Composition comprising isosorbide monoesters and isosorbide diesters

Abstract

What are described are compositions comprising one or more compounds of the formula (I) and one or more compounds of the formula (II) ##STR00001##
in which R, R.sup.a and R.sup.b each independently of one another are straight-chain or branched saturated alkyl groups having 5 to 11 carbon atoms or straight-chain or branched mono- or polyunsaturated alkenyl groups having 5 to 11 carbon atoms, wherein the total amount of the compounds of the formulae (I) and (II), based on the total weight of the compositions, is at least 60% by weight. In an advantageous manner, the compositions are suitable for producing cosmetic, dermatological or pharmaceutical compositions, crop protection formulations, washing or cleaning compositions or paints or coatings.

Claims

1. A method for controlling a fungus, comprising the step of applying a composition comprising at least one or more compound of the formula (I) and at least one compound of the formula (II) ##STR00004## in which R, R.sup.a and R.sup.b are each independently of one another straight-chain or branched saturated alkyl groups having 5 to 11 carbon atoms or straight-chain or branched mono- or polyunsaturated alkenyl groups having 5 to 11 carbon atoms, wherein the total amount of the compounds of the formulae (I) and (II), based on the total weight of the composition, is at least 60% by weight, where the composition, in addition to the compounds of the formulae (I) and (II), comprises at least one other substance selected from the group consisting of sorbitol, sorbitol esters, sorbitan, sorbitan esters, isosorbide and carboxylic acids and the hydroxyl value of the mixture of the compounds of the formulae (I) and (II) and additionally the one or more compounds selected from the group consisting of sorbitol, sorbitol esters, sorbitan, sorbitan esters, isosorbide and carboxylic acids is smaller than or equal to 250.

2. The method as claimed in claim 1, wherein the weight ratio of the one or more compounds of the formula (I) to the one or more compounds of the formula (II) is from 5:95 to 95:5.

3. The method as claimed in claim 1, wherein the radicals R, R.sup.a and R.sup.b in the formulae (I) and (II) are each independently of one another straight-chain saturated alkyl radicals having 7 to 9 carbon atoms.

4. The method as claimed in claim 3, wherein the radicals R, R.sup.a and R.sup.b in the formulae (I) and (II) are straight-chain saturated alkyl radicals having 7 carbon atoms.

5. The method as claimed in claim 1, wherein the composition comprises from 0.1 to 1.0 part by weight of the at least one compound of the formula (II), based on 1.0 part by weight of the at least one compound of the formula (I).

6. The method as claimed in claim 5, wherein the composition comprises from 0.05 to 0.7 part by weight of isosorbide, based on 1.0 part by weight of the at least one compound of the formula (I).

7. The method as claimed in claim 1, wherein the composition comprises from 0.001 to 0.2 part by weight of the at least one compound of the formula (I), based on 1.0 part by weight of the at least one compound of the formula (II).

8. The method as claimed in claim 1, wherein the composition comprises in each case at least one compound of the formula (I) and (II) and additionally at least one sorbitan ester of sorbitan and a carboxylic acid R.sup.cCOOH, where R.sup.c is a straight-chain or branched saturated alkyl group having 5 to 11 carbon atoms or a straight-chain or branched mono- or polyunsaturated alkenyl group having 5 to 11 carbon atoms, and where the weight ratio of the compounds of the formulae (I) and (II) together to the at least one sorbitan ester is from 70:30 to 100:0.

9. The method as claimed in claim 8, wherein the at least one sorbitan ester of sorbitan and a carboxylic acid R.sup.cCOOH is selected from the group consisting of sorbitan esters of sorbitan and caprylic acid.

Description

EXPERIMENTAL EXAMPLES

A) Preparation of Isosorbide Caprylate 1

(1) In a stirred apparatus with distillation head, 190.0 g (1.3 mol) of isosorbide (Sorbon from Ecogreen Oleochemicals) and 187.5 g (1.3 mol) of octanoic acid (caprylic acid) are initially charged at 80 C. together with 0.38 g of aqueous sodium hydroxide solution (18% by weight strength, aqueous) as catalyst. With stirring and under a flow of nitrogen (10-12 liters per hour), the reaction mixture is initially heated to 180 C., where the water of reaction begins to distill off. The reaction is then heated to 190 C. over a period of 1 hour and to 210 C. over a further 2 hours. After 210 C. is reached, the esterification is continued until an acid value of <1 mg KOH/g is reached. This gives 345.7 g of amber isosorbide caprylate (97% of theory). The pH (5% by weight in ethanol/water 1:1) is 5.9. The pH was measured according to DIN EN 1262.

(2) Further analytical characteristics of the isosorbide caprylate 1: Acid value: 0.9 mg KOH/g, measured according to DIN EN ISO 2114 Hydroxyl value: 206 mg KOH/g, measured analogously to DIN 53240-2 according to method OHV-A Saponification value: 204 mg KOH/g, measured according to DIN EN ISO 3681

(3) The isosorbide caprylate 1 has the following composition:

(4) TABLE-US-00001 Substance % by weight caprylic acid 0.4 isosorbide 18.1 isosorbide monocaprylate 50.9 isosorbide dicaprylate 30.6

B) Preparation of Isosorbide Dicaprylate

(5) In a stirred 1 liter apparatus under a stream of nitrogen, 219.0 g (1.5 mol) of isosorbide and 461.4 g (3.2 mol) of caprylic acid are heated with stirring and under a stream of nitrogen to 180 C. The reaction mixture was heated at 180 C. until no more water of reaction distilled off (about 28 h). The temperature was then gradually increased to 210 C. (altogether over about 30 h). The reaction has ended when a residual acid value of <2 mg KOH/g is reached. This gives a clear red-brown solution.

(6) Further analytical characteristics of the reaction product: Acid value: 0.8 mg KOH/g, measured according to DIN EN ISO 2114 Hydroxyl value: 25.2 mg KOH/g, measured analogously to DIN 53240-2 according to method OHV-A Saponification value: 54.6 mg KOH/g, measured according to DIN EN ISO 3681

(7) For further purification, the product was distilled at a pressure of 1 mbar and a bottom temperature of from 210 C. to 240 C. This gives 251.6 g of a clear yellow liquid.

(8) The isosorbide dicaprylate has the following composition:

(9) TABLE-US-00002 Substance % by weight isosorbide monocaprylate 9.4 isosorbide dicaprylate 89.6 remainder 1

C) Determination of the Thickener Performance

(10) Using Genapol LRO (sodium laureth-2 sulfate, 27% by weight in water) and Genagen KB (cocobetain, 30% by weight in water) and additionally water, a 15% by weight mixture in water comprising the two surfactants in a weight ratio of 8:2 (hereinbelow referred to as mixture A) is obtained. The thickener performance of isosorbide caprylate 1, isosorbide dicaprylate and isosorbide in mixture A was determined. The results are shown in Table 1.

(11) TABLE-US-00003 TABLE 1 measured viscosities Substance added to mixture A; amount Viscosity [% by weight] [mPa .Math. s] none 135 isosorbide caprylate 1 [1% by weight] 2510 isosorbide dicaprylate [1% by weight] 2390 isosorbide [1% by weight] 160

(12) As is evident from the results of Table 1, the thickener performance of isosorbide is not worth mentioning, whereas isosorbide caprylate 1 and isosorbide dicaprylate cause significant thickening.

D) Determination of the Antimicrobial Efficacy of Isosorbide Caprylate 1

(13) Below, the antimicrobial efficacy of isosorbide caprylate 1 in butyl polyglycol against bacteria, fungi and yeast is examined. For the tests with bacteria, isosorbide caprylate 1 was diluted with butyl polyglycol and then added to liquid CASO agar (casein-peptone agar) buffered to pH 7 (+/0.2) in various concentrations (hereinbelow referred to as compositions B1, B2, etc.). For the tests with fungi and yeasts, isosorbide caprylate 1 was diluted with butyl polyglycol and then added to liquid Sabouraud 4% dextrose agar buffered to pH 5.6 (+/0.2) in various concentrations (hereinbelow referred to as compositions PH1, PH2, etc.). The compositions B1, B2, etc. and PH1, PH2 etc. were each poured into Petri dishes and each inoculated with identical amounts of bacteria, fungi and yeasts. The minimum inhibitory concentration (MIC) is the concentration at which inhibition of the growth of the bacteria, fungi and yeasts in the compositions B1, B2, etc. and PH1, PH2, etc. occurs.

(14) The values determined for the minimum inhibitory concentrations of isosorbide caprylate 1, stated in Table 2 below, have already been corrected for the dilution effect of the butyl polyglycol.

(15) TABLE-US-00004 TABLE 2 Minimum inhibitory concentrations (MIC) of isosorbide caprylate 1 MIC of isosorbide Bacteria (B), fungi (F) or yeasts caprylate 1 (Y) examined [ppm] Staphylococcus aureus (B) 2500 Pseudomonas aeruginosa (B) 10000 Escherichia coli (B) 7500 Enterobacter aerogenes (B) 10000 Klebsiella pneumoniae (B) 10000 Proteus vulgaris (B) 5000 Pseudomonas oleovorans (B) 10000 Citrobacter freundii (B) 10000 Candida albicans (H) 600 Aspergillus brasiliensis (P) 800 Penicillium minioluteum (P) 600 Aspergillus terreus (P) 600 Fusarium solani (P) 600 Penicillium funicolosium (P) 400

(16) The results listed in Table 2 show that isosorbide caprylate 1 is antimicrobially active, in particular against the yeast Candida albicans and the fungi tested.

E) Use Examples

(17) The following formulations are prepared using the composition according to the invention isosorbide caprylate 1.

Formulation Example 1: Revitalizing Moisturizing Cream

(18) TABLE-US-00005 % by Phase Ingredient weight A Hostacerin SFO 2.0 sunflower seed oil sorbitol esters Velsan CCT 4.5 caprylic/capric triglyceride Cetiol OE 4.5 dicaprylyl ether Lanette 22 4.0 behenyl alcohol Lanette 18 4.0 stearyl alcohol Fucogel 1000 1.0 biosaccharide gum-1 B Coenzyme Q 10 0.1 ubiquinone C water ad 100 glycerol 10.0 Hostaphat CK 100 0.6 potassium cetyl phosphate D phenoxyethanol 1.0 isosorbide caprylate 1 1.0 E NaOH (10% by weight in water) q.s.
Preparation: I The components of A are mixed and the mixture is heated to 80 C. II The components of C are mixed and the mixture is heated to 80 C. III B is added to I. IV II is added to III and the mixture is stirred until it has cooled to room temperature V D is added to IV VI The pH is adjusted to 5.5 using E

Formulation Example 2

(19) TABLE-US-00006 % by Phase Ingredient weight A Hostacerin EWO 16.0 polyglyceryl 2-sesquiisostearate (and) cera alba (and) carnauba wax (and) ethylhexyl stearate (and) magnesium stearate (and) aluminum stearate isopropyl palmitate 10.0 avocado oil 2.0 Velsan CCT 2.5 caprylic/capric triglyceride B Octopirox 0.05 piroctone olamine propylene glycol 1.0 C water ad 100 glycerol 4.0 magnesium sulfate *7 H.sub.2O 0.7 allantoin 0.5 D tocopheryl acetate 0.5 Rosmarinus officinalis (rosemary) leaf oil 0.1 urea 10.0 isosorbide caprylate 1 1.0 phenoxyethanol 0.8
Preparation: I The components of A are mixed and the mixture is heated to 80 C. II The components of B are mixed until all substances have been dissolved (if required with gentle heating) III II is added to I IV The components of C are mixed and the mixture is heated to 50 C. V IV is stirred into I at high speed until the mixture has cooled to 35 C. VI D is added to V at 35 C.

Formulation Examples 3 and 4: Crop Protection Formulations

(20) TABLE-US-00007 Formulation No. 3 4 Amount of the respective ingredient Ingredient [% by weight] atrazine 43.6 43.6 Dispersogen PSL 100 1.7 Genapol LSS 1.6 Dispersogen LFS 2.1 propylene glycol 4.3 4.3 Defoamer SE 57 0.6 0.6 Kelzan S (2% by 7.3 7.3 weight in water) isosorbide caprylate 1 0.3 0.2 phenoxyethanol 1.0 1.0 water ad 100 ad 100
Preparation:

(21) The active ingredient is pre-dispersed with the other ingredients (except for the Kelzan S solution) and then subjected to fine grinding until the mean particle size is <2 micrometers. The Kelzan S solution is then stirred in.

Formulation Example 5: Dishwashing Liquids

(22) TABLE-US-00008 Ingredient % by weight Hostapur SAS 60 40.0 (alkanesulfonate, 60% by weight in water) Hostapur OS liquid 11.0 (sodium C14-16 alkyl sulfonate, 40% by weight in water) Genaminox LA 3.0 (dimethyllauramine oxide, 30% by weight in water) Genagen CAB 3.0 (cocoamidopropyl betaine, 30% by weight in water) isosorbide caprylate 1 0.8 benzyl alcohol 0.8 water ad 100

Formulation Example 6: Surface Cleaners (All-Purpose Cleaners)

(23) TABLE-US-00009 Ingredient % by weight Hostapur SAS 60 5.0 (alkanesulfonate, 60% by weight in water) Genapol UD 080 2.0 (undecanol + 8 EO) Genaminox LA 2.0 (dimethyllauramine oxide, 30% by weight in water) methylisothiazolinone 0.01 isosorbide caprylate 1 1.0 water ad 100

Preparation of Formulation Examples 5 and 6

(24) Half of the amount of water is initially charged and the components are added by mixing in the same order as listed in the tables given for formulation examples 5 and 6. The remaining amount of water is then added. This gives clear aqueous compositions.