Method for manufacturing bromine and bromine-iodine detergents and disinfectants

This is a continuation of application Ser. No. 676,972, filed Apr. 14, 1976 which is a continuation-in-part application of Ser. No. 439,755 filed Feb. 5, 1974, now abandoned.

This invention relates to a method for manufacturing bromine and bromine-iodine agents with detergent and disinfecting properties comprising bromine and bromine-iodine complex compounds with non-ionic surfactants. These agents are characterized by their bactericidal, fungicidal and virusocidal action, as well as by their detergency effects. They may be applied in the prophylaxis and therapy of mycoses, infectious and invasional diseases, as well as to washing and disinfecting in one operation of the equipment, installations and rooms in agriculture, food industry, medicine and veterinary medicine, municipal installations and transport.

Methods for manufacturing this class of complex compounds are not known. The closest art relates to agents with detergent and disinfecting properties prepared by reacting iodine with surfactants.

The methods for the preparation of such agents are described e.g. in British Pat. Nos. 962,955 and 2,977,315, in U.S. Pat. Nos. 2,931,777 and 3,028,299 and in German Pat. Nos. 1,171,112 and 1,642,088 and they consist in the preparation of mixtures of iodine or chlorine with detergents, in particular with non-ionic surfactants, with the optional addition of stabilizers of the acid type, mainly phosphoric and citric acids and alkali halides.

The main drawbacks of these known mixtures of iodine and chlorine with surfactants are their instability and their comparatively smooth decomposition with evolution of iodine or chlorine, which exerts a toxic action against warm-blooded organisms, causing irritation of skin and mucosae, as well as a strong corrosive effect on the surface of the washed and disinfected materials. The main reason for this instability is the fact that these mixtures are not stable, complex bonded compounds of the reactants, but they are only their loosely bonded mixtures. Attempts have been made to improve the stability of the above mentioned agents, e.g. of the iodophors according to the German Pat. No. 1,570,668 by giving them a special structure. The method consisted in lowering the rate of evolving free iodine by the agent by coating its surface with a liquid unsaturated monomer and then polymerizing it in the presence of a catalyst with formation of a sort of protective layer on the surface. The method is however troublesome and requires performing additional operations.

The scope of the present invention is the development of a method for manufacturing stable bromine and bromine-iodine agents having an efficient detergent and washing activity.

The method for manufacturing the bromine and bromine-iodine washing and disinfecting agents according to the invention is characterized by the fact that the synthesis of reactants gives a stable complex compound with no drawbacks of the hitherto known iodophors.

The stable bromine and bromine-iodine complex compounds with non-ionic surfactants are prepared in the synthesis of these compounds due to the application of iodine complex compounds with bromine instead of the hitherto used pure iodine.

The method according to the present invention comprises reacting a complex compound [IBr₂ ]^- or IBr with non-ionic surfactants, e.g. fatty alcohols extended with ethylene oxide, alkylphenols extended with ethylene oxide, amides of fatty acids extended with ethylene oxide, etc.

When the [IBr₂ ]^- is used in the synthesis, a bromine complex compound corresponding to the general formula

R--(OCn H2n)x --OH . . . Br--BR . . . HO--(Cn H2n O)x --R

is obtained, wherein R represents an alkyl, alkylamido, aryl or alkylaryl radical of 6-32 carbon atoms, n is an integer from 2 to 4 and x is an integer from 2 to 50 and represents the number of oxyalkylene groups.

When IBr is used in the synthesis, a bromine-iodine complex compound corresponding to the general formula

R--(OCn H2n)x --OH . . . I--Br . . . HO--(Cn H2n O)x --R

is obtained, wherein R, n and x have the meanings given above.

The course of the synthesis of the bromine complex compounds according to the present invention is, as follows:

To a saturated aqueous solution of an iodide of an alkali metal or of an alkaline earth metal, liquid bromine is added in the stoichiometric or nearly stoichiometric proportion at a temperature in the range of 0°-50° C. and with simultaneous stirring of the reaction mixture -- in the reaction I^- + Br₂ → [Br₂ ]^-. The prepared complex compound is added to a surfactant, which does not contain any water or only small amounts of water, in an amount of not more then 1 mole [IBr₂ ]^- per 2 moles of non-ionic surfactant. This reaction is performed at a temperature not higher than 60° C. Because of the exothermic character of this reaction, the temperature must be controlled by the rate of addition of [IBr₂ ]^- and by cooling the reaction vessels.

The course of the synthesis of the bromine-iodine complex compounds according to the present invention is, as follows:

In a reaction vessel stoichiometric amounts of iodine and bromine are mixed together at a temperature in the range of 0°-60° C., and the thus prepared iodine bromide is added to a non-ionic surfactant which does not contain any water or only small amounts of water, in an amount not more than 1 mole of iodine bromide per 2 moles of the non-ionic surfactant. This reaction is performed at a temperature not higher than 60° C. The temperature of the reaction mixture is controlled by the rate of addition of the iodine bromide and by cooling.

The bromine-iodine complex compounds with the non-ionic surfactants are stabilized additionally by addition of aqueous solutions of bromides of alkali metals or alkaline earth metals, the optimum stabilizing effect being obtained by addition of 1 mole of the bromides of the above mentioned metals per 1 mole of iodine bromide. The Br^- ion formed in the aqueous solution prevents the decomposition of the complex compound.

The bromine and bromine-iodine complex compounds with non-ionic surfactants are prepared for direct application by dissolution in water with addition, if necessary, of the generally known agents increasing the bactericidal and detergency effectiveness, which are normally used in iodophors, such as e.g. organic acids, mineral acids, alkylarylsulfonic acids, alkylsulfonic acids, etc.

The method according to the present invention gives stable detergents and disinfectants with a strong bactericidal, fungicidal and virusocidal action together with high detergency effects, without any side-effects, which do not cause irritation and discoloration of skin, mucosae, and respiratory system and which are non-toxic to warm-blooded organisms. On the basis of these compounds a wide range of efficient disinfectants and disinfectant-detergents may be manufactured which can find application in medicine, veterinary medicine, agriculture, dairy, meat and brewing industries, winemaking, etc.

The following examples illustrate the subject of the present invention.

EXAMPLE I

2 kg potassium iodide are dissolved in 1.4 kg water. 1.93 kg liquid bromine are added dropwise to this solution at a temperature not higher than 60° C. The solution of iodine bromide prepared in this manner is introduced into a reactor fitted with a stirrer and containing 14.84 kg nonylphenol etherified with octaethylene glycol. The reaction mixture is cooled so that its temperature is not higher than 60° C.

In this reaction a liquid bromine-complex compound is obtained, which is soluble in water without signs of decomposition and to which auxiliary agents may be added, e.g. 1 kg sodium dodecylbenzenesulfonate and 2 kg orthophosphoric acid. The product thus obtained, according to its use, is diluted with water for direct application in a weight proportion of 1:5 to 1:200.

EXAMPLE II

2 kg iodine are mixed with 1.26 kg bromine at a temperature not higher than 60° C. The iodine bromide prepared in this manner is introduced into a reactor fitted with a stirrer and containing 16.74 kg stearyl alcohol etherified with octadecylethylene glycol. The reaction mixture is cooled so that its temperature is not higher than 60° C., with a simultaneous addition of 0.94 kg potassium bromide, as stabilizer.

In this reaction a bromine-iodine complex compound is obtained, which is soluble in water without signs of decomposition. As auxiliary agents 0.5 kg sodium dodecylbenzenesulfonate and 1 kg orthophosphoric acid are added.

The product thus obtained, according to its use, is diluted with water for direct application in a weight proportion from 1:5 to 1:200.

EXAMPLE III

1.8 kg sodium iodide are dissolved in 1.4 kg water. 1.93 kg liquid bromine are added dropwise to this solution, at a temperature during this chemical reaction not higher than 60° C.

The solution of iodine bromide prepared in this manner is introduced into a reactor fitted with a stirrer and containing 26.5 kg tallow alcohol etherified with 18 groups of ethylene oxide. The reaction mixture is cooled so that its temperature is not higher than 60° C., and 2.7 kg citric acid are added, as stabilizer.

The product thus obtained, according to its use, is diluted with water for direct application in a weight proportion from 1:5 to 1:200.

EXAMPLE IV

1.61 kg lithium iodide are dissolved in 1.3 kg water. 1.9 kg liquid bromine are added to this solution at a temperature during this chemical reaction not higher than 60° C.

The solution of iodine bromide prepared in this manner is introduced into a reactor fitted with a stirrer and containing 43.5 kg monoethanolamides of tallow acids extended with 35 groups of ethylene oxide. To this reaction mixture cooled to a temperature of 60° C., 12 kg of phosphoric acid are added.

The product thus obtained, according to its use, is diluted with water for direct application in a weight proportion from 1:5 to 1:200.

EXAMPLE V

2 kg iodine are mixed with 1.26 kg bromine at a temperature below 60° C.

The thus obtained iodine bromide is introduced into a reactor fitted with a stirrer and containing 9.1 kg nonylphenol extended with 8 moles of ethylene oxide. The reaction mixture is cooled so that its temperature is not higher than 60° C. with simultaneous addition of 0.81 kg sodium bromide, as stabilizer.

As an auxiliary agent 1.7 kg sodium dodecylbenzenesulfonate are added.

The product thus obtained, according to its use, is diluted with water for direct application in a weight proportion from 1:5 to 1:200.

EXAMPLE VI

2 kg iodine are mixed with 1.26 kg bromine at a temperature below 60° C.

The thus obtained iodine bromide is introduced into a reactor fitted with a stirrer and containing 28.4 kg monoethanolamides of tallow acids extended with 35 moles ethylene oxide. The reaction mixture is cooled so that its temperature is not higher than 60° C., with simultaneous addition of 0.69 kg lithium bromide, as stabilizer.

The product thus obtained, according to its use, is diluted with water for direct application in a weight proportion from 1:5 to 1:200.

EXAMPLE VII

3.26 kg iodine bromide are introduced into a reactor containing 17.3 kg β-naphthol oxyalkylenated with 13 moles propylene oxide of the formula C₁₀ H₇ (OC₃ H₆)₁₃ --OH; to stabilize the reaction mixture 1.05 kg magnesium bromide are added. The bromine-iodine complex compound of formula

C10 H7 (OC3 H6)13 --OH . . . Br--I . . . HO(OC3 H6)13 --C10 H7 

is obtained, which is soluble in water without any sign of decomposition. As an auxiliary agent 1.3 kg sodium dodecylbenzenesulfonate and 1.2 kg citric acid are added. The product thus obtained, according to its use, is diluted with water for direct application in a weight proportion of 1:5 to 1:200.

EXAMPLE VIII

3.26 kg. iodine bromide are introduced into a reactor containing 35.1 kg lauryl alcohol oxypropylenated with 20 moles propylene oxide of the formula C₁₂ H₂₅ --(OC₃ H₆)₂₀ --OH; to stabilize the reaction mixture 1.30 kg sodium bromide are added. The bromine-iodine complex compound of the formula

C12 H25 --(OC3 H6)20 --OH . . . I--Br . . . HO--(C3 H6 O)20 --C12 H25 

is obtained, which is soluble in water without any sign of decomposition. As auxiliary agents 13 kg tartaric acid and 3.2 kg sodium dodecylbenzenesulfonate are added. The product thus obtained, according to its use, is diluted with water for direct application in a weight proportion of 1:5 to 1:200.

EXAMPLE IX

2.06 kg iodine bromide are introduced into a reactor containing 19.8 kg stearyl alcohol etherified with 10 moles butylene oxide of the formula C₁₈ H₃₇ --(C₄ H₈ O)₁₀ --OH; to stabilize the reaction mixture 1.09 kg potassium bromide are added. The bromine-iodine complex compound of the formula

C18 H37 --(C4 H8 O)10 --OH . . . I--Br . . . HO--(C4 H8 O)10 --C18 H37 

is obtained, which is soluble in water without any sign of decomposition. As auxiliary agents 0.5 kg sodium dodecylbenzenesulfonate and 1 kg orthophosphoric acid are added. The product thus obtained, according to its use, is diluted with water for direct application in a weight proportion of 1:5 to 1:200.

EXAMPLE X

0.166 kg potassium iodide are dissolved in 0.21 kg water, 0.16 kg liquid bromine are added dropwise to this solution at a temperature during this chemical reaction not higher than 60° C. The bromide-iodine solution prepared in this manner (having the formula KIBr₂) is introduced into a reactor fitted with a stirrer and containing 2.69 kg lauryl alcohol etherified with 20 groups of propylene oxide, of the formula: C₁₂ H₂₅ --(OC₃ H₆)₂₀ --OH.

The reaction mixture is cooled so that its temperature is not higher than 60° C.

The liquid bromine complex compound of the formula

C10 H7 (OC3 H6)13 --OH . . . Br -- Br . . . HO--(OC3 H6)13 --C10 H7 

is obtained, which is soluble in water without any sign of decomposition.

As a auxiliary agent 0.1 kg sodium dodecylbenzenesulfate and 1.2 kg phosphoric acid are added.

The product thus obtained, according to its use, is diluted with water for direct application in a weight proportion of 1:5 to 1:200.

EXAMPLE XI

0.166 kg potassium iodide are dissolved in 0.21 kg water. 0.16 kg liquid bromine are added dropwise to this solution at a temperature during this chemical reaction, not higher than 60° C.

The bromide-iodine solution prepared in this manner (of formula KIBr₂) is introduced into a reactor fitted with a stirrer and containing 1.98 kg stearyl alcohol etherified with 10 groups of butylene oxide of the formula C₁₈ H₃₇ --(C₄ H₈ O)₁₀ --OH.

The reaction mixture is cooled so that its temperature is not higher than 60° C.

The liquid bromine complex compound of the formula

C18 H37 --(OC4 H8 O)10 --OH . . . Br -- Br . . . OH -- (OC4 H8)10 --C18 H37 

is obtained, which is soluble in water without any sign of decomposition.

As auxiliary agents 0.3 kg dodecyl benzenesulfate and 0.75 kg phosphoric acid are added.

The product thus obtained, according to its use, is diluted with water for direct application in a weight proportion of 1:5 to 1:200.

                                  Table 1__________________________________________________________________________Comparison between properties of substrates andproducts according to invention                     Characteristics ofSpecification of   Substrates        the product according tothe property   Name of characteristics                     invention__________________________________________________________________________Action against   Iodine bromide           Caustic, causes                     No caustic and stain-skin of man and   IBr     slow-healing in-                     ing action; skin mayanimals         juries of skin                     be washed and disin-           and its browning                     fected with aqueous                     solution of the pro-                     duct without any de-                     trimental effectsAction against   Iodine bromide           Strong caustic,                     No vapors of IBr overmucosa          suffocating and                     the product and no cau-           poisoning action                     stic, suffocating and                     poisoning actionAction against   Iodine bromide           Strong corrod-                     No corroding actionmetals and      ing action                     against metals, except AgplasticsWater solubility   Iodine bromide           Water decomposes                     Soluble in water in           it with precipi-                     any proportion with-           tation of metallic                     out precipitation of           iodine    metallic iodineColor   Iodine bromide           Dark grey                     Brown-orange   Non-ionic sur-           Colorless   factantQuantitative   Iodine bro-           In a strictly de-                     Not more than 1 mole IBrway of joining   mide plus           fined weight ratio,                     per 2 moles of surfac-the substrates   non-ionic           and not in an arbit-                     tant. At ratios above   surfactant           rary ratio, as in a                     1:2, e.g. 1.1:2           mixture   metallic iodine pre-                     cipitatesChanges in   Non-ionic           No changes in the                     No changes in the po-IR-spectra   surfactant           spectrum in rela-                     sition of character-           tion to the pro-                     istic absorption           duct      bands in relation to                     the substrateChanges in   Non-ionic           No changes in the                     No changes in chemicalNMR-spectrum   surfactant           spectrum in rela-                     shifts of signals of   with QH-end-           tion to the pro-                     individual groups and   group blocked           duct comprising                     in their appearance in   by CH3 -group           non-ionic sur-                     relation to the spectrum           factant with                     of substrate - thus, the           blocked OH-group                     product is a mixture           plus iodine bro-           mideIdem    Non-ionic           Signal of proton                     A substantial change in   surfactant           in the image of                     the appearance and in   without OH-group has a                     the values of chemical   blocking of           typical appear-                     shifts of the proton   OH-group           ance - it is low                     of OH-group in relation           and broadened                     to the substrate. A           due to inter-                     sharp signal of the           change    proton of OH-group and                     its shifting to higher                     frequencies is observed;                     thus, the product is a                     chemical compound__________________________________________________________________________

                                  Table 2__________________________________________________________________________Studies on determining the maximum molar ratio ofiodine bromide bound by non-ionic surfactantsSeries I     Series II Series III                            Series IVNSF   MR Clear     ppt.        MR Clear               ppt.                  MR Clear                         ppt.                            MR Clear                                   ppt.__________________________________________________________________________A  0.9:2 yes no 1:2           yes no 1.1:2                     no  yes                            1.5:2                               no  yesB  0.9:2 yes no 1:2           yes no 1.1:2                     no  yes                            1.5:2                               no  yesC  0.9:2 yes no 1:2           yes no 1.1:2                     no  yes                            1.5:2                               no  yes__________________________________________________________________________ Abbreviations and symbols: MR -- molar ratio NSF -- non-ionic surfactant ppt. -- precipitate of I2? A -- C9 H19 --C6 H4 ---(OC2 H4)8 B -- CH3 (CH2)17 --(OC2 H4)18 --OH C -- CH3 (CH2)16 --CONH--(C2 H4 O)36 --H

A comparison of halogen content of the compounds of the prior art as illustrated by Kaplan et al U.S. Pat. No. 3,285,816, issued Nov. 15, 1966 and the corresponding products made according to the present invention is given in Table 3.

The method used to prepare the compounds of U.S. Pat. No. 3,285,816 is given in Examples 1b and 16 of said patent. Example 1b refers to the chlorine derivatives and Example 16 refers to the bromine derivatives.

The method of Example V was used to prepare the products according to the invention, using appropriate oxyethylenated phenols as starting materials. The percentages of halogen represent in maximum possible with the process of the invention.

              Table 3______________________________________Series  %I       %Br       %Cl    Kaplan______________________________________A-1     8.82     5.55A-2     21.56              5.57   Example 14aA-3     20.40    9.73             Example 14bB-1     2.87     1.81B-2     11.64              3      Example 11bC-1     8.85     5.57C-2     21.34              3      Example 2b______________________________________ A -- based on C9 H19 --C6 H4 ---(OC2 H4)9 --OH B -- based on (C9 H19)2 --C6 H3 --(OC2 H4)40 --OH C -- based on C12 H25 --C6 H4 --(OC2 H4)8 --OH