DE2231162A1 - Cold-resistant esters - of higher liq fatty acids with polyols, used eg as leather oiling agents and lubricants - Google Patents

Abstract

A fatty acid mixt contg. (A) 3-50 wt.% 2-22C fatty acids with single unsatn. (B) 97-50 wt.% 12-18C fatty acids with single or multiple unsatn. and (C) 0-15 wt.% 12-18C satd. fatty acids, is esterified with (D) 2-10C alcohols contg. 2-6 OH gps. to give an end prod. with OH value of =30. Amount of (A) is pref. 5-30 wt.% and OH value of the end prod. is =17. Up to 65 wt.% (D) may be replaced by a 10-22C monohydric alcohol with single or multiple unsatn. They are suitable as lubricants for precision machinery, oiling agents for leather, textiles, etc. brake and hydraulic fluids. cold stability and lubricating props. are excellent, and they are produced from readily available natural fats.

Description

Process for the production of cold-resistant esters of higher liquids Fatty acids with polyhydric alcohols The invention relates to a process for the preparation Cold-resistant ester of higher liquid fatty acids with polyhydric alcohols, in particular as a fatliquor for the leather industry and as cold-resistant Lubricants as well as brake and pressure fluids can be used.

In a wide variety of fields of application, such as B.

as an industrial fatliquor, as a lubricant in precision engineering, As brake and pressure fluids, fatty acid esters are used in large quantities, especially Fatty acid triglycerides are required, which must have a high resistance to cold. The products must neither solidify nor should they set at low temperatures separate solid components within certain temperature limits. Also needed the leather industry large quantities of well-softening fatty acid esters, which optionally can be used in partially sulphated form and have a soft, musky leather handle should result.

Natural fatty substances that meet the requirements mentioned are for example the cold-filtered nipple oil or the cold-filtered native sperm oil - both Fatty substances However, they are not available in sufficient quantities or

awkward to win.

Processes are known by mechanical or distillative separation certain fatty acid fractions from fatty acid mixtures and subsequent esterification to produce relatively cold-resistant oils with polyhydric alcohols. In practice However, it has been shown that the process is either too cumbersome to carry out are, or that the cold resistance and the lubricating properties of the obtained thereby Esterification products leave something to be desired (DP. 767 256, DP. 9o8 174, DAS 1 268 139 and DAS 1 275 533).

The aforementioned disadvantages are avoided according to the invention.

The claimed products assume easily accessible natural ones Fatty substances and lead to synthetic fatty acid esters, which are excellent Have cold stability and lubricity. They excel in this regard the well-known synthetic products.

The invention relates to a method for producing cold-resistant ones Esters of higher liquid fatty acids with polyhydric alcohols, characterized in that that you have a fatty acid mixture of 3 to 50 percent by weight of monounsaturated Fatty acids of chain lengths C20 to C22 and 97 to 50 percent by weight essentially mono- or polyunsaturated fatty acids of chain lengths C12 to C18 with a Content of a maximum of 15 percent by weight of saturated fatty acids with chain lengths of C12 up to C18 with polyhydric alcohols that have 2 to 6 hydroxyl groups and 2 to 10 carbon atoms contain, esterified up to an OH number of the end product of a maximum of 30.

The unsaturated fatty acids of chain lengths c20 to C22 can be made from certain naturally occurring vegetable or animal fatty substances Saponification or cleavage and fractional distillation of the fatty acids obtained be won. Suitable starting materials are, for example, R & ps- or rapeseed oil, peanut oil, tall oil, etc.. The proportion of these fatty acids in the mixture should be about 5 to 50 percent by weight, preferably 5 to 30 percent by weight. the Greasing and lubricating properties of the mixture are better, the higher is the proportion of such long-chain fatty acids in the mixture.

Besides these long-chain unsaturated fatty acids, that contains too esterifying mixture, preferably a predominant proportion of single or multiple unsaturated fatty acids with chain lengths of C12 to C18, preferably C16 and 018. It is mainly oleic acid, but depending on the starting material, it can also be used Subordinate amounts of linoleic and / or linolenic acid and other unsaturated Fatty acids of chain lengths C12 to C16 are present. The proportion of these fatty acids in the mixture is 97 to 50 percent by weight, preferably 95 to 70 percent by weight. Up to 15 percent by weight of these fatty acids can be obtained from saturated fatty acids Chain lengths C12 to C18 must be replaced. A higher percentage of saturated fat has an unfavorable effect on the low-temperature behavior of the stressed esters.

The fatty acid mixtures are conventionally, optionally in Presence of catalysts such as isopropyl titanate tin (II) chloride, zinc dust, trisodium phosphate or the like esterified with the polyhydric alcohols. The esterification product should have an OH number up to a maximum of Do, preferably a maximum of 17.

The polyhydric alcohols are those with 2 to 10 carbon atoms and 2 up to 6 hydroxyl groups, optionally through ether bridges Connected can be considered such. B. (; lycol, diglycol, glycerin, trimethylolproparl, Pentaerythritol, Dipcntaerythritol, Sorbitol and other sugar alcohols. The multi-valued ones Alcohols can up to a proportion of 65 percent by weight by essentially Mono- or polyunsaturated monohydric alcohols of chain lengths C1 to C22 be replaced.

Examples of this are a fatty alcohol mixture obtained from rapeseed oil fatty acids the chain lengths C18 to C22 or the distillation residues of unsaturated technical Fatty alcohol holes with an iodine number of around 9o to 10o. The co-realization of such Fatty alcohols during esterification increase the lubricity of the claimed ester mixtures, without the cold stability being reduced in an unacceptable manner.

The ester mixtures prepared according to the invention are clear, weak yellowish to light brown oils, the cold cloud points between about 80 and 180 C. They can be as a result of their excellent lubricating effect and extraordinary high resistance to aging as a lubricant in the fine mechanical industry e.g. B. for clocks, measuring devices and the like. They serve as a substitute for that expensive and not always sufficiently accessible neat foot oil.

A particularly important area of application is leather oiling, where the claimed products as a substitute for sperm oil with outstanding success are usable. They can be used in an organic solvent such as gasoline, Chlorinated hydrocarbons or the like or as an aqueous emulsion with addition of anionic and non-ionic emulsifiers.

Higher fatty alcohol sulfates, for example, are used as emulsifiers.

or fatty alcohol polyglycol ether sulfates or ethylene oxide adducts higher fatty alcohols, alkylphenols, fatty amines, fatty acid ethanolamides or the like into consideration. The claimed esterification products can also be partially sulfated Form are used, the sulfonation in the usual way with technical sulfuric acid, oleum or with an air-bisulfite mixture. It a degree of sulfonation of about 20 to 60.0 is aimed for. The sulfated esters can be emulsified in water without the addition of emulsifying agents and in this Form used to lick leather.

The leached with the ester mixtures or their sulfonation products Leathers show a very good failure, the handle is pleasantly musky and the Good light resistance. The properties of the products largely correspond to this natural sperm oil, which they have in terms of resistance to cold and the oiling effect z. T. even surpass them.

They are therefore an ideal replacement product for the increasingly difficult to procuring sperm oil.

Furthermore, the claimed products can be used as fatliquoring and lubricating agents for other fibrous materials, such as textiles, or for special smear effects serve on metal surfaces.

The mixed esters of the following examples were made in the following manner manufactured.

The esterification components were mixed with one another at about 500.degree and brought to 160 ° C. within 2 hours with stirring. Another increase in temperature took place at 10.degree. C. per hour, so that a temperature of 230.degree. C. was reached after 7 hours was. During the heating time, the vacuum gradually decreased with the reaction temperature increased so that at 2300 C a vacuum of 5o Torr was reached. Under these Conditions took place an extensive esterification, with the water of reaction with any volatile fractions of excess alcoholic components are distilled off became.

In the following examples: SZ = acid number VZ = saponification number JZ = iodine number OHZ = OH number Example 1 A mixture of 600 g olein (SZ: 202, VZ: 204, JZ: 92, cloud point: 4 ° C) 400 g fatty acids from rapeseed oil (SZ: 185, VZ: 190, JZ: 103) 112 g of glycerol 1 g of isopropyl titanate as an esterification catalyst was used in the esterified manner specified. Approx. 1060 g of mixed esters (SZ: 1.4, VZ: 187, JZ: 91, OHZ: 1)) with a cloud point of -13 ° C.

The fatty acids present in the esterification mixture consisted of 25.6 % By weight of monounsaturated fatty acids C20 and C22 65> 3% by weight single and multiple Unsaturated fatty acids C14 to C18 9.1% by weight, saturated fatty acids C12 to C18 rist 2 1 in a mixture of 3236 g olein (key figures according to example 1) o g technical Fatty acid fraction of chain lengths C20 to C22 from rapeseed oil (SZ: 175, JZ: 92) 430 g pentaerythritol 4 g isopropyl titanate was esterified in the manner indicated. the The yield was about 5650 g of mixed esters (AN: 2.2, VZ: 189, JZ: 91, OILZ: 5).

The cloud point was -1) ° C.

The fatty acids present in the esterification mixture consisted of 7, o Weight percent of monounsaturated fatty acids C20 and C22 81.9 percent by weight Mono- and polyunsaturated fatty acids C14 to C18 11.1 percent by weight saturated Fatty acids C12 to C18 Example 5 A mixture of 1,000 g of olein (key figures as in example 1) 112 g technical fatty acid fraction with chain length C20 to C22 from rapeseed oil (SZ: 173J JZ: 91, VZ: 176) 125 g of pentaerythritol 210 g of distillation residue from the distillation unsaturated technical fatty alcohols (SZ: o, 9, VZ:) 9, OHZ: 93, JZ: 85) 1.5 g IsoDropyl titanate was esterified as indicated. The yield was approx. 1350 g of mixed esters (SZ: 2,3, VZ: 170, JZ: 85, OHZ: 9) with a cloud point of -10 ° 0.

The fatty acids present in the esterification mixture consisted of: 10.3 Weight percent monounsaturated fatty acids C20 and C22 7.8 weight percent monounsaturated and polyunsaturated fatty acids C14 to C18 lo> 9 percent by weight saturated fatty acids C12 to C18 Example 4 A mixture of 400 g tall oil fatty acids (SZ: 189, VZ: 37J JZ: 17J resin acid content 3.5%) 200 g olein (corresponding to key figures Example 1) 400 g of fatty acid from rapeseed oil (key figures according to Example 1) 30 g Propylene glycol 20 g ethylene glycol 60 g glycerol 1 g isopropyl titanate was as indicated esterified. The yield was approx. 1055 g of mixed esters (AN: 2.9, VN: 186, JZ: 107, OHT: 17) with a cloud point of -17 ° C.

The fatty acids present in the esterification mixture (without resin acid content) consisted of: 25.2 percent by weight of monounsaturated fatty acids 020 and C22 69.6 Weight percent of monounsaturated and polyunsaturated fatty acids C14 to C18 5.2 percent by weight saturated fatty acids C12 to C18 Example 5 A mixture of looo g liquid fractions of peanut oil fatty acids (AN: 201, VZ: 20), JZ: 98, cloud point 5 C) 41 g trimethylolpropane 6o g pentaerythritol 25 g glycerol 2 g tin-II-chloride was esterified as indicated. The yield was approx. 1065 g mixed esters (AN: 2.1, VZ: 191, JZ: 94, OHZ: 10) with a cloud point of -11 ° C.

Example 6 A mixture of 1230 g of olein (characteristics as in Example 1) 137 g technical fatty acid fraction with chain lengths C20 to C22 from rapeseed oil (SZ: 173r JZ: 91) 155 g of a mixture of pentaerythritol and dipentaerythritol such as 80 : 20 125 g fatty alcohol mixture of chain lengths C16 to C22 from rapeseed oil (VZ: 1.3, OHN: 192, JZ: 92) 5 g zinc dust was esterified as indicated. The yield was approx. 1550 g mixed ester (SZ: 2.1, VZ: 177, JZ: 85, OHZ: 6) with one cloud point from 80 C.

The fatty acids present in the esterification mixture were as follows Composition: 9.5 percent by weight of monounsaturated fatty acids C20 and C22 79.6 percent by weight of monounsaturated and polyunsaturated fatty acids C14 to C18 lo, 9 percent by weight of saturated fatty acids C12 to C18 Example 7 A mixture from 720 g olein (Keno numbers as in Example 1) Soo g rapeseed oil (VZ: 171, JZ: 97) 80 g Glycerin 2 g trisodium phosphate were esterified as indicated. The yield was 126o g mixed ester (SZ: 1.5, VZ: 19), JZ: 92, OIIZ: 6) with a cloud point of 1600. The ester mixture is particularly suitable as a lubricant for precision mechanics Instruments.

The fatty acids present in the esterification mixture were as follows Composition: 7.0 percent by weight of monounsaturated fatty acids C20 and C22 82.4 percent by weight of mono- and poly-saturated fatty acids C14 to C18 10.6 Percent by weight of saturated fatty acids C12 to C18.

Example 8 A self-emulsifying oil for oiling leather is used produced in the following way: A mixture of 3950 g technical oleic acid (tallowolein) 500 g fatty acid mixture from rapeseed oil (SZ: 185, VZ: 9o, JZ: lo) 550 g pentaerythritol 5 g isopropyl titanate as a depesterification analyzer was used in the specified Esterified way. The yield was 5005 g of a bright yellow-brown oil (AN: 5.7, VZ: 197, JZ: 8c3.5 OIIZ: 7, o) with a cloud point of 14.50 C. The zur The fatty acid mixture used for esterification contained 6.3 percent by weight monounsaturated Fatty acids with chain lengths of C20 to C22.

The ester mixture was sulfated in the usual manner with 18 percent oleum and neutralized with an ammonia water. After separating the salt water it was adjusted with water to a content of fatty substance of approx. 80 percent by weight.

Ear-tanned and vegetable-tanned upper leathers were also included 5-6% fatty substance of the mixture of -70 of the above sulfation product and 30 ß of the corresponding unsulfated ester in 100% liquor at Sun to 600 Licked C for 45 minutes and dried and finished in the usual way. Man received a full, soft, grippy upper leather.

Example 9 A product also suitable as a leather fatliquor was obtained in the following way: A mixture of 3350 g of technical oleic acid (tallowolein) 500 g fatty acid mixture from rapeseed oil (SZ: 185, VZ: 190, JZ: 103) 750 g distillation residue from the distillation of unsaturated technical fatty alcohols (SZ: 0.9, VZ: 39, OiIZ: 9), JZ: 85) 420 g of pentaerythritol 5 g of isopropyl titanate as Esterification catalyst was esterified as indicated. The yield was 5025 g of a yellow-brown bare oil (SZ: 5.0, VZ: 172.5, JZ: 87.5, OIIZ: 10) with a Cloud point of 160 ° C. Contained the fatty acid mixture used for the esterification 7.5 percent by weight of monounsaturated fatty acids with chain lengths of C20 and 022.

The esterification mixture was sulfated in the usual way with 18% oleum and neutralized with 5% ammonia water. After separating the salt water it was adjusted with water to about 80 percent by weight of fatty substance.

Ear-tanned and synthetically retanned upper leathers were rated 5 up to 6 fatty substance of the mixture of: 70% of the above sulphonation product and 30 10 of the corresponding unsulfated ester in 100% liquor in the usual way Licked at 600 C for 45 minutes, dried and finished. One received a full, grippy and soft upper leather.

Claims (6)

P A T E N T A N S P R Ü C ft E 1. Process for the production of cold-resistant esters of higher liquids Fatty acids with polyhydric alcohols, characterized in that a fatty acid mixture is used from 5 to 50 percent by weight of monounsaturated fatty acids with chain lengths of C20 up to C22 and 97 to 50 percent by weight of essentially mono- or polyunsaturated Fatty acids with chain lengths of C12 to C18 with a maximum proportion of 15 percent by weight saturated fatty acids of chain lengths C12 to C18 with polyhydric alcohols, which contain 2 to 6 hydroxyl groups and 2 to 10 carbon atoms, up to an OH number of the end product esterified by a maximum of 5o. 2. The method according to claim 1, characterized in that the proportion Monounsaturated fatty acids with chain lengths from C20 to CS2 5 to 5 percent by weight amounts to. 3. The method according to claim 1 and 2, characterized in that the OH number of the end product is a maximum of 17. 4. The method according to claim 1 to), characterized in that the polyhydric alcohols up to a proportion of 65 percent by weight by essentially Mono- or polyunsaturated monohydric alcohols of chain lengths from 01o to C22 are replaced. 5. Use of the ester mixtures prepared according to Claims 1 to 4 as a lubricant for precision mechanical devices and as a fatliquor for leather, Textiles and the like. 6. Use of the ester mixtures prepared according to claims 1 to 4 in partially sulphated form for licking leather.