US3501341A - Method of permanently sterilizing textiles with a solution of at least one n - pentachlorophenylamine compound - Google Patents

Method of permanently sterilizing textiles with a solution of at least one n - pentachlorophenylamine compound Download PDF

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US3501341A
US3501341A US464203A US3501341DA US3501341A US 3501341 A US3501341 A US 3501341A US 464203 A US464203 A US 464203A US 3501341D A US3501341D A US 3501341DA US 3501341 A US3501341 A US 3501341A
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pentachlorophenyl
solution
textiles
water
compound
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Arno Spange
Horst-Gunter Bellinger
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Dr Th Boehme KG Chemie Fabrik GmbH and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/06—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals
    • C07D295/073—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals with the ring nitrogen atoms and the substituents separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/06—Nitrogen directly attached to an aromatic ring system
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/907—Resistant against plant or animal attack
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2525—Coating or impregnation functions biologically [e.g., insect repellent, antiseptic, insecticide, bactericide, etc.]

Definitions

  • Pathogenic bacteria and fungi are known to adhere to textiles which are worn in direct contact with the skin and thereby cause a spreading of skin diseases and/or continuous reinfection of the wearer of the textiles. These germs cannot be eliminated or sufficiently destroyed by the mild detergents usually used for washing these textiles or by the temperatures employed in fine washing of fabrics such as nylon.
  • the process of the invention for making textiles permanently sterile comprises impregnating the textile with a solution of at least one N-pentachlorophenylamine com pound selected from the group consisting of compounds of the formula wherein R is selected from the group consisting of hydrogen, alkyl of l to 6 carbon atoms and R R is R is an alkylene of l to 6 carbon atoms and n is an integer from to 4 and water-soluble acid addition salts thereof at a liquor ration of 1:20 to 1:40, removing the textile from the solution and drying the textile to obtain a textile which will remain sterile through repeated washings.
  • N-pentachlorophenylamine com pound selected from the group consisting of compounds of the formula wherein R is selected from the group consisting of hydrogen, alkyl of l to 6 carbon atoms and R R is R is an alkylene of l to 6 carbon atoms and n is an integer from to 4 and water-soluble acid addition salts thereof at a liquor ration
  • the compounds used to impregnate the textiles possess excellent antibacterial and antimycotic properties and are particularly efiective against pathogenic skin fungi such as Kaufmann-Woltf epidermophyton.
  • the antimicrobic impregnations obtained in fine linens are very constant and even after repeated launderings, the treated textiles retain their antimicrobic activity and, therefore, are capable of effectively preventing the transmission of pathogenic bacteria and fungi for long periods of time.
  • the textiles to be treated by the process of the invention are articles which come in more or less direct contact with the skin such as underwear, stockings, bed linens, physicians smocks, hairdressers jackets, surgical and orthopedic article, etc.
  • the textiles may be made of any known natural or synthetic fibers such as wool, rayon, nylon, etc.
  • the impregnation treatment is especially suitable for textiles made of polyamide, polyurethane and albumin fibers.
  • N-pentachlorophenyl amine compounds are N-pentachlorophenyl-ethylenediamine, N- pentachlorophenyl 1,3 diaminopropane, N-pentachlorophenyl 12-diaminopropane, N-pentachlorophenyl-N',N'- dimethyl 1,3-diaminopropane, N-pentachlorophenyll,4- diaminobutane, N-pentachlorophenyl-1,6-diaminohexane, N-pentachlorophenylpiperazine, N-pentachlorophenyl-N- methyl-1,3-diaminopropane, N-pentachlorophenyl-diethylenetriamine, N pentachlorophenyl-dipropylenetriamine, N-p'entachlorophenyl-dihexamethylenetriamine, N pentachlorophenyl-
  • suitable acids for the formation of watersoluble acid addition salts of the said N-pentachlorophenyl amino compounds are inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, etc. and low molecular weight organic acids such as formic acid, acetic acid, lactic acid, citric acid, etc.
  • the organic acids are preferred.
  • the said N-pentachlorophenyl amino compounds can be prepared by reaction of hexachlorobenzene with aliphatic or cyclic dior polyamines containing at least one free amino hydrogen atom in the molecule in the presence of alkali, if necessary, as described, for example, in United States Patent No 2,829,164.
  • the process described therein is advantageously varied so that the reaction is carried out with an essentially smaller excess of amine.
  • the separation of the N-pentachlorophenyl amino compound from unreacted starting amine and hexachlorobenzene as well as from by-products simultaneously formed and from inorganic salts may be effected by treating the reaction mixture first with water, which removes the starting amine and inorganic salts, and then by means of extraction with hot, dilute acetic acid in which only the desired N pentachlorophenyl amino compound is soluble
  • the majority of the product is the monopentachlorophenyl amino compound which may also contain small amounts of constituents substituted with several pentachlorophenyl radicals. A separation of these latter products is unnecessary as a rule.
  • the solvents used to form the impregnating solutions may be organic solvents in which the N-pentachlorophenyl amino compounds are soluble such as lower alkanols, lower alkyl ketones, aliphatic hydrocarbons, etc. or water in which the acid addition salts of the N-pentachlorophenyl amino compounds are soluble.
  • N-pentachlorophenyl amine compounds required in the impregnation bath depend on the textile material treated, on the impregnation method employed and on the eltect to be attained.
  • the padding or blocking method about 2 to 10 gin/liter
  • 0.5 to gm./liter of the compounds are used at a liquor ratio of about 1:20 to 1:40.
  • the impregnating solutions preferably contain 1 to 3 gm./liter of a non-ionic and/or anionic surface-active agent.
  • suitable surface active agents are non-ionics such as the condensation products of 5 to 40 moles of lower alkylene oxides such as ethylene oxide with 1 mole of high molecular weight aliphatic alcohols, amines, carboxylic acids and amides, etc. and anionics such as alkali metal salts of aliphatic and aromatic sulfonates such as dodecyl sulfonate, dodecylbenzene sulfonate, tetrapropylenebenzene sulfonate, etc.
  • the impregnation of the textiles may be accomplished in the usual way such as the padding or blocking process.
  • Particularly useful is the glazing process since the N-pentachlorophenyl amine compounds can be easily applied in substantial amounts on the textile from dilute aqueous solution of their acid addition salts.
  • the degree of glazing can be increased in known methods by increasing the solution temperature, increasing the pH value about 5 and/or by the addition of additives such as the surface active agents.
  • a particular advantage of the process is that the impregnation can be effected simultaneously with dyeing of the textiles by adding the said N-pentachlorophenyl amine compounds to the dye bath.
  • the moderately cooled mixture was stirred into about 500 liters of water and the undissolved substance was suction-filtered, thoroughly washed with hot water and then treated with 1 liter of hot 7% acetic acid -with addition of decolorizing carbon.
  • the hot acetic acid solution was filtered and the N-pentachlorophenyl piperazine acetate was recovered from the cooled filtrate as a finely crystalline mass, which was suction. filtered, washed with ice water and then dried to obtain 280 gm. of the said product with a melting point of 166 to 170 C. After recrystallization from water and alcohol, the product had a melting point of 171 to 172.5 C.
  • the liquor bath was heated to 80 C. and a piece of knitted nylon fabric, weighing about 2.5 gm., was placed therein and left for about 30 minutes with constant stirring while maintaining the bath temperature at 80 C. Then the fabric sample was rinsed with water having a temperature of 50 C. and then dried for 2 hours at 60 C. The amount of impregnation, ascertained by weighing the textile before and after the impregnation and by micro-analytical chlorine determination, amounted to approximately 2% of the weight of the fabric.
  • the impregnated fabric sample was cut up in four pieces of practically identical size. Three pieces were subjected to a variable number of the customary fine washings for nylon fabrics and one piece remained unwashed. Each fine washing consisted of a treatment for 10 minutes with a warm (40 C.) solution, which contained 2 term and wort agar for the fungi. Then the arrested areas developed around the textile samples were measured. Table I represents the results.
  • the raw dia cetate of N-pentachlorophenyl-diethylenetriamine had a melting point of 92 to 100 C. and upon recrystallization from acetic acid had a melting point of 104 to 106 C.
  • the dihydrochloride of N-pentachlorophenyl-diethyle netriamine was repaired with excess alcoholichydrochloric acid and contained 15.59% chlorine (calculated 16.73%).
  • N-pentachlorophenyl-N',N-dimethyl-( 1,3 diaminopropane 61.4 gm. (0.6 mole) of N,N-dimethyl-(1,3)-diamino propane and 85.5 gm. (0.3 mole) of hexachlorobenzene were heated together to reflux with stirring in a threenecked flask equipped with a stirrer, reflux condenser and thermometer placed in a steam bath maintained at a temperature of about 170 C. The hexachlorobenzene gradually started to dissolve.
  • a dye bath containing 1% of a dispersion dye (Perliton Brown G), 4% of N-pentachlorophenyl-piperazine acetate and 2% of a mixture of sodium tetrapropylenebenzene sulfonate and a fatty alcohol polyethyleneglycol ether (all percentage data are based on the weight of the textile to be d'yed) was prepared.
  • a sample of nylon fabric weighing about 2.5 gm. was placed in 100 ml. of this bath heated to 40 C. with a liquor bath ratio about 1:40. Over 15 minutes, the temperature of the liquor bath was raised to 90 C. and maintained there for 15 minutes. The sample was taken out of the bath and rinsed in water. Whereas the dyeing obtained showed no differences in comparison with those which had been obtained without any addition of N-pentachlorophenyl-piperazine acetate, the antimicrobic effect corresponded with those values obtained in step A of Example 1.
  • step A N-pentachlorophenyl-( 1,3 -diaminopr0pane diacetate Using the method described in step A, samples of nylon fabric were treated with 0.25% solutions of N-pentachlorophenyl-(IQ)-diaminopropane diace'tate. The bath treatment was effected for 30 minutes at a temperature of C. followed by rinsing and drying as in step A.
  • N-pentachlorophenyl-diethylenetriamine acetate 0.025% liquor baths of the compound were prepared and adjusted to a pH value of 5.5 or 8.5 by adding sodium acetate or ammonium hydroxide. While stirring continuously, five samples of nylon fabric, each weighing about 500 mg., were left in 100 ml. of this bath heated to 80 C. for 30 minutes. The samples were rinsed and dried as described in step A.
  • a process for making textiles permanently sterile which comprises impregnating the textile with a solution of at least one N-pentachlorphenylamine compound se" lected from the group consisting of compounds of the formula:
  • R is selected from the group consisting of hydrogen, alkyl of l to 6 carbon atoms and R R is R is an alkylene of l to 6 carbon atoms and n is an integer from 0 to 4 and water-soluble acid addition salts thereof at a liquor ratio of 1:20 to 1:40, removing the textile from the solution and d 1 ying th e textile.
  • impregnating solution contains 1 to 3 grams of at least one agent selected from the group consisting of anionic and non-ionic surface-active agents per liter of solution.
  • the impregnating solution is an aqueous solution of a low molecular weight organic acid addition salt of the N-pentachlorophenyl amine compound.
  • N-pentachlorophenyl amine compound is a water-soluble acid addition salt of N-pentachlorophenyl-piperazine.
  • N-pentachlorophenyl amine compound is a water-soluble acid addition salt of N-pentachlorophenyl-1,3-diaminopropane.
  • N-pentachlorophenyl amine compound is a water-soluble acid addition salt of N-pentachlorophenyl-diethylenetriamine.
  • N-pentachlorophenyl amine compound is a water-soluble acid addition salt of N-pentachlorophenyl-N,N'-dimethyl-1,3-diaminopropane.
  • N-pentachlorophenyl amine compound is a water-soluble acid addition salt of N-pentachlorophenyl-N-methyl-l,3-diaminopropane.
  • a composition for impregnating textiles to render them permanently sterile comprising a solution of 2 to 10 grams of at least one water-soluble acid addition salt of N-pentaghlorophenyd-piperaaine and 1 to 3 grams of at least one agent se l'ected from the group consisting of anionic and non-ionic surface active agents in water.

Description

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Patented Mar. 17, 1970 METHOD OF PERMANENTLY STERILIZING TEXTILES WITH A SOLUTION OF AT LEAST ONE N PENTACHLOROPHENYLAMINE COMPOUND Arno Spange, Dusseldorf-Benrath, and Horst-Gunter liellinger, Dusseldorf, Germany, assignors to Bolhme Chemie Gesellschaft mit beschrankter Haftung, Dusseldorf-Benrath, Germany No Drawing. Filed June 15, 1965, Ser. No. 464,203
Claims priority, applicatiosn G frmany, Aug. 7, 1964,
,00 Int. Cl. A611 1/00, 13/00 US. Cl. 117138.5 12 Claims ABSTRACT OF THE DISCLOSURE A process for making textiles permanently sterile by treatment with a pentachlorophenylamine compound and to the novel impregnated textiles produced thereby.
PRIOR ART Pathogenic bacteria and fungi are known to adhere to textiles which are worn in direct contact with the skin and thereby cause a spreading of skin diseases and/or continuous reinfection of the wearer of the textiles. These germs cannot be eliminated or sufficiently destroyed by the mild detergents usually used for washing these textiles or by the temperatures employed in fine washing of fabrics such as nylon.
OBJECTS OF THE INVENTION The process of the invention for making textiles permanently sterile comprises impregnating the textile with a solution of at least one N-pentachlorophenylamine com pound selected from the group consisting of compounds of the formula wherein R is selected from the group consisting of hydrogen, alkyl of l to 6 carbon atoms and R R is R is an alkylene of l to 6 carbon atoms and n is an integer from to 4 and water-soluble acid addition salts thereof at a liquor ration of 1:20 to 1:40, removing the textile from the solution and drying the textile to obtain a textile which will remain sterile through repeated washings.
The compounds used to impregnate the textiles possess excellent antibacterial and antimycotic properties and are particularly efiective against pathogenic skin fungi such as Kaufmann-Woltf epidermophyton. The antimicrobic impregnations obtained in fine linens are very constant and even after repeated launderings, the treated textiles retain their antimicrobic activity and, therefore, are capable of effectively preventing the transmission of pathogenic bacteria and fungi for long periods of time.
The textiles to be treated by the process of the invention are articles which come in more or less direct contact with the skin such as underwear, stockings, bed linens, physicians smocks, hairdressers jackets, surgical and orthopedic article, etc. The textiles may be made of any known natural or synthetic fibers such as wool, rayon, nylon, etc. The impregnation treatment is especially suitable for textiles made of polyamide, polyurethane and albumin fibers.
Examples of suitable N-pentachlorophenyl amine compounds are N-pentachlorophenyl-ethylenediamine, N- pentachlorophenyl 1,3 diaminopropane, N-pentachlorophenyl 12-diaminopropane, N-pentachlorophenyl-N',N'- dimethyl 1,3-diaminopropane, N-pentachlorophenyll,4- diaminobutane, N-pentachlorophenyl-1,6-diaminohexane, N-pentachlorophenylpiperazine, N-pentachlorophenyl-N- methyl-1,3-diaminopropane, N-pentachlorophenyl-diethylenetriamine, N pentachlorophenyl-dipropylenetriamine, N-p'entachlorophenyl-dihexamethylenetriamine, N pentachlorophenyl-tetraethylenepentamine, etc.
Examples of suitable acids for the formation of watersoluble acid addition salts of the said N-pentachlorophenyl amino compounds are inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, etc. and low molecular weight organic acids such as formic acid, acetic acid, lactic acid, citric acid, etc. The organic acids are preferred.
The said N-pentachlorophenyl amino compounds can be prepared by reaction of hexachlorobenzene with aliphatic or cyclic dior polyamines containing at least one free amino hydrogen atom in the molecule in the presence of alkali, if necessary, as described, for example, in United States Patent No 2,829,164. The process described therein is advantageously varied so that the reaction is carried out with an essentially smaller excess of amine. The separation of the N-pentachlorophenyl amino compound from unreacted starting amine and hexachlorobenzene as well as from by-products simultaneously formed and from inorganic salts may be effected by treating the reaction mixture first with water, which removes the starting amine and inorganic salts, and then by means of extraction with hot, dilute acetic acid in which only the desired N pentachlorophenyl amino compound is soluble According to this process, the majority of the product is the monopentachlorophenyl amino compound which may also contain small amounts of constituents substituted with several pentachlorophenyl radicals. A separation of these latter products is unnecessary as a rule.
The solvents used to form the impregnating solutions may be organic solvents in which the N-pentachlorophenyl amino compounds are soluble such as lower alkanols, lower alkyl ketones, aliphatic hydrocarbons, etc. or water in which the acid addition salts of the N-pentachlorophenyl amino compounds are soluble.
The amounts of N-pentachlorophenyl amine compounds required in the impregnation bath depend on the textile material treated, on the impregnation method employed and on the eltect to be attained. As a rule, when working according to the padding or blocking method, about 2 to 10 gin/liter, and when working according to the glazing process, 0.5 to gm./liter of the compounds are used at a liquor ratio of about 1:20 to 1:40.
The impregnating solutions preferably contain 1 to 3 gm./liter of a non-ionic and/or anionic surface-active agent. Examples of suitable surface active agents are non-ionics such as the condensation products of 5 to 40 moles of lower alkylene oxides such as ethylene oxide with 1 mole of high molecular weight aliphatic alcohols, amines, carboxylic acids and amides, etc. and anionics such as alkali metal salts of aliphatic and aromatic sulfonates such as dodecyl sulfonate, dodecylbenzene sulfonate, tetrapropylenebenzene sulfonate, etc.
The impregnation of the textiles may be accomplished in the usual way such as the padding or blocking process. Particularly useful is the glazing process since the N-pentachlorophenyl amine compounds can be easily applied in substantial amounts on the textile from dilute aqueous solution of their acid addition salts. The degree of glazing can be increased in known methods by increasing the solution temperature, increasing the pH value about 5 and/or by the addition of additives such as the surface active agents. A particular advantage of the process is that the impregnation can be effected simultaneously with dyeing of the textiles by adding the said N-pentachlorophenyl amine compounds to the dye bath.
In the following examples there are described several preferred embodiments to illustrate the invention. However, it should be understood that the invention is not intended to be limited to the specific embodiments.
EXAMPLE 1 N-pentachlorophenyl-piperazine acetate In a 1 l ter, three-necked flask equipped with a stirrer, thermometer and condenser tube, a mixture of 259 gm. (3 mole) of substantially anhydrous piperazine and 285 gm. (1 mole) of hexachlorobenzene was gradually heated with stirring until the piperazine started to boil. The hexachlorobenzene dissolved slowly. The temperature of the reaction mixture rose in the course of 4 hours, calculated from the initial boiling point, from 147 to about 160 C. After this time, the moderately cooled mixture was stirred into about 500 liters of water and the undissolved substance was suction-filtered, thoroughly washed with hot water and then treated with 1 liter of hot 7% acetic acid -with addition of decolorizing carbon. The hot acetic acid solution was filtered and the N-pentachlorophenyl piperazine acetate was recovered from the cooled filtrate as a finely crystalline mass, which was suction. filtered, washed with ice water and then dried to obtain 280 gm. of the said product with a melting point of 166 to 170 C. After recrystallization from water and alcohol, the product had a melting point of 171 to 172.5 C.
(A) 0.25 gm. of N-pentachlorophenyl-piperazine acetate were dissolved in about 95 ml. of water and the pH of the solution was adjusted to a value of 5.5 by the addition of small amount of acetic acid and sodium acetate. The volume of the solution was brought to 100 ml. to obtain a liquor bath which was used for the following impregnation.
The liquor bath was heated to 80 C. and a piece of knitted nylon fabric, weighing about 2.5 gm., was placed therein and left for about 30 minutes with constant stirring while maintaining the bath temperature at 80 C. Then the fabric sample was rinsed with water having a temperature of 50 C. and then dried for 2 hours at 60 C. The amount of impregnation, ascertained by weighing the textile before and after the impregnation and by micro-analytical chlorine determination, amounted to approximately 2% of the weight of the fabric.
The impregnated fabric sample was cut up in four pieces of practically identical size. Three pieces were subjected to a variable number of the customary fine washings for nylon fabrics and one piece remained unwashed. Each fine washing consisted of a treatment for 10 minutes with a warm (40 C.) solution, which contained 2 term and wort agar for the fungi. Then the arrested areas developed around the textile samples were measured. Table I represents the results.
TABLE I Arrested-area widths in mm. for
Epidermophyton No. of washings Micrococcus aureus Kaut'mann-Wollf TABLE II Arrested area widths in mm. for-- Epidermophyton No. of washings Micrucoccus aureus Kaufmann-Woltf In a 250 cc. three-necked flask equipped with a stirrer, thermometer and reflux condenser, a mixture of 37.5 gm. (0.5 mole) of propylenediamine-(1,3) and 28.5 gm. (0.1 mole) of hexachlorobenzene was heated over one hour to reflux with stirring and maintained at reflux for one hour. The temperature of the reaction mixture rose from 125 to 140 C. Then, the excess initial amine was dis tilled off under water-jet vacuum and the distillation residue was poured into water. The recovered oil was separated from the aqueous layer, dissolved in dilute acetic acid, filtered off from a small amount of undissolved substance, and the filtrate was made alkaline with sodium hydroxide. The oil thus separated solidified while cooling to obtain N pentachlorophenyl-propylenediamine-( 1,3) having a melting point of 36 to 40 C. Upon recrystallization from cyclohexane, the product had a melting point of 42 to 43.5 C.
(A) A 0.5% solution of the acetate of the amine in water was prepared by dissolving N-pentachlorophenylpropylenediamine-(1,3) in dilute acetic acid, and adjust ing the pH value of 8.5 by the addition of dilute ammonium hydroxide. The impregnation of a knitted nylon fabric in this liquor bath and its subsequent treatment following the impregnation was accomplished according to the method described in step A of Example 1. The results of the microbiological examinations are given in Table III.
TABLE III 7 Arrested-area widths in mm. for
Epidermophyton N0. of washings Micrococcus aureus Kautrnann-Wolfl As nutrient medium, bouillon agar was used for the bac- EXAMPLE 3 N-pentachlorophenyl-diethylenetriamine Over a period of half an hour, 28.5 gm. (0.1 mole) of hexachlorobenzene were slowly added to 41.6 gm. (0.4 mole) of diethylenetriamine, which had been heated to 120 C. The mixture was held at theindicated temperature for 90 minutes, then it was stirred into 250 ml. of water. The undissolved oil was separated and the aqueous layer was extracted with several portions of ether. The solution, obtained by the combination of the ether extracts with the oil was dried over sodium sulfate and the ether was removed by distillation to obtain 31.6 gm. of a light brown, viscous oil, almost all of which dissolved in dilute acetic acid.
The raw dia cetate of N-pentachlorophenyl-diethylenetriamine had a melting point of 92 to 100 C. and upon recrystallization from acetic acid had a melting point of 104 to 106 C. The dihydrochloride of N-pentachlorophenyl-diethyle netriamine was repaired with excess alcoholichydrochloric acid and contained 15.59% chlorine (calculated 16.73%).
(A) A 0.25% solution of the amine acetate in water was prepared from N-pentachlorophenyl-diethylenetriamine and dilute acetic acid and the pH value was adjusted to 8.5 by addition of dilute ammonium hydroxide. The impregnation of a sample of nylon fabric in this liquor bath and its subsequent treatment was accomplished in the manner described in step A of Example 1. The amount ofimpregnation was 2.8% of the weight of the material. The results of the microbiological examinations are presented in Table IV.
TAB LE IV Arrested-area widths in mm. for
Epidermophyton N0. of washings Micrococcus aureus KaufmannWolff EXAMPLE 4 N-pentachlorophenyl-N',N-dimethyl-( 1,3 diaminopropane 61.4 gm. (0.6 mole) of N,N-dimethyl-(1,3)-diamino propane and 85.5 gm. (0.3 mole) of hexachlorobenzene were heated together to reflux with stirring in a threenecked flask equipped with a stirrer, reflux condenser and thermometer placed in a steam bath maintained at a temperature of about 170 C. The hexachlorobenzene gradually started to dissolve. The temperature of the re= action mixture rose from 138 to 162 C. over a period of three and one half hours. After this period, the reaction mixture was poured into about 300 m1. of water and the oil thus separated was worked up in the manner described in Example 2 to obtain 80 gm. of N-pentachlorophenyl-N',N-dimethyl-1,3-diaminopropane having a melting point of 40.5 to 41 C.
(A) A 0.25% solution of the amine acetate, based on free amine, was prepared from N-pentachlorophenyl- N,N'-dimethyl-diaminopropane-(1,3) and dilute acetic acid and the pH value was adjusted to 6.3. The impregnation of a sample of nylon fabric in this liquor bath and its subsequent treatment following the impregnation was carried out in the manner described in step A of Example 1. The amount of impregnation was 2.6% of the weight of the material. The microbiological examination of the impregnated samples are shown in Table V.
TABLE V Arrested-area widths in mm. for
A dye bath containing 1% of a dispersion dye (Perliton Brown G), 4% of N-pentachlorophenyl-piperazine acetate and 2% of a mixture of sodium tetrapropylenebenzene sulfonate and a fatty alcohol polyethyleneglycol ether (all percentage data are based on the weight of the textile to be d'yed) was prepared. A sample of nylon fabric weighing about 2.5 gm. was placed in 100 ml. of this bath heated to 40 C. with a liquor bath ratio about 1:40. Over 15 minutes, the temperature of the liquor bath was raised to 90 C. and maintained there for 15 minutes. The sample was taken out of the bath and rinsed in water. Whereas the dyeing obtained showed no differences in comparison with those which had been obtained without any addition of N-pentachlorophenyl-piperazine acetate, the antimicrobic effect corresponded with those values obtained in step A of Example 1.
EXAMPLE 6 The pH relation to the penetrating ability of N-pentachlorophenyl-piperazine acetate, N pentachlorophenyl- (1,3)-diaminopropane acetate and N-pentachlorophenyldiethylenetriarnine acetate on nylon fabric was observed in the tests described hereinafter.
(A) N-pentachlorophenyl-piperazine acetate Layer in percent Adjustment of the pH value of weight of goods with pH value Formic acid o Sodium acetate Ammonia .1
(B) N-pentachlorophenyl-( 1,3 -diaminopr0pane diacetate Using the method described in step A, samples of nylon fabric were treated with 0.25% solutions of N-pentachlorophenyl-(IQ)-diaminopropane diace'tate. The bath treatment was effected for 30 minutes at a temperature of C. followed by rinsing and drying as in step A.
TABLE VII Layer in percent of weight of goods Adjustment of the pH value wlthpH value Sodium acetate None Ammonia.
(C) N-pentachlorophenyl-diethylenetriamine acetate 0.025% liquor baths of the compound were prepared and adjusted to a pH value of 5.5 or 8.5 by adding sodium acetate or ammonium hydroxide. While stirring continuously, five samples of nylon fabric, each weighing about 500 mg., were left in 100 ml. of this bath heated to 80 C. for 30 minutes. The samples were rinsed and dried as described in step A.
7 TABLE VIII Epidermophyton No. of washings DIZ'CTOCOCLWS aureus KauImann-Wolfi Ad ustment oi the pH value Layer in percent withpH value of weight of goods 5 1% V (mean values) 4 4 5 Sodium acetate 5.5 1. 20 4 (10) Ammonium hydroxide 8. 5 2.
7 EXAMPLE 7 The microbic effectiveness of some N-pentachlorophenyl-alkylene amine compounds or their acetates described in the preceding examples and used for the anti-microbic impregnation of textile samples was characterized by determination of the arrest-concentrations in relation to one each of gram-positive and gram-negative types of bacteria as well as two specimens of fungi. The evaluation of the arrest-concentrations was accomplished with the aid of the dilution test according to the direction of the Deutsche Gesellschaft fiier die Pruefung chemis'cher Desinfections Mittel (Germany Society for Hygiene and Microbiology for the Examination of Chemical Disinfectants). The incubation temperature was 37 C. for bacteria and 30 C. for fungi. The results are summarized in Table IX.
Various modifications of the compositions and method of the invention may be made without departing from the spirit or scope thereof.
We claim:
1. A process for making textiles permanently sterile which comprises impregnating the textile with a solution of at least one N-pentachlorphenylamine compound se" lected from the group consisting of compounds of the formula:
C1 Cl and.
wherein R is selected from the group consisting of hydrogen, alkyl of l to 6 carbon atoms and R R is R is an alkylene of l to 6 carbon atoms and n is an integer from 0 to 4 and water-soluble acid addition salts thereof at a liquor ratio of 1:20 to 1:40, removing the textile from the solution and d 1 ying th e textile.
2. The process of claim 1 wherein the impregnating solution contains 1 to 3 grams of at least one agent selected from the group consisting of anionic and non-ionic surface-active agents per liter of solution.
3. The process of claim 1 wherein the impregnating bath has a pH greater than 5.
4. The process of claim 1 wherein the impregnating solution is an aqueous solution of a low molecular weight organic acid addition salt of the N-pentachlorophenyl amine compound.
5. The process of claim 1 wherein the N-pentachlorophenyl amine compound is a water-soluble acid addition salt of N-pentachlorophenyl-piperazine.
6. The process of claim 1 wherein the N-pentachlorophenyl amine compound is a water-soluble acid addition salt of N-pentachlorophenyl-1,3-diaminopropane.
7. The process of claim 1 wherein the N-pentachlorophenyl amine compound is a water-soluble acid addition salt of N-pentachlorophenyl-diethylenetriamine.
8. The process of claim 1 wherein the N-pentachlorophenyl amine compound is a water-soluble acid addition salt of N-pentachlorophenyl-N,N'-dimethyl-1,3-diaminopropane.
9. The process of claim 1 wherein the N-pentachlorophenyl amine compound is a water-soluble acid addition salt of N-pentachlorophenyl-N-methyl-l,3-diaminopropane.
10. Textiles produced by the process of claim 1.
11. Textiles produced by the process of claim 5.
12. A composition for impregnating textiles to render them permanently sterile comprising a solution of 2 to 10 grams of at least one water-soluble acid addition salt of N-pentaghlorophenyd-piperaaine and 1 to 3 grams of at least one agent se l'ected from the group consisting of anionic and non-ionic surface active agents in water.
References Cited UNITED STATES PATENTS 1,648,433 11/1927 White "s 817 2,489,363 11/ 1949 Bersworth 260-5705 2,829,164 4/1958 Rocklin 260570.5 2,859,242 11/1958 Moyle et a1 260570.5 X
WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner US. Cl. X.R.
US464203A 1964-08-07 1965-06-15 Method of permanently sterilizing textiles with a solution of at least one n - pentachlorophenylamine compound Expired - Lifetime US3501341A (en)

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US1648433A (en) * 1924-04-16 1927-11-08 Vivatex Processes Inc Textile material and method of dyeing the same
US2489363A (en) * 1947-08-05 1949-11-29 Frederick C Bersworth Chlorinated derivatives of alkylene polyamines
US2829164A (en) * 1955-09-13 1958-04-01 Dow Chemical Co Method of making pentachloroaniline and certain new n-substituted pentachloroanilines and alkyl tetrachloro analogs
US2859242A (en) * 1957-10-04 1958-11-04 Dow Chemical Co N-[2-(pentachloroanilino)-ethyl] carboxamic acids

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US2951786A (en) * 1955-01-14 1960-09-06 Spencer Chem Co Bactericidal and fungicidal compositions comprising pentahalophenyl n-(phenyl) carbamates
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US1648433A (en) * 1924-04-16 1927-11-08 Vivatex Processes Inc Textile material and method of dyeing the same
US2489363A (en) * 1947-08-05 1949-11-29 Frederick C Bersworth Chlorinated derivatives of alkylene polyamines
US2829164A (en) * 1955-09-13 1958-04-01 Dow Chemical Co Method of making pentachloroaniline and certain new n-substituted pentachloroanilines and alkyl tetrachloro analogs
US2859242A (en) * 1957-10-04 1958-11-04 Dow Chemical Co N-[2-(pentachloroanilino)-ethyl] carboxamic acids

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Publication number Priority date Publication date Assignee Title
US20180008496A1 (en) * 2013-03-14 2018-01-11 Liko Research & Development Ab Split drum for lift strap in ceiling lift
US10646392B2 (en) * 2013-03-14 2020-05-12 Liko Research & Development Ab Split drum for lift strap in ceiling lift
US11679049B2 (en) 2013-03-14 2023-06-20 Liko Research & Development Ab Split drum for lift strap in ceiling strap

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