DE2153810C3 - - Google Patents

Description

a benzene, cyclohexane, cyclohexene or cyclo- ' ⁵ hexadiene ring.

2. Process for the preparation of monoglycerides according to claim 1, characterized in that cyclic carboxylic acids of the general formula (CH ₂ J ₁ -COOH

(CH ₂ ), -H

in the χ, ν and

30th

the above meanings, are esterified in known manner with a 0.5- to 5-fold molar excess of glycerol at temperatures of 200 to 25O ⁰ C and the reaction product obtained after separation of the majority of the excess glycerol is optionally further purified by molecular distillation.

3. Use of the monoglycerides according to claim! as a gel former,

4. Use of the monoglycerides according to claim 3, characterized in that they are in one Concentration of at least 60 percent by weight, preferably not less than 90 percent by weight, be applied.

5. Use of the monoglycerides according to claim 1 as emulsifiers, advantageously in cosmetic Preparations such as skin care products, sun protection creams or oils, hair care products and shaving creams.

6. Use of the monoglycerides according to claim 1 as impregnation and coating agents for porous materials and fabrics, such as building materials, textiles, leather, as a fixative for Flavors and / or fragrances and for coating razor blades.

60

The invention relates to monoglycerides of cyclic carboxylic acids with advantageous properties, in particular with a pronounced ability to form gel, a process for their preparation and their Use as gelling agents and emulsifiers.

Carrier materials that are suitable for both hydrophilic and lipophilic products can be found on various technical fields, for example in cosmetics. Gel forming with water If the gels are stable enough, monoglycerides are eminently suitable as such carriers.

It is known that high-percentage monoglycerides of saturated, straight-chain fatty acids with at least 14 carbon atoms when heated above their melting point, which is usually above 60 ° C Water form firm gels. After G. Y. B rο k a w and W C. Lyman, Journal of the American Oil Chemists Society, vol. 35, p. 49 ff. (1958), these gels contain about 15 to 25 percent by weight of water. However, their stability is completely inadequate with regard to technical application, since the gels destroyed on cooling below the melting point of the monoglyceride as a result of progressive Krisii flisation will.

According to US Pat. No. 2,895,879, it is also known that high-percentage monoglycerides from mixtures of unsaturated fatty acids with at least 16 carbon atoms, for example oil. Linoleum and Linolenic acid, when mixed with water at room temperature, form relatively firm, clear gels. Such Monoglycerides of unsaturated fatty acids are, however, especially in the case of those which are liquid at room temperature containing linoleic or linoleic acid. highly sensitive to oxidation and therefore only has a limited shelf life. This low durability significantly limits their technical uses.

The invention is based on the object of producing glycerides that are already present with water Form gels stable at room temperature, their stability. Strength and resistance to oxidation the gels of the corresponding known products are significantly improved and are based on the most diverse Areas suitable as emulsifiers.

According to the invention this object is achieved in that as compounds which form gel with water Monoglycides of cyclic carboxylic acids of the general formula

(CH ₂ ^ -COOC ₃ H ₅ (OH) ₂

in der.χ and y = Oor 1 to 11 denied.tenand.x + .V = II and

a benzene, cyclohexane, cyclohexene or cyclohexadiene ring are to be made available.

The monoglycerides according to the invention have advantageous properties for many technical purposes. On contact with water, the monoglycerides according to the invention show, including in particular, monoglycerides according to the invention Monoglycerides of cyclohexane monocarboxylic acids have an exceptionally good ability to form that significantly exceeds that of the known monoglycerides, with particularly solid ones. stabiU Gels are formed.

The monoglycerides according to the invention are colorless and tasteless at room temperature loose to light yellow, surface-active cracks with an oily consistency. In contrast to dci known monoglycerides of the saturated, straight

chain fatty acids with the same carbon number do not only take place when heated above about 60 "C, but Even at temperatures around OT, gels with a waxy consistency are spontaneously stable as soon as they are used Come into contact with water, where they can absorb up to 35 percent by weight of water. she stand out compared to the known monoglyccrides of unsaturated, straight-chain fatty acids and their Mixtures are advantageous in that they are stable to oxidation despite their low melting points and Form gels of relatively high strength. The monoglycerides preferred according to the invention are more saturated cyclic monocarboxylic acids have a particularly high resistance to oxidation and form with water Gels of extremely high strength.

The strength of the gels was determined by determining the so-called C-values of the penetration with a Penetrometer from summer and stanchion below Use of the 40 ° cone determined with a load of 80 g. The results of these measurements are compiled in Tables 1 and 2, with the monoglycerides according to the invention preceded and then known monoglycerides are listed for comparison. Thus, in Table I under the Serial numbers 1 to 3 and in Table 2 under serial numbers 1 and 2 the monoglycerides according to the invention listed, on the other hand in Table 1 under numbers 4 to 7 and in Table 2 under the Numbers 3 to 5 the known monoglycerides used for comparison.

table

- 1 Monouhceride *!
out purity
the used Clear melting point C-value of the penetralion 5 seconds. • 1020 Gel at 2 (1 C I.fd.
No _._ ..._ fatty acids or texture
of monoglyceride measured on MV ₁ , H _; O * "| unsaturated cycli 93% at room temperature 22% H, O *) K9 cal carboxylic acids fluid 141 148 [according to example a)] saturated cyclic 93% WHERE 3 Carboxylic acids fluid 725 (26% H ₂ oil [according to example b)] 325 aromatic 96% No gel formation 93 4th Carboxylic acids fluid 100 5 [according to example c) J 6th oleic acid 99% 485 7th Linoleic acid ****) 98% 31.5 C 280 Linolenic acid 96% fluid No gel formation Linseed oil fatty acids about 100% fluid 82 fluid with fixed shares

*) All monoglycerides had a u +, / - monoglyceride content of 90%.

**) Production of "egg gels" according to USA patent 2 895 Sv79, example la.

** ·) Preparation of the gels according to US Pat. No. 2,895,879. Example 2a.

****) Gel made from it cannot be stored at room temperature.

table

Monoghccrid shown ans
following ictls.iurciiemisclicn

93% saturated cyclic
Carboxylic acids
(according to example 2)
6% saturated fatty acid
as serial no. I.
70% linoleic acid
26% oleic acid.
4% saturated fat

4 **) 57% linoleic acid
40% oleic acid

3% saturated fat
5 linseed oil fatty acid =
65% linoles-14% linole-15% oil-6% saturated fatty acids

* | Cloudiness after about 2 weeks.
**) According to USA patent specification 2 895X7 '). Example la.
** ·! Not molecularly distilled.

n + / f mono

ghceride content according to

Brokiiw

97

67 ***) 99

100

92

Klür-üchmcl / point or nature of the monoglyccide at room temperature

fluid

27 C

27 C

fluid with
fixed shares

Appearance of the gels
at room temperature

clear

cloudy
clear*)

clear
cloudy

C value of penetration. 5 seconds, measured on the gel at 20 ° C
22% H ₂ O

1020

150
560

600
100

Another important advantage of the invention Monoglyceride is the practically unlimited shelf life of your gels even at temperatures up to about 0 ° C. The gels produced from the monoglycerides according to the invention give when standing on the Air removes its water content through evaporation, whereby liquid monoglyceride is recovered. If you replace a certain part of the water with glycerine, you get gels that are also in the air are indefinitely stable because they do not give off water through evaporation. Because of their very little Water solubility, the gels are stable under water.

Another advantageous property of the invention Monoglycerides, which are similar to the monoglycerides of saturated, straight-chain fatty acids The number of carbon atoms that differs is their good solubility in organic solvents such as methanol, ethanol, isopropanol, benzene, petroleum ether, n-hexane, Diethyl ether, ethyl acetate, methylene chloride, carbon tetrachloride, dioxane, dimethylformamide, dimethyl sulfoxide and tetrahydrofuran and their unlimited miscibility with fatty oils and mineral oils such as Olive, castor or paraffin oil.

Mixtures of the monoglycerides according to the invention with such oils are always clear in contrast to mixtures of oils and, for example, stearic acid monoglyceride, which are not homogeneous even with a large excess of oil. Furthermore, the invention Monoglycerides can be colored with both oil-soluble and water-soluble dyes.

In contrast to the monoglycerides of straight-chain, saturated C _M - to C, _g -fatty acids, the monoglycerides according to the invention with cyclic carboxylic acids of the same number of carbon atoms have very low pour points. So z. B. the pour point of an approximately 92% mixture of α- and ^ -monoglycerides prepared according to Example 1 from saturated cyclic carboxylic acids, the value of which for χ + y = 11, -3 ° C, measured according to ASTM D-97-66. For example, a 95% monoglyceride produced from cyclic unsaturated carboxylic acids according to Example 1 had a pour point of -25 ° C., a 99% monoglyceride produced from aromatic carboxylic acids according to c) had a pour point of -18 ° C.

The process according to the invention for the preparation of monoglycene cyclic carboxylic acids is characterized in that one cyclic carboxylic acid the general formula

CH ₂ ) _X -COOH

(CH ₂ ), -H

in which χ and y = 0 or 1 to 11 and χ + y = \\ and

a benzene, cyclohexane, cyclohexene or cyclohexadiene ring, stvJd in a manner known per se with a 0.5- to S-fold molar excess of glycerol at temperature;)) esterified from 200 to 250 ° C and after separation of the bulk of the excess

Glycerin obtained reaction product, if appropriate

further purifies by molecular distillation. One can also triglycerate these carboxylic acids with a

Transesterification of excess glycerine. The esterification

s product without molecular distillation contains 60 to

70 weight percent monoglycerides. That distilled

The product consists of at least 90 percent by weight of monoglycerides according to the invention.

Used as the starting material for the manufacture of the

ίο Monoglycerides according to the invention required cyclic Carboxylic acids of the structure given above can be prepared by known methods, e.g. B. by alkali cyclization of triple or higher olefinically unsaturated fatty acids or Ulen, which are such fatty acids included, e.g. B. wood oil, linseed oil or fish oils, or by catalytic aromatization of esters or polyunsaturated fatty acids and subsequent enrichment of the desired cyclic Carboxylic acids and optionally their hydrogenation be won.

The reaction products with a low Monoglyceride content forms gels with water, but the relatively low C values of penetration show. For special purposes, e.g. B.

τ $ a'.s consistency generator for cosmetics, however, this gel-forming capacity is sufficient: in this case, there is no need for further enrichment of the monoglycerides.

In the case of the hydrogenated cyclic carboxylic acid monoglycerides, the higher the gels, the more solid they are the monoglycerides used are concentrated.

On the basis of the above, the invention Monoglycerides used in water gel-forming agents in such an amount.

that the content of these monoglycerides is at least 60%, preferably not less than 90%.

The monoglycerides according to the invention are also useful because of their low-lying pour points even at temperatures below 0 ⁿ C as emulsifiers.

They can also be beneficial cosmetic preparations such. B. added sunscreen creams and oils will. While the usual sunscreen preparations when bathing to a greater or lesser extent Washed off the skin and therefore reapplied after each stay in the water have to be effected by adding the monoglycerides according to the invention. that when wetting the moisturized skin becomes waxy with water. A viscous gel layer forms, which is washed out and washed off which prevents the skin protective cream, which prevents re-application of the cream after bathing becomes superfluous. The effect is similar when the substances according to the invention are used in hair care products, because they are difficult or impossible to wash out during bathing or horror.

The monoglycerides according to the invention are also used as additives to skin care products such as Hautpflegemi.ch very beneficial, as they not only improve and stabilize the consistency of the cosmetics, but also after applying such cosmetics to the skin after evaporation of that contained in the cosmetic Water form an oil film on the skin, which holds the components that protect and care for the skin. For the same reasons, it is also an additive to clear shampoos, waterproof make-up, cleansing creams or milk and the like are advantageous. An addition to toothpaste improves the fixation of essential oils and other flavors.

Hin Zusal /. to shaving creams has a beneficial effect on their consistency and lubricity. as well an application to razor blades is advantageous, since the monoglyceride on contact with the aqueous Shaving foam forms a gel-like layer that increases the effect of the surface and thus makes shaving easier.

The ability of the inventive monoglycerides Forming a stable, waxy gel on contact with water also makes them suitable for use Impregnation of porous materials or fabrics, e.g. B. for impregnating building materials or for Waterproofing textiles and leather are particularly suitable, e.g. B. as an additive to shoe care products. Also a use of the geis as underwater putty for alone or as an addition to other underwater kills and as a component of artificial bait for fishing is beneficial.

The preparation and use of the monoglyccrides according to the invention are illustrated in the following Examples explained in more detail.

Source material

a) The cyclic carboxylic acids were prepared by alkali cyclization of linseed oil in aqueous solution Medium based on R. E. Beal, R. A. E i s e η h a u e r and V. E. Sohns, J. Am. Oil (Hem. Soc. Vol. 42, p. 1115 (1965). Here, monomeric cyclic carboxylic acids of the following composition and with the following analytical characteristics receive:

Cyclic C, _a -carboxylic acids 93%

Straight chain fatty acids 6%

Unsaponifiable and other 1%

Acid number (AN) 194

Saponification number (VZ) 201.5

Iodine number (JZ) 123.5

b) The cyclic carboxylic acids prepared above under a) were hydrogenated with a nickel catalyst in a manner known per se. The product had the following composition and key figures: Saturated cyclic carboxylic acids .. 93.2%
Saturated linear carboxylic acids .... 5.8%

Aromatic carboxylic acids do not

verifiable

Unsaponifiable content 0.44%

SZ 202.3

VZ 202.0

n- 1.4721

c) The production of aromatic cyclic carboxylic acids was carried out according to D. E. F 1 ο y d, R. F. P a s c h k e, D. H. Wheeler and W. S. B a 1 d w i η, J. Am. Oil Chem. Soc., Vol. 33, p. 609 (1956). The isolated monomeric aromatic cyclic carboxylic acids had the following composition or key figures:

Aromatic, monocyclic

Cjg carboxylic acids 96%

Bicyclic C ₁₈ carboxylic acid 1.5%

Not aromatic cyclic

C _ia carboxylic acids, about 1%

Unsaponifiable content 0.9%

SZ 192.5

VZ 198.5

JZ 6.9

ni- 1.5041

example 1

Monoglyceride from saturated cyclic carboxylic acids

564 g (2MoI) saturated cyclic carboxylic acids (see. Test b) and 106Og (11.5 mol) of glycerol (99.5 to 99.8% pure) was added with good stirring and passing of N ₂ in about one hour at 25O ^f C heated and esterified for 8 hours under these conditions. After cooling, the two layers were

ίο with the addition of 1 I IO% aqueous NaCl solution and 750 ml of ethyl acetate separated. The aqueous Glycerinphasc was several times with 250 ml Ethyl acetate extracted and the combined ethyl acetate phases several times with 10% Shaken out NaCl solution, the ethyl acetate is distilled off from the glyceride mixture and the crude Glyceride dried in a rotary vacuum evaporator at 90 ° C. The yield from two batches was 1359 grams of monoglyceride.

Analysis of the raw monoglyceride:

61.6% it- + / i-monoglyceride (determined by the method of Brokaw, Perry and Ly man, J. Am. Oil Chemists Soc, Vol. 32, 194 (1955),
0.03% free glycerin.

The molecular distillation of 1290 g of this crude product at 173 ° C and a vacuum of 10 "Torr yielded 798 g of monoglyceride.

analysis

a- + / f-monoglyceride (Brokaw) .. 95.9%

Free glycerin 0.49%

Unsaponifiable content 0.22%

SZ 0.55

VZ 158.5

Color:

(Lovibond 2 ") 0.6 yellow

Orot

If 2 g of this molecularly distilled monoglyceride from saturated cyclic carboxylic acids were added to 10 ml of water in a test vial, a solid, clear gel was formed immediately. A repetition of the experiment with ^{water cooled to about 0 °} C. and monoglyceride likewise immediately gave a clear gel. The monoglycerides Jer obtained according to experiments a) and c) are obtained in a corresponding manner.

To test the emulsifying properties of monoglycerides saturated cyclic carboxylic acids, the interfacial tension of peanut oil, 0.1 to 1.0% prepared according to Example 1 was contained monoglyceride of about 96% purity, at 25 and 70 ⁰ C to

measured double-distilled water. The measurements were carried out with a tensiometer according to Dο g η ο η —A br ibat from the company “Prolabo” (Paris), which works according to the static measuring method of WiI hei my. The reading was taken 5 minutes after the plaque was immersed; no influence of time on the measured values was found thereafter. Length of the platinum plate 19.35 mm. The mean deviation in 5 measurements was a maximum of ± 0.1 dyn · cm " ¹ .

The results (see Table 3) clearly show the decrease in the interfacial tension of the oil compared to water by adding the monoglycerides according to the invention to the oil, especially at 25 ° C,

409648/321

emerged. However, a reduced interfacial tension between oil and water means an improved one Emulsifiability of the oil.

Table 3

Ulphasc

Purified
Peanut oil

the same

the same

the same

the same

additive

on mono

glyceride

(Weight percent)

0.1
0.2
0.5
1.0

Interfacial tension!

of oil against water

in dyn ■ cm 'at

25 "C

30.5

24.0 19.8 13.4

7.3

TO-C

30.8

28.2 25.6 20.8 15.6

The use of the compounds according to the invention as gel formers and emulsifiers is described in the the following examples.

Example 2 hand milk

Weight percent

Vaseline oil 10.5

Monoglyceride according to Example 1 5.0

Woilfett 2.0

Polyoxyethylene ether of a saturated

Fatty alcohol 2.0

Trioleyl-o-phosphate 0.25

Polyoxyethylene sorbitan mono-

laurate 0.30

High molecular weight carboxyvinyl

polymer 0.15

Triethanolamine 0.19

Methyl hydroxyethyl cellulose 1.00

Citric acid 0.01

Methyl p-hydroxybenzoate 0.25

Perfume 0.18

Glycerin (85%) 5.00

Water 73.17

35

40

Example 3

100.00

45

Skin cream

Weight percent

Monoglyceride according to Example 1 6.37

Trioleyl-o-phosphate 3.18

Polyoxyethylene ether of a saturated

Fatty alcohol ⁶ * ⁶³

ParafSnöI 13.22

Perfume 0.50

Water 70.10

100.00 Example 4

Sunscreen milk

Weight percent

Branched-chain, liquid fatty acid ester (made from the fat content of the Puerperal gland secretion van Enten, known under the name "Purcelhn oil") ⁵ > °

Isopropyl myristate 1> 5

55

60

Cetyl alcohol 2.0

Monoglyceride according to Example 1 5.0

Beeswax 1.0

Stearic acid 0.9

Polyoxyethylene sorbitan monooleate 1,2

Polyethylene glycol fatty acid glyceride 1,2

Triethanolamine 0.4

Ethoxylated p-aminobenzoic acid .. 1,5 A light filter substance with absorption at 280 to 315 μΐη 1.0

Plant extract prepared with glycols 1.0

Perfume 0.3

Water, desalinate 78.0

Example 5

100.0

Hair care products

Weight percent

Mixture of higher saturated fatty alcohols with a non-ionic one

Emulsifier 10.0

Wool wax 3.0

Cetyl alcohol 2.0

Sorbitol 5.0

Monoglyceride according to Example 1 1.0

Perfume 0.2

Water, desalinate 78.8

100.0

Example 6

Aerosol foam bath

Weight percent

Sodium Lauryl Ether Sulphate 66.32

Sodium salt of fatty acid

sarcosinates, 65% 1.94

Sodium C, ₂ _ ₁₄ alkyl benzene

sulfonates, 75% 3.38

Higher molecular weight polymeta-

phosphates 1.69

Polyaldehyde 0.08

Ricmus fatty acid monoglyceride 0.84

Plant extract 1.68

U-propylene glycol 1.69

Perfume 1.69

Monoglyceride according to Example 1 2.20

Menthol 1.32

Dye and water 5.17

Difluorodichloromethane / ^ l ^ -Tetra-

fluorine dichloroethane 1: 1 12.00

Example 7

100.00

Aerosol sun protection

Weight percent

Isopropyl myristate 5.50

Monoglyceride according to Example I 2.00

2-ethoxyethyl-p-methoxycinnamate

(Light protection agent) 1.50

Menthol 0.05

Perfume 0.50

Ethanol, 85% 10.45

Monofraortrichloromethane / Difluor-

dichloromethane 3: 1 80.00

100.00

Example 8

Aerosol sun protection

Weight percent

Dipropylene glycol 18.20

Monoglyceride according to Example I 3.50

2-ethoxyethyl p-methoxycinnamate

(Light stabilizer) 0.95

Perfume 0.80

Ethanol, 85% 11.55

Monofluorotrichloromethane / difluoro-

dichloromethane 1: 1 65.00

IO

Example 9

deodorant

Weight percent

Monoglyceride according to Example 1 6.00

Sucrosc octa acetate 0.06

Perfume 0.44

Ethanol, 85% 33.50

Monofluorotrichloromethane / difluoro-

dichloromethane 65:35 60.00

100.00 100.00

Example of impregnating leather

A molecularly distilled monoglyceride of about 96% purity, prepared according to Example 1 was applied to the upper leather, the sole and the seam of a dry street shoe with a cotton swab applied in full.

After a few minutes the monoglyceride was in the pores of the leather and in the Gaps drawn in between the upper leather and the sole.

The shoe thus treated was found to be complete when repeatedly used on snow-wet roads waterproof, whereas an untreated, otherwise identical shoe would get soaked in a short time. The impregnation with the monoglyceride did not have to be renewed over the observation period of 6 weeks but remained fully effective, so that the leather despite daily alternation between moist and did not become brittle when dry.

Claims (1)

Patent claims: 1. Monoglycerides of the general formula
(CH ₂ ) _X -COOC, H _S (OH) ₂ or 1 to 11 and in the χ and y =
χ + y = 11 and