US3806530A - Organo tin derivatives of tetrafluoro-cyclo-butyl acrylic acids - Google Patents

Abstract

WHEREIN R1, R2, R3 AND R4 ARE INDENTICAL OR DIFFERENT AND REPRESENT ALKYL RADICALS HAVING 1 TO 8 CARBON ATOMS, PHENYL RADICALS OR PHENYL RADICALS SUBSTITUTED BY LOWER ALKYL RADICALS AND R5 REPRESENTS HYDROGEN OR THE METHYL GROUP AND THE USE OF THESE COMPOUNDS FOR THE ANTIMICROBIAL FINISHING OF TEXTILES.

CYCLOBUTANE

1,1,2,2-TETRA(F-),3-(R1-SN(-R2)(-R3)-OOC-C(-R5)=CH-),4-R4-

TIN-ORGANIC COMPOUNDS OF THE FORMULA 1

Description

FIPtSF-Ul United States Patent 3,806,530 ORGANO TIN DERIVATIVES 0F TETRAFLUOR0- CYCLO-BUTYL ACRYLIC ACIDS Christoph Dorfelt, Burghausen, Salzach, Klaus Fischer, Kelkheim, Taunus, and Walter Dittmar, Hofheim, Taunus, Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main, Germany No Drawing. Filed July 7, 1972, Ser. No. 269,867 Claims priority, application Germany, July 9, 1971,

P 21 34 358.8 Int. Cl. C07j 7/22 US. Cl. 260-429.7 4 Claims ABSTRACT OF THE DISCLOSURE Tin-organic compounds of the Formula I R1 R Sn-O-CC=OHOHCHRr Ra l I ls CFr-CFT- (1') wherein R R R and R are identical or different and represent alkyl radicals having 1 to 8 carbon atoms, phenyl radicals or phenyl radicals substituted by lower alkyl radicals and R represents hydrogen or the methyl group and the use of these compounds for the antimicrobial finishing of textiles.

The present invention relates to the antimicrobial finishing of textiles.

It is already known how to provide textiles with an antimicrobial finishing, by treating them with the tinorganic compounds such as tributyl tin oxide or triphenyl tin oxide (cf. Textilver-edlung 5 (1970), 1 p. 9). These compounds have the disadvantage that they cannot be fixed on textiles, especially textiles made of synthetic fibre materials, with a resistance to washing and to chemical cleansing. Furthermore, these compounds do not possess any bacteriostatic activity Another disad vantage is that they adversely affect the dry creasing angles when they are applied together with crease-resistant finishing agents.

It has now been found that the disadvantages described of the known tin-organic compounds may be eliminated if for an antimicrobial finishing of textiles tin-organic compounds of the general Formula I are used, wherein R R R and R represent identical or different alkyl or aryl radicals and R represents hydrogen or the methyl group.

In the Formula I R R R and R 4 may stand above all for alkyl radicals having 1 to 8 carbon atoms, phenyl radicals or phenyl radicals substituted by lower alkyl radicals; R R and R preferably represent butyl or phenyl radicals and R is a methyl, ethyl, butyl, propyl or phenyl radical.

The present invention relates to tin-organic compounds of the general Formula I wherein R R R and R are identical or different and represent alkyl radicals having 1 to 8 carbon atoms, phenyl radicals or phenyl radicals substituted by lower alkyl radicals and R represents hydrogen or the methyl group.

The invention further relates to a process for preparing these compounds, in which 1 mol of a bi-organic tin oxide of the Formula II is condensed with about 2 mols of a carboxylic acid of the Formula 111 R4-OHCH-GH'=G-COOH CFz- Fr Rt (III) the radicals R to R having the meanings mentioned in the Formula I.

The invention also relates to a process for the anti= microbial finishing of the textiles, in which tin-organic compounds of the above-mentioned general Formula I are applied onto textiles form solutions or dispersions, the textiles are dried and then expediently heated to high temperatures.

Among the compounds of the Formula I to be used ac-= cording to the invention for the antimicrobial finishing of textiles, there may be mentioned the following com pounds, without any restriction being made:

Tributyltin-B-tetr afluorcyclobutylacrylate, Triphenyltin-fl-tetrafluorocyclobutylacrylate,

Tributyltin- 3-methyl-tetrafiuorocyclobutylacrylate, Triphenyltin-B-methyl-tetrafiuorocyclobutylacrylate, Tributyltin-fl-tetrafluorocyclobutylmethacrylate, Tributyltin-B-methyl-tetrafluorocyclobutylmethacrylate, Triphenyltin-fl-tetrafiuorocyclobutylmethacrylate, Triphenyltin-fi-methyl-tetrafiuorocyclobutylmethacrylate.

The compounds of the Formula I possess a good fungi static and bactoriostatic activity. Attention must also be paid to the resistance to washing and to chemical cleansing with halogenated hydrocarbons of the finishes on textiles obtained with the compounds according to the invention. The resistance to washing of these finishes may be further improved, if the compounds applied on the textile ma= terial are subjected to an alkaline after-treatment. When being applied, the compounds of the Formula I have the surprising advantage that they provide on synthetic fibres such as polyamide and polyacrylonitrile fibres, anti microbial effects fast to washing. On the cellulose fibre textiles even 'boilproof finishes may be prepared. In the application of the compounds of the Formula I a further advantage is that these compounds do not lead to a. yellowing of the textile material. As compared with many antimicrobial agents, they do not cause any additional soiling, for example on textile floor covering.

Textiles and other materials which may be anti= microbially finished with the compounds of the Formula I are for example woven and knitted superficial materials, yarns, fleeces, reinforced fleeces, textile laminated mate rials, feathers as well as synthetic leather. The textiles to be antimicrobially finished may consist of natural fibres such as cellulose fibres, wool, silk or synthetic fibres, as for example polyamide, polyacrylonitrile, polyester fibres, polyvinyl chloride-elastomeric fibres, inorganic fibres, asbestos and glass fibres and mixtures of such fibres, as

for example made of polyester fibres/cotton, polyester fibres/spun rayon, polyacrylonitrile fibres/spun rayon,

polyester fibres/linen, polyester fibres/wool or polyamide fibres/ cotton etc.

The preparation of the compounds of the Formula I by reacting bis-organic tin oxides of the Formula II, for example bis-tributyl tin oxide, with carboxylic acids of the Formula III, for example fi-tetrafluoro-cyclobutyl acrylic acid or methyl-tetrafluoro-cyclobutyl acrylic acid may be carried out according to known processes in a suitable organic solvent such as benzene, toluene and xylene. The reaction proceeds at elevated temperature, expediently at the boiling temperature of the solvent under reflux, whereby according to the reaction desired, about 2 mols of the carboxylic acid of the Formula III per mol of the bis-organic tin oxide of the Formula II are used. The water formed during condensation was eliminated together with the solvent by azeotropic distillation. The substance left after distilling off the solvent may be used, if desired, directly, without any further purification, for the antimicrobially finishing according to the invention.

The tin-organic compounds of the Formula I are soluble in many organic solvents. Particularly suitable solvents with regard to the textile application of these compounds are lower aliphatic alcohols, especially those having 1 to 4 carbon atoms. The tin-organic compounds according to the invention are also soluble in an aqueous, alkaline medium, for example in aqueous solutions of alkali hy= droxides, alkali carbonates or -bicarbonates. When being applied onto textiles, they may therefore be applied from organic solvents, from mixtures of solvent and water and at pH-values above 7 from aqueous solutions or emulsions, for example those consisting of chloroor fluorohydrcarbons with water or alcohol. For the antimicrobial finishing of textiles there are generally used solutions which show a content of about 10 to 100 g., preferably 15 to 40 g., of the tin-organic compounds of the For mula I per liter of bath. This concentration of the finish-= ingbaths mostly insures an effective amount of deposit depending on the squeezing out effect. The minimum of the effective amount required is about 0.3%, calculated on the goods weight. There is no upper limit for the amounts of tin-organic compounds to be applied. HOW- ever, an amount to be applied exceeding about 5% cannot be considered practical for economical reasons. 7

For the antimicrobial finish of textiles, the tin-organic compounds of. the Formula I may be used as such and together with other finishing and binding agents. It is also possible to apply the tin-organic compounds together with. optical brighteners or antistatically effective agents. For finishing textiles whichv consist of cellulose fibres or contain cellulose fibres, the tin-organic compounds are expediently applied onto the textile material with crease resistant finishing agents. In this processespecially in the case of cross-linking under dry conditions-good boilproof .fungistatic effects can be achieved. The tin-organic compounds may also be used in the known cross-linking processes of textiles in the presence of more or less amounts of water. Particularly advantageous is the use of tin-organic compounds together with finishing agents which are cross-linking in an alkaline medium. The tinorganic compounds may also be used in the dyeing of textiles and may be added for example to the dyestuff bath or printing paste. By this way, antimicrobial effects are simultaneously obtained with the dyeing or printing. A special advantage is the application of the tin-organic compounds together with dyestuffs which can be fixed in an alkaline medium. It is furthermore possible to apply the tin-organic compounds onto the textile material together with hydrophobing, oleophobing and flame-proof finishing agents.

The tin-organic compounds of the Formula I may be applied onto the good to be finished in any manner desired, for example by padding, slop padding, spraying,

doctoring or according to the exhaustion process. The textiles treated with the solutions or dispersions of the tin-organic compounds are dried at room temperature or elevated temperature and expediently heated for about 1 second to 5 minutes up to high temperatures. The choice of the temperature depends on the heating time and on the textile material. There are generally used temperatures in the range of about to 220 C. It has turned out advantageous to subject the textiles treated with the tin-organic compounds of the Formula I and dried, with solutions of diluted alkalis or to apply the compounds of the Formula I to textiles pretreated with alkalis and alkaline reaction.

It is also possible to incorporate the tin-organic compounds according to the invention into pastes, pigment mixtures and the like for coating purposes. The use of the tin-organic compounds together with plastic disper sions, such as polyacrylate, polyurethane, butadiene-co polymer, polyvinylacetate dispersions or natural latex, is particularly important, if floor covering, for example car pets, needle felts, mats or fleeces shall be finished fun gistatically and bacteriostatically.

In the following examples parts and percentages are by weight unless stated otherwise.

The antimicrobial eificiency of the textile finishes in the following examples was tested according to the meth od described in the periodical Textilveredlung 5 (1970), pp. 12 to 14. For this purpose, Petri dishes of plastics were fed each with 20 ml. of malt extract-dextrose-agar and the germs were applied onto the solidified surface as inoculating layer. The ends of the layers were covered with a test cloth (2 x 2 cm.) of the finished good. After an incubation time of 8 days at 28 C., the growth of the germs on the textile material and in its surroundings (in cubation zone) was estimated as follows:

Findings Mark The agar layer over the fabric sample shows the same growth intensity of the test germ as the surroundings.= :3. On the agar layer over the sample only some colonies are grow ing; inhibition of growth in contradistinction. to the surround= in s 2 The agar layer over the fabric sample does not show any colonies of microorganisms W. un 3 No growth on the agar layer above the sample; an inhibition zone not larger than 2 mm. is clearly visible around the sample... 4

Around the fabric sample there is any inhibition zone of more han2rnm EXAMPLE 1 Fabric samples made of polyamide fibres were impregnated in each case with the following solutions:

ing machine were compiled in Table L TABLE 1 Growth inhibition (mark) Trichoph. Aspen Solution meat. niacr EXAMPLE 2 The samples of a polyacrylonitrile fabric were treated in each case with the following solutions:

Solution A:

Tributyl-tin-fi-(methyl)-tetrafiuoro cyclobutyl acry= late in isopropanol/water (3:1 parts by volume), Solution B:

Triphenyl tin-fi-(methyl)-tetrafluoro-cyclobutyl acrylate in isopropanol/water (3:1 parts by volume) and Solution C (comparison) Tributyl tin oxide in isopropanol/ water (3:1 parts by volume).

The squeezing off effect was 50% by weight The fabric samples were dried at 100 C. and fixed for one minute at 150 C, The finishes prepared with the solutions A and B have excellent fungistatic effects against dermatomycetes and soil fungi and yeast.

The following Table 2 resumes the antimicrobial effects after three washing processes in a washing machine:

TABLE 2 Growth inhibition (mark) Candida Candida Trichoph, albicam albz'cam Asperqillua Solution meat, St 1 604 niger 533 A t 3 3 3 3 B u 3 3 3 3 C l 1 1 1 EXAMPLE 3 The samples of a cotton poplin were impregnated with solutions of the following composition indicated;

The squeezing off effect was 50% by weighti After pad-dyeing the fabric was dried and fixed by heat ing for one minute to 180 C, The textiles finished with the solutions A to C have an excellent fungistatic and a. bacteriostatic effect,

As solvent there is used a mixture of 3 parts by volume of isopropanol and 1 part by volume of water;

After pad-dyeing the samples were dried at C on a stretching frame and then condensed for 5 minutes at 150 C. The samples of the finished fabrics show a marked fungistatic effect against dermatoinycetes, soil fungi and blastomycetes and a bacteriostatic effect against Sraphylw coccus aureuso After two processes in a washing machine, a clear in hibition of growth of Trichophyton mentagrophytes (den matomyces) and Aspergillus niger (soil fungus) could be demonstrated in the case of the samples A to C, On the sample D, however, no efficiency of the finish was ob== served. Whereas the tin-organic compounds in the solu= tions A to C have practically no influence on the dry creasing angles of the fabrics, the tributyl tin oxide of the sample D causes a considerable diminution of the dry crease angle EXAMPLE 4 Samples of a cotton fabric were impregnated in each case with a bath consisting of Solution A:

10 g./l. of tribuytl tin-,B-tetrafiuoro-cyclobutyl acry1- late and, Solution B;

101 g./l., of tributyl tin-/3-tetrafiuorocyclobutyl acry= atew squeezed off until reaching a weight increase of 70% and dried at 100 C; Isopropanol/water (3:1 parts by volume) is used as solvent, The dried fabric samples were then treated with 5 gt/lu of sodium hydroxide solution (32% rolled together and packed in a foilr After storing for 18 hours in this state, the samples were rinsed, neutralized and dried.

The fabrics have an excellent fungistatic effect against: dermatomycetes, yeasts and soil fungi and a bacteriostatic effect. It must be mentioned that these samples show after two processes in washing machines a strong inhibition of the growth of the fungi on the fabric sample and at the periphery of the sample in the case of Trichophyton mentagrophytes, Candida albicans and Aspergillus nigelg, furthermore in the case of Staphylococcus aureuso EXAMPLE 5 A polyester fibre fleece was impregnated on the padding machine with a bath which contained 25 parts of a 42% aqueous dispersion of a copolymer consisting of 52% of butyl acrylate, 25% of acrylo-= nitrile, 21% of styrene and 2% of acrylamide,

2 parts of tribuytl tin- 3-(methyl)-tetrafiuorocyclobutyl acrylate and 33 parts of isopropanola After squeezing off to reach a weight increase of 509% the whole was dried and condensed for 7 minutes at C" The reinforced fleece showed in the test a fungistatic and bacteriostatic effect against Trichophyton mentagrm phytes, Aspergillus niger and Staphylococcus amen-r0 T7 5% We claim: References Cited 1., Tin-organic compounds of the Formula I UNITED STATES PATENTS 3,133,942 5/1964 Hahl mmmmmmmmmm m 260-=429.7

5 3,409,652 11/1968 Horrocks m- 260429.7 R: 8 R, Jan-6F, 3,651,107 3/1972 Stanback et ai M--. 260429.7

wherein R R R and R are identical or different and a 5 represent alkyl radicals having 1 to 8 carbon atoms, phenyl DANIEL WYMAN Pnmary Exammer radicals or phenyl radicals substituted by lower alkyl' A P. DEMERS, Assistant Examiner radicals and R represents hydrogen or the methyl group 10 2. Tributyl tin-[5-tetrafiuoro-cyclobutyl acrylate. U51, CL

3, Tributyl tin-jS-rnethyl-tetrafluoro-cyclobutyl acrylate 160-15 r,

4c Triphenyl tin-p-methyl-tetrafiuoro-cyclobutyl acry= late,