OLIGOMERIC HALOGENATED DIPHENYL ETHER COMPOUNDS

Abstract: The invention describes oligomeric halogenated diphenyl ether compounds of formula (1), in which Y is the radical of formula (1a); (1b); or (1c); R1 and R2 independently of one another are F, Cl or Br; R3 is the radical of an initiator molecular for the free-radical polymerization; R4 is hydrogen; or C1-C5 alkyl; R5 is the radical of an initiator molecule for the anionic or cationic polymerization; A1 is a fragment from the recombination or from a chain transfer reaction; A2 is the counterion in the ionic polymerization; Q1 is a bivalent radical of formulae: (1d); (1e); (1f); or (1g); m is 1 to 3; n is 1 or 2; p1 is 0, or 1; q1 is 1, 2 or 3; and r1, r2 and r3 independently of one another are 2-20. The oligomeric diphenyl ether compounds according to the invention have excellent antimicrobial properties and are stable to migration.

Description: - 1 - Oligomeric halogenated diphenyl ether compounds The present invention relates to oligomeric halogenated diphenyl ether compounds, to a process for the preparation of these compounds, to their use as antimicrobial active substance in polymeric materials and to polymeric compositions comprising these compounds. It is known that certain halogenated diphenyl ether compounds have excellent antimicrobial activity. These compounds are therefore widely used, for example as active substances for the antimicrobial finishing of medical items and household articles, as detergent additive and in the hygiene sector, for example in soaps or dental hygiene products. Polymeric materials can be antimicrobially finished by incorporating halogenated diphenyl ether compounds, the active substance being, as a result of its excellent migration properties, constantly conveyed to the surface of the corresponding material ("slow release"). For certain industrial applications, this effect is undesired since the long-term effect of antimicrobially finished materials such as textiles, paper, plastics, cellulose sponges etc. is reduced at the same time. The object of the present invention is thus to provide diphenyl ether compounds which have antimicrobial activity and which, at the same time, are stable to migration. Surprisingly, it has been found that certain oligomeric halogenated diphenyl ether compounds satisfy these requirements. The present invention thus provides oligomeric halogenated diphenyl ether compounds of the formula (1) in which Y is the radical of the formula (1 a) R 3 - c— -CH 2 A, ; (1 b) R 5 - -CH; — CH-O- I ( (9H 2 or (1 c) R 5 - -O— CH— CH- (CH 2 ) r R-i and R 2 independently of one another are F, Cl or Br; R 3 is the radical of an initiator molecule for the free-radical polymerization; R is hydrogen; or C 1 -C 5 alkyl; R 5 is the radical of an initiator molecule for the anionic or cationic polymerization; Ai is a fragment from the recombination or from a chain transfer reaction; A 2 is the counterion in the ionic polymerization; Qi is a bivalent radical of the formula (1d) \=o ; (1e) — P — ; (1f) _^ C H 2 _ ; or(1g) -0-{ - m is 1 to 3; n is 1 or 2; P is 0; or 1 ; q, is 1 ; 2; or 3; and η; r 2 and r 3 independently of one another are 2-20. C C 5 alkyl and C C 5 alkoxy are straight-chain or branched alkyl radicals, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert- amyl and methoxy, ethoxy, propoxy, butyloxy, pentyloxy, amyloxy or isoamyloxy. Ai is, in particular, hydrogen. A 2 is, in particular, an alkali metal ion, such as Li + , Na + , K + or a halogen anion, such as, for example, F. Interesting compounds of the formula (1) are those in which Ai is hydrogen; - 3 - A 2 is an alkali metal ion; or a halogen anion; R 3 is C C 5 alkyl; C 1 -C 5 alkoxy; hydroxy; phenyl; or benzoyloxy; and R 4 is hydrogen; or CrC 5 alkyl; R 5 BF 2 ; C 1 -C 5 alkyl; C r C 5 alkoxy; or phenyl. Particular preference is given to oligomeric halogenated diphenyl ether compounds of the formula (1 ) in which Y is a radical of the formula (1b). Very particular preference is given to compounds of the formula (1) in which, in formula (1b), R 5 is C C 5 alkoxy; A 2 is hydrogen; or alkali metal; and qi is 1. Other preferred oligomeric halogenated diphenyl ether compounds of the formula (1 ) are those in which Y is a radical of the formula (1 a); R 3 is C C 5 alkoxy; R 4 is hydrogen; or CrC 5 alkyl; ri is 2-20; and Pi is 0. - 4 Also of interest are novel oligomeric compounds of the formula (1) in which Y is a radical of the formula (1 h) R 3 c ? 4 - -CH; ; (i i) R 3 - C CH 2 -H (1 k) or ^=0 R_ (11) R 3 - n -CHr -H In the above mentioned formulae (1h)-(1 l), R 3 is Cι-C 5 alkyl; Ci-C 5 alkoxy; hydroxyl; phenyl; or benzoyloxy; R is hydrogen; or C C 5 alkyl; and ri is 2-20. Particular preference is given to compounds of the formula (1) in which Ri and R 2 are chlorine; m is 2; and n is 1 ; or compounds of the formula (1), in which Ri and R 2 are chlorine; and m and n are 1. Of particular interest are compounds of the formula Cl O-Y O -Y (2a) r^γ ° γ^jj and (2b) Y is as defined in formula (1). Illustrative novel oligomeric diphenyl compounds conform to the formulae -5- R,- -O- -CH^ 2-C lH— O- -o- -CHr— CH— O- 2-20 2-20 (3a) ;(3b) Cl o o C! Cl Cl Cl HC-CH, -R, HC-CH -R, :θ 2-20 '2-20 (4a) Cl o ;(4b) o Cl Cl Cl Cl CH, CH, C-CH^ -C-CH :θ 2-20 2-20 (5a) ; (5b) Cl O Cl Cl Cl Cl 6- R, -CH, -CH, CH- CH- (6a) ;(6b) 2-20 2-20 Cl o o o Cl Cl Cl Cl H 2 C H 2 C R,- CH R -CH A (7a) ; (7b) :Cj =0J - 1 2-20 - 1 2-20 Cl O Cl Cl Cl Cl A, ^CH- -H 2 C- A,— cH H 2 C^— R 3 2-20 Cl o 2-20 (8a) ; (8b) O Cl Cl Cl Cl (9a) or (9b) 2-20 In the formulae (3) to (9), R 3 is CrC 5 alkyl; C C 5 alkoxy; hydroxyl; phenyl; or benzoyloxy; Ai is hydrogen; and A 3 is Na + ; or K + . The novel halogenated oligomeric diphenyl ether compounds are readily obtainable synthetically in high yields. Compounds of the formula (1 ), in which Y is a radical of the formula (1a), are obtainable, for example, by reaction of 1 mole of the compound of the formula O - Y, (R,) π o (10) (R 2 )n in which Yi is a radical of the compound of the formula (10a) — ( Q ,) — CH=CH 2 , with from 0.02 to 0.4 mol of a free-radical initiator, such as, for example, AIBN, dicumyl peroxide, dilauroyl peroxide, potassium peroxidisulphate or a mixture of H 2 O 2 /FeCI 2 . Compounds of the formula (1 ) in which Y is a radical of the formula (1 b), are obtainable, for example, by reaction of 1 mole of the compound of the formula (R,)π (10) O" in which o Yι is a radical of the formula (2b) cH j CH (CH 2 ) — t with from 0.05 to 0.5 mol of an alkali metal C C 5 alkoxide compound. The reaction is preferably carried out at temperatures of from 80 to 180°C, in the absence or presence of an inert organic solvent, such as, for example, xylene or toluene. The reaction times usually range from 1 to 10 hours. The oligomeric diphenyl ether compounds according to the invention are thermally stable and antimicrobially active compounds of low volatility which have a severely reduced tendency to migrate. They are therefore preferentially suitable for use in polymeric compounds, for example in plastics, rubbers, paints, surface coatings, (textile) fibres or paper, that are exposed to microbial contamination. Examples of polymers and other substrates which can be antimicrobially finished in this way are: - polymers of mono- and diolefins, - polyolefins, - copolymers of mono- and diolefins with one another or with other vinyl monomers, - hydrocarbon resins, - polystyrene, - copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, - graft copolymers of styrene or α-methylstyrene, - halogen-containing polymers, - 9 - - polymers derived from α,β-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, - polymers derived from unsaturated alcohols and amines or acyl derivatives or acetals thereof, - homo- and copolymers of cyclic ethers, polyacetals, polyphenylene oxides and polyphenylene sulfides and mixtures thereof with styrene polymers or polyamides, - polyurethanes derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other, and precursors thereof, - polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, - polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, poly- hydantoins and polybenzimidazoles, - polyesters, - polycarbonates and polyester carbonates, - polysulphones, polyether sulphones and polyether ketones, - crosslinked polymers derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins, - drying and non-drying alkyd resins, - unsaturated polyester resins, - crosslinkable acrylic resins, - alkyd resins, polyester resins and acrylate resins, - crosslinked epoxy resins, - natural polymers, such as cellulose, natural rubber, gelatin, and derivatives thereof which are modified chemically in a polymer-homologous manner, such as cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers, such as methylcellulose; and also rosins and derivatives. The invention thus also provides a composition comprising (A) an organic material to be antimicrobially finished and (B) a compound of the formula (1). The invention also relates to a process for the antimicrobial finishing of an organic material, which comprises adding at least one compound of the formula (1 ) thereto, and to the use of the compound of the formula (1) for the antimicrobial finishing of polymeric materials. - 10 - The amount of antimicrobial active substance to be used depends on the organic material to be antimicrobially finished and on the intended use of the material finished in this way. The composition according to the invention generally comprises, per 100 parts by weight of component (A), from 0.01 to 15 parts by weight, in particular from 0.05 to 10 parts by weight, and especially from 0.1 to 5 parts by weight of the antimicrobial active substance (component (B)). The antimicrobial active substance (compound (B)) can also be a mixture of two or more compounds of the formula (1 ). The compounds according to the invention can, in addition to the compounds according to the invention, also comprise other additives, for example antioxidants or light protection agents. Incorporation into the organic polymers, for example into the synthetic organic, in particular thermoplastic, polymers can take place by adding the halogenated oligomeric diphenyl ether compound according to the invention and, if desired, other additives by the methods customary in the art. Incorporation can expediently take place before or during shaping, for example by mixing the pulverulent components or by adding the antimicrobial active substance(s) to the melt or solution of the polymer, or by applying the dissolved or dispersed compounds to the polymer, if desired with subsequent evaporation of the solvent. Another method of incorporating the composition according to the invention into polymers involves adding the former before or during polymerization of the corresponding monomers or before crosslinking. The compositions according to the invention can also be added to the organic polymers to be finished in the form of a masterbatch which comprises these compounds, for example, in a concentration of from 2.5 to 25% by weight. The resulting antimicrobially finished polymer compositions can be converted into shaped articles, for example fibres, films, tapes, sheets, multi-wall sheets, containers, tubes and other profiles, by conventional methods, for example by hot pressing, spinning, extrusion or injection moulding. - 11 - The novel oligomeric diphenyl ether compounds of the formula (1 ) are also suitable for the antimicrobial finishing of undyed and dyed or printed fibre materials made, for example, of silk, wool, polyamide or polyurethanes, and in particular for the finishing of cellulosic fibre materials of all types. Examples of such fibre materials are the natural cellulose fibres, such as cotton, linen, jute and hemp, and also pulp and regenerated cellulose. Preference is given to textile fibre materials made of cotton. The oligomeric diphenyl ether compounds according to the invention are also suitable for the antimicrobial finishing of hydroxyl-group-containing fibres which are present in mixed fibres, for example, of mixtures of cotton with polyester fibres or polyamide fibres. The oligomeric diphenyl ether compounds according to the invention can be applied to the fibre material and fixed to the fibre in different ways, in particular in the form of aqueous dispersions or printing pastes. For this purpose, one or more compounds of the formula (1 ) are advantageously applied to the textile fibre material in an amount of from 0.01 to 5% by weight, preferably 0.1-3% by weight, and in particular from 0.25 to 2% by weight, based on the weight of the fibre material, in a process analogous to dyeing. The textile fibre materials finished using the compounds of the formula (1) according to the invention have excellent and long-lasting antimicrobial protection. The examples below serve to illustrate the invention. 12 Preparation examples of novel compounds Example 1 : Reaction scheme: H-C-C-O potassium tert-butoxide Cl -o- // W // toluene 110°C (101a) (101 ) 5 g (14.5 mmol) of the compound of the formula (101a), 160 mg (1.45 mmol) of potassium tert-butoxide and 10 ml of toluene are introduced under argon into a 50 ml round-bottom flask provided with magnetic stirrer and reflux condenser. The mixture is heated to reflux and stirred overnight. The dark, clear solution is cooled to room temperature and poured onto 100 ml of methanol. The precipitated polymer is separated off. 3 g (60%) of a fine powder are obtained. Elemental analysis Calculated Found C 52.13% 53.17% H 3.21% 3.50% Cl 30.77% 29.09% H-NMR (CDC- M: 2.35 ppm tert-butyl end group of the initiator 2.5-3 ppm no CH and CH 2 signals of the epoxy ring of the monomer (compound of the formula (101a)) - 13 - TGA (= "Thermal Gravimetric Analysis") (air, 2°C/min heating rate): A 10 % weight loss of the polymer occurs at 297°C. Example 2: The procedure is as described in Example 1 except that 40 g (115 mmol) of the compound of the formula (101a) are reacted with 1.3 g (11.5 mmol) of potassium tert-butanol in 20 ml of xylene. After heating under reflux for 4 hours, monomer can no longer be detected in GC. All of the solvent is then evaporated off under high vacuum. 40.3 g of a solid polymer are obtained. Elemental analysis: Calculated Found C 52.13 % 52.09 % H 3.21% 3.37% Cl 30.77% 29.93% GPC analysis: ("Gel Permeation Chromatography"): Mn =1200 Mw = 2100 MALDI-MS ("Matrix Assisted Laser Desorption"): Mn = 1200 (Mn = number-average molecular mass) Mw = 1600 (Mw = weight-average molecular mass) TGA (air. 2°C/min): 10% weight loss at 292°C. Example 3: 100 g (289 mmol) of the compound of the formula (101a) and 3.24 g (28.9 mmol) of potassium tert-butyloxide and 100 g of xylene are weighed into a 250 ml round-bottom flask fitted with magnetic stirrer, condenser and argon balloon. The mixture is heated to reflux, and the homogeneous solution is left in this way for 5 hours. GC analysis indicates <0.5% of monomer in the reaction solution. Yield: 102 g - 14 - TGA (air. 2°C/min,: 10% weight loss at 293°C MALDI-MS: Mn = 1200, Mw =1520 Example 4: Determination of the antimicrobial activity of the compound of the formula (101 ) Test method: An agar well test is carried out (method CG 126) with the following modifications: Medium: Casein Soybean flour peptone agar (Caso-agar) Test bacteria: Staphylococcus aureus ATCC 9144 Escherichia coli NCTC 8196 Procedure: 500 ml of Caso-agar are inoculated with 3.5 ml of a 1 :100 diluted overnight culture of the bacteria, and Caso plates with a volume of about 18 ml are poured. After the plates have cooled, wells having a diameter of 1 cm are cut out using a cork borer (1 well per plate; all test substance concentrations are measured twice). 100 μl of a dilution of the compound of the formula (101 ) are poured into each well and the plates are incubated at 37°C for 24 hours. Dilutions of the compound of the formula (101 ) are prepared in 96% analytical grade ethanol. 15 - Results: Table 1 : Substance Cone. r%l Diameter of zone of inhibition (mm) E.coli S. aureus Compound of the formula 1.0 10/10 18/19 (101) 0.1 8/8 15/15 0.01 5/5 10/11 The results in Table 1 show that the compound of the formula (101) has very good antimicrobial activity toward Staphylococcus aureus and Escherichia coli even at concentrations of 0.01%. Example 5a: Reaction scheme: CH„ CH -=CH, / * 2 O ■ CICH-CH=CH 2 (102b) Cl -Cl Na 2 C0 3 (102a) (102c) 51 g of compound of formula (102a) is dissolved in 500 ml of acetone at 60°C under reflux. To this solution 22.1 g of Na 2 CO 3 is added and dissolved. The mixed solution is again heated for 30 minutes. 15.3 g of compound of formula (102b) is added into the mixed solution over a period of 30 minutes. The mixture is allowed to be heated at 80°C under reflux for another 30 minutes. At the completion of the reaction, the solvent acetone is stripped off on a Rotavapor and the residues are redissolved in 200 ml of toluene followed by filtration to remove any solid substances. The filtered solution is then twice extracted with deionized water. After the extraction, anhydrous Na 2 SO 4 is added to the organic phase and remained overnight to remove any moistures present in the solution. The solvent toluene is then evaporated under a Rotavapor and produce of formula (102c) is collected. Yield of product of formula (102c): 49.5 gram 16 - Example 5b: Co-polymerisation with styrene Reaction scheme: CH : =CH, (102c) (102d) CH 5 0.2% AIBN, 80°C (102e) 2 grams of freshly prepared compound of formula (102c) is added into 98 grams of styrene (10d, CH 2 =CH-C 6 H 5 ) which was already prepared by extraction with water to remove polymerisation inhibitor. To this mixture, 0.2 gram of AIBN (2,2 ' -azo-bisisobutyronitrile) is added as initiator for polymerisation. The mixture is heated to 80°C and maintained at this temperature overnight. The resulting product is a co-polymer of the formula (102e) of styrene and compound of formula (102c). 17 - Example 5c: Co-polymerisation with methyl methacrylate Reaction scheme: — CH H 3 C- :CH„ θ O— CH, (102f) (102g) 3 g of compound of formula (102c) is added into 97 gram methyl methacrylate (compound of formula (102f)) which was previously prepared by extraction with water to remove polymerisation inhibitor. Into the mixture 0.2 g of AIBN(2,2 ' -azo-bisisobutyronitrile) is added as initiator for polymerisation. The mixture is then heated to 50°C to allow pre-polymerisation for about 2 hours. Finally the reaction temperature is risen to 70°C and allowed to carry out overnight. The resulting polymer (102g) is a copolymer of compounds of formula (102c) and methyl methacrylate. Example 6: Microbiological test for the polymer Polymer samples of the compounds of formula (202e) and (202g) are tested for antimicrobial efficacy. For polymer, 5 g of sample is taken from the polymer prepared as shown in examples 5b and 5c. The sample is then pulverised into fine granules followed by heat compress into specimens in the form of discs (diameter 2cm, thickness 2mm). Microbiological evaluation: Determination of the bacteriostatic activity according to the bacterial growth inhibition test (agar diffusion test, CG 147). - 18 Samples: - Polystyrene placebo unmodified and commercially available - Poly(DCS-Styrene) Co-polymer of compound of formula (102c) and styrene - Poly(methyl methacrylate) unmodified and commercially available poly (methyl methacrylate) Poly(DCS-methyl Co-polymer of compound of formula (102c) and methyacrylate) methyl methacrylate Test principle: For the preparation of the agar plates a bottom layer of 15 ml sterile agar medium is poured in petri dishes and after solidification of the agar, 6 ml of a germ-containing agar are evenly distributed on the bottom agar layer. In order to prepare the germ-containing agar 3.5 ml of an 1 :100 (Staph. aureus) and 1 :1000 (E. coli) diluted over-night culture of the bacteria are mixed with 500 ml molten agar at 47°C. After solidification the samples (20 mm discs) are applied in the middle of the inoculated plates (upper- and under-side; one sample per plate). Each test is performed twice. All plates are then incubated for 24 hours at 37°C. After incubation the zones of inhibition were measured and reported in Table 2. Test bacteria: Staphylococcus aureus ATCC 9144 Escherichia coli NCTC 8196 Nutrient medium: Casein soy meal pepton agar Incubation: 18-24 hours at 37°C All samples are tested twice and both results are given in Table 2: 19 Table 2: Microorganisms Staph. aureus Escherichia coli ATCC 9144 NCTC 8196 Samples zr VR zi VR Polystyrene placebo 0 3 /0 0/0 0/0 0/0 Poly(DCS-styrene) 3/3 4 4 /4 1/1 4/4 Poly(methyl methacrylate) placebo 0/0 0/0 0/0 0/0 Poly(DCS-methyl methacrylate) 5/4 4/4 1/2 4/4 Zone of inhibition in millimetres Vinson rating, for growth under the disc 0 = strong growth (no activity) 4 = no growth (very good activity)

Claims: 20 WHAT IS CLAIMED IS: 1. An oligomeric halogenated diphenyl ether compound of the formula (1) y . (R 2 )n in which Y is the radical of the formula (1 a) R 3 - -c- -CH; A ; (1 b) R 5 - -CH; — CH-O- A ; <9ι)„. (9 H 2 ) or (1 c) R 5 - -O— CH— CH- (9H 2 Ri and R 2 independently of one another are F, Cl or Br; R 3 is the radical of an initiator molecule for the free-radical polymerization; R 4 is hydrogen; or Cι-C 5 alkyl; R 5 is the radical of an initiator molecule for the anionic or cationic polymerization; AT is a fragment from the recombination or from a chain transfer reaction; A 2 is the counterion in the ionic polymerization; Qi is a bivalent radical of the formula (1d) \=o ; (1 e) — P — ; Of) -\ ^^ " ; or (1g) ~ ^CH\° : m is 1 to 3; n is 1 or 2; Pi is 0; or 1 ; q, is 1 ; 2; or 3; and r r 2 and r 3 independently of one another are 2-20. 21 2. A compound according to Claim 1 of the formula (1 ), in which Ai is hydrogen 3. A compound according to Claim 1 or 2 of the formula (1 ), in which A T is hydrogen; A 2 is an alkali metal ion; or a halogen anion; R 3 is C C 5 alkyl; C C 5 alkoxy; hydroxyl; phenyl; or benzoyloxy; and R 5 is BF 2 ; C 1 -C 5 alkyl; C Cs alkoxy; or phenyl. 4. A compound according to Claim 1 of the formula (1 ), in which Y is a radical of the formula (1 b). 5. A compound according to claim 4, wherein, in formula (1 b) R 5 is C C 5 alkoxy; A 2 is hydrogen; or alkali metal; and qi is 1. 6. A compound according to Claim 1 , wherein Y is a radical of the formula (1a), in which R 3 is C C 5 alkoxy; R 4 is hydrogen; or C C 5 alkyl; r-i is 2-20; and P T is 0. 7. A compound according to Claim 1 , wherein Y is a radical of the formula (1 h) -CH; -H ^o in which R 3 is CrC 5 alkyl; C C 5 alkoxy; hydroxyl; phenyl; or benzoyloxy; R 4 is hydrogen; or Cι-C 5 alkyl; and r, is 2-20. 22 - 8. A compound according to Claim 1 , wherein Y is a radical of the formula R„ (1 i) R 3 " -CH; -H L ^ in which R 3 is C C 5 alkyl; C C 5 alkoxy; hydroxyl; phenyl; or benzoyloxy; R 4 is hydrogen; or C C 5 alkyl; and n is 2-20. 9. A compound according to Claim 1 , wherein Y is a radical of the formula (1 k) R 3 - -CH; in which R 3 is C 1 -C 5 alkyl; C C 5 alkoxy; hydroxyl; phenyl; or benzoyloxy; R is hydrogen; or C 1 -C 5 alkyl; and n is 2-20. 10. A compound according to Claim 1 , wherein Y is a radical of the formula R I . (11) R„- -CH 2 -f-H in which R 3 is C Cs alkyl; Cι-C 5 alkoxy; hydroxyl; phenyl; or benzoyloxy; R 4 is hydrogen; or CrC 5 alkyl; and 23 r, is 2-20. 11. A compound according to any one of Claims 1 to 10 wherein, in formula (1 ), R T and R 2 are chlorine; m is 2; and n is 1. 12. A compound according to any one of Claims 1 to 10 wherein, in formula (1), Ri and R 2 are chlorine; and m and n are 1. 13. A compound according to Claim 1 , which conforms to the formula Cl O - Y .O (2a) cr in which Y is as defined in Claim 1. 14. A compound according to Claim 1 which conforms to the formula O -Y .O . (2b) cr in which Y is as defined in Claim 1. 15. A process for the preparation of the compounds of the formula (1 ), in which Y is a radical of the formula (1a), by reaction of 1 mole of the compound of the formula ( A ° _ Y ' (10) " o ° (R 2 )„ in which - 24 - R. Yi is a radical of the compound of the formula (10a) — (Q,)— CH-----:cH 2 Pi with from 0.02 to 0.4 mol of a free-radical initiator such as, for example, AIBN, dicumyl peroxide, dilauroyi peroxide, potassium peroxidisulphate or a mixture of H 2 O 2 /FeCI 2 . 16. A process for the preparation of the compound of the formula (1 ), in which Y is a radical of the formula (1 b), by reaction of 1 mole of the compound of the formula O -Y, (R,) π (2) ^ (R 2 )n in which o Y T is a radical of the formula (10b) CH 2 CH — (CH 2 ) — ; °.1 with from 0.05 to 0.5 mol of an alkali metal CrCs alkoxide compound. 17. A process according to Claim 16, which comprises carrying out the reaction at temperatures of from 80 to 180°C. 18. A process according to Claim 16 or 17, which comprises carrying out the reaction with an inert organic solvent such as, for example, xylene or toluene. 19. A process according to any one of Claims 15 to 18, wherein the reaction time is from 1 to 10 hours. 20. A process for the antimicrobial finishing of an organic material, which comprises adding at least one compound of the formula (1) thereto. 21. The use of the compounds according to any one of Claims 1 to 14 for the antimicrobial finishing of polymeric materials, - 25 - 22. A composition comprising (A) an organic material to be antimicrobially finished and (B) as antimicrobial active substance at least one compound according to any one of claims 1 to 14.

Inventors: HUEGLIN DIETMAR, MAO JIANWEN, OCHS DIETMAR, STEINMANN ALFRED, HUEGLIN, DIETMAR, MAO, JIANWEN, OCHS, DIETMAR, STEINMANN, ALFRED
Applicants: CIBA GEIGY AG, HUEGLIN DIETMAR, MAO JIANWEN, OCHS DIETMAR, STEINMANN ALFRED, CIBA SPECIALTY CHEMICALS HOLDING INC., HUEGLIN, DIETMAR, MAO, JIANWEN, OCHS, DIETMAR, STEINMANN, ALFRED
Application year: 1999
Main classification: C07C43
IPC codes: C07C43, C08G65