 1 to 20 carbon atoms optionally substituted by a hydroxyl group, a benzyl group, or a benzyl group bearing on the benzene moiety one alkyl group having from 2 to 20 carbon atoms; A is a divalent hydrocarbon radical containing 1 to 10 carbon atoms or a divalent hydrocarbon radical containing 1 to 10 carbon atoms and also containing an oxygen atom as an ether group; B is a divalent hydrocarbon radical containing 1 to 10 carbon atoms, said divalent hydrocarbon radical being substituted by at least one hydroxyl group or a substituent substituted by at least one hydroxyl group; n is a whole number from 2 to 30, with the proviso that if A and B are identical, then n is a whole number from 1 to 15; and wherein the polymer may be capped on one or both ends with a quaternary ammonium group of formula wherein X₁, X₂ and X₃ are as defined above and wherein R³, R⁴ and R⁵, which can all be the same or different, are alkyl groups having from 1 to 20 carbon atoms optionally substituted by a hydroxyl group, or R³ and R⁴ taken together with the nitrogen atom to which they are attached form a saturated heterocyclic ring having from 5 to 7 ring atoms. Substituent A may be substituted or unsubstituted. Preferably, however, A is substituted by at least one hydroxyl group or a substituent substituted by at least one hydroxyl group. A preferred class of ionene trihalides are those in which A is an alkylene radical and B is an alkylene, aryl, arylalkylene or alkylenearylalkylene radical. Preferred substituents for both the A and B moieties, which can be identical or different, include C n H 2n OH, wherein n ranges from 1 to 10, and more preferably CH₂OH, and also hydroxyaryl, and more preferably hydroxyphenyl. The most preferred compounds are poly [(dimethyliminio)-2-hydroxypropylene triiodide] of the formula wherein A and B are identical and n is from 1 to 15; poly[oxyethylene-(dimethyliminio)hydroxypropylene (dimethyliminio)ethylene di(triiodide)] of the formula wherein n is from 2 to 30; and poly[2-hydroxyethylene(dimethyliminio) ethylene (dimethyl-iminio)-methylene di(triiodide)] of the formula wherein n is from 2 to 30. The present invention also provides a method for inhibiting the growth of a microorganism in an aqueous liquid susceptible to growth of said microorganism which comprises the step of adding to said aqueous liquid a polymeric quaternary ammonium compound as hereinbefore defined in an amount effective to inhibit the growth of said microorganism. X₁, X₂ and X₃ in the polymeric quaternary ammonium compound each preferably represent iodine atoms, and an effective quantity of such a compound is conveniently 0.1 to 100 ppm, preferably 0.3 to 25 ppm. Representative bacteria against which the method according to the invention is active include Enterobacter aerogenes , Staphylococcus aureus , and Salmonella choleraesuis . A typical fungus is Aspergillus niger while examples of algae include Chlorella pyrenoidosa and Phormidium inundatum . The aqueous liquid may be contained in a bathing vessel, such as a swimming pool, spa or hot tub, or may be contained in a water cooling device. The method according to the invention is also suitable when the aqueous liquid is to be used for sanitation purposes, for example toilet bowl water. A further aspect of the invention provides a method of disinfecting a surface which comprises the step of contacting said surface to be disinfected with a polymeric quaternary ammonium compound as hereinbefore defined in an amount effective to disinfect said surface. Preferred compounds for use in the methods according to the invention include the novel compound poly [(dimethyliminio)-2-hydroxypropylene triiodide] described hereinafter. A yet further aspect of the invention provides a method of disinfecting the skin of an animal which comprises the step of contacting said skin to be disinfected with a polymeric quaternary ammonium compound as hereinbefore defined in an amount effective to disinfect said skin. The method of disinfecting skin is preferably applied to a human subject. In particular, the polymeric quats according to the invention can kill bacteria and fungi very quickly and can be functional as hard surface disinfectants used in hospitals, food handling facilities, and the like. The polymeric quats of the invention can specifically be used to sanitize toilets and to disinfect the skin of humans and other animals. Ionene polymers belong to a well-known class of compounds, which together with methods for their preparation are described in U.S. Patent Nos. 3,874,870, 3,931,319, 4,025,627, 4,027,020, and 4,506,081. The trihalides of ionenes, such as the triiodides in particular, can be prepared by replacing the halogen, preferably chloride or bromide, with trihalide anion, as described in U.S. Patent No. 3,778,476. For example, a triiodide solution is prepared by mixing iodine and an alkali metal iodide, preferably potassium or sodium iodide, in water. On adding a solution of polymeric quaternary ammonium chloride or bromide to this triiodide solution, a dark solid precipitates. After decanting the aqueous layer, the triiodide compound is obtained. The triiodide compound can be used in the solid form or solubilized in acetone or some other suitable polar organic solvent or combination of solvents to yield an effective formulation. Formulations of ionene trihalide and in particular, ionene triiodide, can be added to various water systems to control the growth of undesirable microorganisms, including fungi. The effectiveness against fungi that can be obtained is surprising in view of the lack of efficacy of conventional ionenes, i.e., those having single halogen ions as the counter ions to the positive charges, against fungi. Ionene trihalides, such the triiodides, can also be used to disinfect or sanitize surfaces. The time required to completely kill bacteria on a hard surface can be much less for the trihalide salt than that for conventional halide salts. The solid form of the triiodide can be added to water systems, such as cooling towers or swimming pools, to provide a continuous release microorganism control agent. The ionene trihalides of this invention are novel over those described in the prior art, such as U.S. Patent Nos. 3,778,476 and 3,898,336, because the B substituent described above contains at least one pendant hydroxyl group, i.e., at least one hydroxyl group substituent attached directly to the main polymer chain (the divalent hydrocarbon radical) or at least one substituent (pendant group) itself substituted by at leat one hydroxyl group, the substituent being attached directly to the divalent hydrocarbon radical. This difference improves the solubility in water and provides an advantage when used in aquatic systems. The invention will be further clarified by the following examples, which are intended to be merely illustrative of the present invention. Example 1 Preparation of poly[oxyethylene-(dimethyliminio) ethylene(dimethyliminio)-ethylene di(triiodide)] (Compound 1) A solution of 12.7 g (0.05 mole) of iodine and 20.0 g (0.12 mole) of potassium iodide in 1 litre of water was prepared. To the above vigorously-stirred solution were added dropwise 21.6 g (0.05 molar equivalents of chloride ion) of poly[oxyethylene-(dimethyliminio) ethylene-(dimethyliminio)ethylene dichloride] (60% aqueous solution available commercially as Busan 77 polymer). During this addition, a dark brown solid precipitated out of the solution, and the amount of solid increased with the increasing amount of polymer dichloride that was added. After the addition was complete, the reaction mixture was stirred at room temperature for an additional two hours. Most of the aqueous layer was decanted and the precipitate was filtered and collected. A 73.7% yield (35.0 g) of this dark brown solid was obtained. An elemental analysis (in duplicate) of the solid showed it to be poly[oxyethylene(dimethyliminio)ethylene-(dimethyliminio)ethylene di(triiodide)]. The results are given in Table 1. Element % Calculated % Found (1) % Found (2) C 12.63 13.14 13.20 H 2.53 2.64 2.55 I 80.21 79.23 79.14 N 2.95 3.08 3.04 The solubility of this compound was determined by stirring 1 gram in 1 liter of deionized water for 2 hours. Supernatant solution was analyzed for quaternary ammonium salts using the bromophenol blue titration method and for iodide using a selective ion electrode. The amount of the dissolved polymeric quaternary ammonium triiodide was found to be 183 ppm, which is well above the effective level in water as subsequent examples show. This compound can be formulated at 5% in N-methyl-pyrollidone using Atlox 3409 surfactant. Example 2 Preparation of poly[(dimethyliminio)-2-hydroxypropylene triiodide] (Compound 2). The procedure described in Example 1 was followed using poly[(dimethyliminio)-2-hydroxypropylene chloride], a product commercially available as Busan 1055 polymer. Elemental analysis of the product gave the expected results, shown in Table 2. Element % Calculated % Found C 12.42 13.00 H 2.48 2.67 I 78.88 77.58 N 2.89 3.04 Example 3 Effectiveness of Compound 1 and Compound 2 against bacteria The effectiveness of the Compounds 1 and 2 prepared in Examples 1 and 2 was determined against Enterobacter aerogenes at pH 8.0 using the method described in U.S. Patent No. 2,881,070 with the modification described in Example 22 of U.S. Patent No. 4,054,542. Effectiveness of each polymer was determined at various contact times. The results are given in Table 3. In comparison to these results, the dichloride used as the starting material in Example 1, Busan 77 polymer, has an MIC of 10 ppm for 8 hours contact time and 20 ppm for 4 hours contact time. Minimum Inhibitory Concentration (MIC) of two triiodinated polymers to produce 90% kill of Enterobacter aerogenes in a basal salts solution at pH 8.0 after multiple contact times Contact Time (hours) MIC in parts per million Compound 1 Compound 2 2 0.3 2 4 0.3 2 6 0.3 2 8 0.3 2 24 0.3 2 Example 4 Disinfectant effectiveness of Compound 1 and Compound 2. In this example, the effectiveness of the compounds prepared in Examples 1 and 2 was determined against Staphylococcus aureus and Salmonella Cholerasuis using the A.O.A.C. Use-Dilution test described in the Official Methods of Analysis (1984) 14th Ed., AOAC, Washington, DC, Secs. 4.007-4.011. The results are given in Table 4. Test material Maximum dilution providing kill in 10 of 10 replicates in 10 min. vs. Staphylococcus aureus Salmonella choleraesuis Compound 1 1:1000 1:1000 Compound 2 1:2500 1:2500 Example 5 Zone Inhibition Study with Compounds 1 and 2 The inhibitory properties of the two ionene triiodides prepared in Examples 1 and 2 were assayed against Enterobacter aerogenes and Staphylococcus aureus using a zone of inhibition technique. In this assay, nutrient agar was inoculated with E. aerogenes and poured into a sterile petri dish. When the agar was solidified, a measured disc of the solid test compound was placed on the surface of the inoculated agar. Following incubation, the clear zone surrounding the measured disc was measured. This procedure was repeated with S. aureus . Inoculated agar plates to which no test compound was added were included as controls. The results are shown in Table 5. Zone of Inhibition of Enterobacter aerogenes and Staphylococcus aureus by Compounds 1 and 2 after 24 hours incubation. Test material Zone of inhibition in millimeters vs. E. aerogenes S. aureus Control 0 0 Compound 1 7 5 Compound 2 Complete Complete Example 6 Effectiveness of Compounds 1 and 2 against fungi. The effectiveness of the compounds prepared in Examples 1 and 2 against the fungus Aspergillus niger was determined in a mineral salts medium. The medium is composed of the following: Glucose 10.0 g Ammonium nitrate 3.0 g Potassium phosphate (K₂PO₄) 1.0 g Potassium chloride 0.25 g Magnesium sulfate 0.25 g Tween 80 0.5 g HCl-Trizma buffer 6.0 g Deionized water 1000 ml Forty-gram portions of the medium are added to 250-ml Erlenmeyer flasks fitted with loose metal caps and then sterilized. The following substances are then added to each bottle in the order listed: 1. Sterile mineral salts solution as required in each individual case to bring the total weight of the contents of each flask to 50 g, after allowing for all subsequent additions specified hereinafter, including inoculation with the aqueous suspension of spores. 2. Solution of toxicant to be evaluated in such individual volumes to give the concentration desired in the test; the amount is computed in parts per million by weight. Duplicate controls containing no toxicant are used. 3. Inoculum consisting of 1 ml of an aqueous suspension of spores and/or mycelial fragments of the test organism. After the inoculant suspensions of the test fungus have been added, the flasks are incubated at 30 ± 1 °C for a period adequate for growth in the controls. The customary period of observation is 14 days. Growth is recorded at 7 days and 14 days on the basis of the following key: 4 = excellent growth 3 = good 2 = poor 1 = very poor, scant, questionable 0 = no growth A toxicant is considered an effective fungicide if it scores 0 (no growth) at the recommended use concentration at the 14-day observation period. The results of the test with Compound 1 and Compound 2 are given in Table 6. In comparison, the chloride analog of Compound 1, Busan 77 polymer, will not control A. niger at 1000 ppm, the highest level tested. Inhibition of Aspergillus niger by two triiodinated polymers after 14 days. Test material Concentration in ppm Growth Rating Compound 1 1 4 5 4 25 0 Compound 2 1 4 5 4 25 0 Example 7 Effectiveness of Compounds 1 and 2 against algae. The growth inhibiting activity of the compounds made in Examples 1 and 2 was evaluated in Difco Algae Broth, the content of which was as follows: Compound Grams per liter Sodium nitrate 1.000 Ammonium chloride 0.050 Calcium chloride 0.058 Magnesium sulfate 0.513 Dipotassium phosphate 0.250 Ferric chloride 0.003 Forty-gram portions of the algae medium were added to 250 ml Pyrex Erlenmeyer flasks fitted with loose metal caps and then sterilized. Each of the following substances was then added to the flasks in the order listed: 1. Sterile algae medium as required to bring the total weight of the contents of each flask to 50 grams, after allowing for all subsequent additions specified hereinafter. 2. Solution of toxicant or control agent to be evaluated in each test, to give the concentration desired in parts per million by weight. 3. Chlorella pyrenoidosa and Phormidium inundatum in amounts sufficient to give excellent growth in the controls after 14 days. This was achieved by adding 1 milliliter of a 14 day old culture having luxuriant growth. The Chlorella pyrenoidosa culture was obtained from American Type Culture Collection No. 7516; Phormidium inundatum , Wisconsin No. 1093, was obtained from the University of Washington. After the inoculum of the test algae was added, the flasks were incubated at a temperature of 28 ± 2 °C under fluorescent illumination of 250 foot-candle intensity (8 hours light, 16 hours darkness) for a period adequate for growth in the controls (those portions of medium which contained no toxicant). Observations of growth were made at 7 day intervals on the basis of the following key: 4 = excellent growth 3 = good 2 = poor 1 = very poor, scant, questionable 0 = no growth The results are given in Table 7. Inhibition of algae by Compounds 1 and 2. Test Organism Concentration in ppm Compound 1 Compound 2 Chlorella pyrenoidosa 1 1 3 5 0 0 10 0 0 25 0 0 Phormidium inundatum 1 1 1 5 0 0 10 0 0 25 0 0

Claims: Claims for the following Contracting States : AT, BE, CH, DE, DK, FR, GB, GR, IT, LI, LU, NL, SE A polymeric quaternary ammonium compound of the formula wherein X₁, X₂ and X₃ are each a halogen atom and can all be the same halogen or different halogens and wherein R¹ and R², which can be the same or different, each represent an alkyl group having from 1 to 20 carbon atoms optionally substituted by a hydroxyl group, a benzyl group, or a benzyl group bearing on the benzene moiety one alkyl group having from 2 to 20 carbon atoms; A is a divalent hydrocarbon radical containing 1 to 10 carbon atoms or a divalent hydrocarbon radical containing 1 to 10 carbon atoms and also containing an oxygen atom as an ether group; B is a divalent hydrocarbon radical containing 1 to 10 carbon atoms, said divalent hydrocarbon radical being substituted by at least one hydroxyl group or a substituent substituted by at least one hydroxyl group; n is a whole number from 2 to 30, with the proviso that if A and B are identical, then n is a whole number from 1 to 15; and wherein the polymer may be capped on one or both ends with a quaternary ammonium group of formula wherein X₁, X₂ and X₃ are as defined above and wherein R³, R⁴ and R⁵, which can all be the same or different, are alkyl groups having from 1 to 20 carbon atoms optionally substituted by a hydroxyl group, or R³ and R⁴ taken together with the nitrogen atom to which they are attached form a saturated heterocyclic ring having from 5 to 7 ring atoms. A compound as claimed in claim 1, wherein X₁, X₂ and X₃ are all iodine. Poly[(dimethyliminio)-2-hydroxypropylene triiodide]. Poly[oxyethylene(dimethyliminio)hydroxypropylene (dimethyliminio)ethylene di(triiodide)]. Poly[2-hydroxyethylene(dimethyliminio)ethylene - (dimethyliminio)-methylene di(triiodide)]. A method for inhibiting the growth of a microorganism in an aqueous liquid susceptible to growth of said microorganism which comprises the step of adding to said aqueous liquid a polymeric quaternary ammonium compound as claimed in any one of claims 1 to 5 in an amount effective to inhibit the growth of said microorganism. A method as claimed in claim 6, wherein X₁, X₂ and X₃ in said polymeric quaternary compound each represent iodine atoms. A method as claimed in claim 6 or claim 7, wherein said effective amount is from 0.1 to 100 parts per million of said aqueous liquid. A method as claimed in any one of claims 6 to 8, wherein said microorganism is a bacterium, a fungus or an alga. A method as claimed in any one of claims 6 to 9, wherein said aqueous liquid is contained in a bathing vessel or a water cooling device. A method as claimed in any one of claims 6 to 9, wherein said aqueous liquid is water used for sanitation purposes. A method of disinfecting a surface which comprises the step of contacting said surface to be disinfected with a polymeric quaternary ammonium compound as claimed in any one of claims 1 to 5 in an amount effective to disinfect said surface. A method as claimed in any one of claims 6 to 12, wherein said polymeric quaternary ammonium compound is poly [(dimethyliminio)-2-hydroxypropylene triiodide]. A compound as claimed in any one of claims 1 to 5 for use as a skin disinfectant. Claims for the following Contracting State : ES A method for inhibiting the growth of a microorganism in an aqueous liquid susceptible to growth of said microorganism which comprises the step of adding to said aqueous liquid a polymeric quaternary ammonium compound of the formula wherein X₁, X₂ and X₃ are each a halogen atom and can all be the same halogen or different halogens and wherein R¹ and R², which can be the same or different, each represent an alkyl group having from 1 to 20 carbon atoms optionally substituted by a hydroxyl group, a benzyl group, or a benzyl group bearing on the benzene moiety one alkyl group having from 2 to 20 carbon atoms; A is a divalent hydrocarbon radical containing 1 to 10 carbon atoms or a divalent hydrocarbon radical containing 1 to 10 carbon atoms and also containing an oxygen atom as an ether group; B is a divalent hydrocarbon radical containing 1 to 10 carbon atoms, said divalent hydrocarbon radical being substituted by at least one hydroxyl group or a substituent substituted by at least one hydroxyl group; n is a whole number from 2 to 30, with the proviso that if A and B are identical, then n is a whole number from 1 to 15; and wherein the polymer may be capped on one or both ends with a quaternary ammonium group of formula wherein X₁, X₂ and X₃ are as defined above and wherein R³, R⁴ and R⁵, which can all be the same or different, are alkyl groups having from 1 to 20 carbon atoms optionally substituted by a hydroxyl group, or R³ and R⁴ taken together with the nitrogen atom to which they are attached form a saturated heterocyclic ring having from 5 to 7 ring atoms, in an amount effective to inhibit the growth of said microorganism. A method as claimed in claim 1, wherein X₁, X₂ and X₃ in said polymeric quaternary ammonium compound each represent iodine atoms. A method as claimed in claim 1 or claim 2, wherein said effective amount is from 0.1 to 100 parts per million of said aqueous liquid. A method as claimed in any preceding claim, wherein said microorganism is a bacterium, a fungus or an alga. A method as claimed in any preceding claim, wherein said aqueous liquid is contained in a bathing vessel or a water cooling device. A method as claimed in any one of claims 1 to 4, wherein said aqueous liquid is water used for sanitation purposes. A method of disinfecting a surface which comprises the step of contacting said surface to be disinfected with a polymeric quaternary ammonium compound of the formula wherein X₁, X₂ and X₃ are each a halogen atom and can all be the same halogen or different halogens and wherein R¹ and R², which can be the same or different, each represent an alkyl group having from 1 to 20 carbon atoms optionally substituted by a hydroxyl group, a benzyl group, or a benzyl group bearing on the benzene moiety one alkyl group having from 2 to 20 carbon atoms; A is a divalent hydrocarbon radical containing 1 to 10 carbon atoms or a divalent hydrocarbon radical containing 1 to 10 carbon atoms and also containing an oxygen atom as an ether group; B is a divalent hydrocarbon radical containing 1 to 10 carbon atoms, said divalent hydrocarbon radical being substituted by at least one hydroxyl group or a substituent substituted by at least one hydroxyl group; n is a whole number from 2 to 30, with the proviso that if A and B are identical, then n is a whole number from 1 to 15; and wherein the polymer may be capped on one or both ends with a quaternary ammonium group of formula wherein X₁, X₂ and X₃ are as defined above and wherein R³, R⁴ and R⁵, which can all be the same or different, are alkyl groups having from 1 to 20 carbon atoms optionally substituted by a hydroxyl group, or R³ and R⁴ taken together with the nitrogen atom to which they are attached form a saturated heterocyclic ring having from 5 to 7 ring atoms, in an amount effective to disinfect said surface. A method as claimed in any preceding claim, wherein said polymeric quaternary ammonium compound is poly [(dimethyliminio)-2-hydroxypropylene triiodide] A process for the preparation of polymeric quaternary ammonium compounds of the formula wherein X₁, X₂ and X₃ are each a halogen atom and can all be the same halogen or different halogens and wherein R¹ and R², which can be the same or different, each represent an alkyl group having from 1 to 20 carbon atoms optionally substituted by a hydroxyl group, a benzyl group, or a benzyl group bearing on the benzene moiety one alkyl group having from 2 to 20 carbon atoms; A is a divalent hydrocarbon radical containing 1 to 10 carbon atoms or a divalent hydrocarbon radical containing 1 to 10 carbon atoms and also containing an oxygen atom as an ether group; B is a divalent hydrocarbon radical containing 1 to 10 carbon atoms, said divalent hydrocarbon radical being substituted by at least one hydroxyl group or a substituent substituted by at least one hydroxyl group; n is a whole number from 2 to 30, with the proviso that if A and B are identical, then n is a whole number from 1 to 15; and wherein the polymer may be capped on one or both ends with a quaternary ammonium group of formula wherein X₁, X₂ and X₃ are as defined above and wherein R³, R⁴ and R⁵, which can all be the same or different, are alkyl groups having from 1 to 20 carbon atoms optionally substituted by a hydroxyl group, or R³ and R⁴ taken together with the nitrogen atom to which they are attached form a saturated heterocyclic ring having from 5 to 7 ring atoms, said process comprising reacting a corresponding polymeric quaternary ammonium halide to replace the halide anion with a trihalide anion. A process as claimed in claim 9 wherein the polymeric quaternary ammonium halide is reacted to form a polymeric quaternary ammonium triiodide. A process as claimed in claim 9 wherein a poly[(dimethyliminio)-2-hydroxypropylene halide] is reacted to form poly[(dimethyliminio)-2-hydroxypropylene triiodide]. A process as claimed in claim 10 wherein a poly[oxyethylene(dimethyliminio)hydroxypropylene (dimethyliminio)ethylene dihalide] is reacted to form poly[oxyethylene(dimethyliminio)hydroxypropylene (dimethyliminio)ethylene di(triiodide)]. A process as claimed in claim 10 wherein a poly[2-hydroxyethylene(dimethyliminio)ethylene - (dimethyliminio)-methylene dihalide] is reacted to form poly[2-hydroxyethylene(dimethyliminio)ethylene - (dimethyliminio)-methylene di(triiodide)].

Inventors: HOLLIS CECIL GEORGE, RAYUDU SREEDHAR RAO, HOLLIS, CECIL GEORGE, RAYUDU, SREEDHAR RAO
Applicants: BUCKMAN LABOR INC, BUCKMAN LABORATORIES INTERNATIONAL, INC.
Application year: 1990
Main classification: A01N33
IPC codes: C08G73, A01N33, A61K31, A61L2, C02F1, A61P17, A61K33