JPS6011078B2 - Method for producing cold-resistant liquid fatty acid ester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the production of cold-resistant liquid fatty acid esters which can be used in place of natural fish oil (Tran) or spermaceti oil as a zero fat agent, especially in the leather industry.

In the leather industry, large amounts of highly softening fatty acid esters are used as fatliquors, sometimes in partially sulfated form, and are to impart a soft, oily feel to the leather. I need.

For this purpose, in the past primarily natural fatty substances were used, such as, for example, high-quality fish oil or whale oil or spermaceti oil. However, these fatty substances are not always available in sufficient quantities at will or must be obtained from naturally occurring raw materials by complicated purification methods, such as cryofiltration or distillation. In particular, fish oils are increasingly not uniform in their composition, and they may also be partially degraded to fatty acids and contaminated by salt separation. Attempts have therefore already been made to produce uniform and qualitatively more valuable products by splitting fish oil into the corresponding fatty acids and subsequent re-esterification.
However, this method is complicated and does not give satisfactory results. The subject of the present invention is a method for producing a cold-resistant liquid fatty acid ester containing higher unsaturated fatty acids, in which: (1) on average 2.1% per fatty acid chain;
Chain length C2 with 3 solid double bonds.

to C24 higher unsaturated fatty acids 10 to 6% by weight
adduct of 1 to 10 mol of ethylene oxide and/or propylene oxide to a fish oil fatty acid or a liquid fatty acid mixture containing fish oil fatty acids having a content of chain length C, substantially free of higher unsaturated fish oil fatty acids. or esterified with a liquid fatty acid or fatty acid mixture containing 75% by weight or more of unsaturated fatty acids with one or two C22 unsaturated bonds, or [B} substantially containing higher unsaturated fish oil fatty acids. No, chain length C,.

An adduct of 1 to 10 moles of ethylene oxide and/or propylene oxide to a liquid fatty acid or a fatty acid mixture containing 75% by weight or more of unsaturated fatty acids having one or two unsaturated bonds of C2 to C22, with a chain length of C2. The above-mentioned method for producing a liquid fatty acid ester is characterized in that the above liquid fatty acid ester is esterified with a mixture containing fish oil fatty acids or fish oil fatty acid having a content of 10% to 6% by weight of higher unsaturated fatty acids of C24 to C24. . In general, the low temperature stability of liquid fatty acid esters (typically those based on a single unsaturated fatty acid such as olein) is substantially improved by the inclusion of highly unsaturated fish fat esters. However, due to the sensitivity of fish fatty acids to oxidation, the proportion should not be higher than the absolutely necessary amount, and its range is therefore limited to that defined in the claims. In the preparation of fatty acid alkylene oxide adducts, the starting point is fish oil fatty acids, such as those obtained from herring oil, menhafen oil, or sardine oil. Such fish oil folic acid is C
2. to C24, preferably C2. 10% to 6% by weight of higher unsaturated fatty acids having a chain length of C22 to C22
Indicates the content of The number of double bonds in these fatty acids varies according to the origin of the fish oil, with an average of 2.1 per fatty acid chain.
and 5.3 to 5.3 double bonds. The remaining fatty acids of the mixture consist mostly of unsaturated fatty acids with one or a few unsaturated bonds, of chain length C.4 to C.8, and a minor portion of chain length C,. Consists of saturated fatty acids from Naimi C crab. As long as a target product with a higher degree of low temperature resistance is desired, the proportion of saturated fatty acids should be as low as possible and should not exceed 35% by weight of the total fatty acids. In some cases,
The proportion of solid fatty acids can be reduced by distillation or other known purification methods. For the addition of alkylene oxides, mixtures of fish fat and other liquid fatty acids or fatty acid mixtures, such as those obtained from vegetable or animal oils, may be used, as long as the composition of the total fatty acid mixture is within the ranges mentioned above. One can start from a fatty acid mixture.

The above fish oil fatty acids are 1% to 10% per mole of fatty acid.
It is reacted with 2 to 4 moles of ethylene oxide and/or propylene oxide.

The addition reaction is carried out in a known manner using alkaline catalysts, preferably under pressure and at elevated temperature. The content of alkylene oxide groups influences the HLB of products used in particular as leather fatliquors.

As is clear from the examples below, a usable product is already obtained with 2 to 3 alkylene oxide units.
If one or more solid alkylene oxide units are present in the molecule, there will be disadvantages such as poor low temperature stability and increased hydrophilicity. Preferably 2 to 4 alkylene oxides are added. The fish oil fatty acid-alkylene oxide adduct has a chain length C, which is substantially free of higher unsaturated fish oil fatty acids.

or C22 unsaturated bond 1 or 2 fatty acids 75
It is further esterified with a liquid fatty acid or fatty acid mixture having a content of more than % by weight. Preferably, oil acids, linoleic acids, such as naturally occurring fatty substances such as beef tallow, lard, peanut oil, Ikuko oil, rapeseed oil, tall oil and others.
It is a fatty acid mixture mainly containing gadolic acid and/or erucic acid. Here, too, it is expedient to keep the proportion of saturated fatty acids as low as possible if good low temperature resistance of the final product is desired. Optionally, the saturated fatty acid fraction can be separated from the liquid fatty acid by cryogenic filtration, rolling, distillation or screening methods, the residual fraction of saturated fatty acids should not exceed 2% by weight. It is.

The esterification is carried out by the usual method using isopropyl titanate,
Using known catalysts such as tin (D) chloride, zinc powder, trisodium phosphate, tin powder and the like, preferably at elevated temperature and under vacuum, with the removal of the water formed during the reaction. It will be held in

The molar ratio of each component is approximately 0.8:1 to 1.2:1, preferably approximately 1:1, thus yielding an esterified product having an OH number of 30 or less. In case {B}, the production of the product involves first adding 1 to 10 moles of ethylene oxide and/or propylene oxide onto a liquid fatty acid or fatty acid mixture essentially free of fish oil fatty acids, and then esterification. is carried out using fish oil fatty acids.

The course and results of the reaction correspond to the product prepared according to ①. According to method W or [B), it is outstanding in that it contains various fat brewing components in one molecule,
A uniformly structured fatty acid gester of polyglycol is obtained. They are therefore distinguished in characteristic respects from polyglycol-fatty acid esters, such as those obtained by esterification of 1 mole of polyglycol with 2 moles of the corresponding fatty acid mixture. Mixed esters of this type containing a statistical distribution of fatty acid residues exhibit other, less advantageous properties for many applications. The ester mixture according to the invention is a pale yellow to brown oil with good cold resistance.

Owing to their high content of longest-chain fatty acids, they can be used in place of fish or whale oils, which are not always available in consistent quality and composition, or in the place of peppered whale oil, which is currently relatively expensive and not available in sufficient quantities. It is an excellent fatliquoring agent for fatliquing leather. Use as a leather fatliquor:
It is carried out in organic solvents such as benzine, chlorinated hydrocarbons or the like, or as an aqueous emulsion with the addition of anionically active or nonionic emulsifiers.

Suitable emulsifiers include, for example, higher fatty alcohol sulfates or fatty alcohol polyglycol ether sulfates or ethylene oxide adducts to higher fatty alcohols, alkylphenols, fatty amines, fatty acid ether/alamides and the like. The esterified products according to the invention can also be used in partially sulphated or sulphited form, for which they can be treated in known manner with technical sulfuric acid, fuming sulfuric acid or air-sulfuric acid.
Reacted with a sulfite mixture. Approximately 15 to 60
% of sulfonation degree (Sumem sgad) is desired. The sulfonated esters can be emulsified in water without further addition of emulsifiers and used in this form for fatliquoring leather. Leather fatliquored with the products according to the invention exhibits a pleasant, greasy feel and a relatively light color.

This product therefore surpasses natural marine animal oil and its rectified products in terms of its quality and properties, and is even comparable to peppered whale oil, making it a very suitable substitute. The products can also be used advantageously in areas other than fatliquoring and lubricants, for example as spinning oils for textile fibers or for producing special lubricating effects on metal surfaces.

Example 1 Liquid portion from tallow fatty acid (industrial olein, acid value: 202; saponification value: 205; iodine value: 92) and fish oil fatty acid) acid value: 0.9; saponification value: 121: iodine value :73: OH number: 142) Addition product of 3 moles of ethylene oxide to 1 mole: A mixture of 413 women was mixed under vacuum with 7 g of isopropyl titanate in a round flask with a distillate diverter under vacuum for up to 8 hours. 140 'C to 2
Heat to 380℃, and as the temperature increases, reduce the vacuum to 10℃.
The Hg level was lowered from 2000 Hg to 3000 Hg.

The esterification was completed after a total of 18 reaction waters had been distilled off. Light brown liquid ester (acid value: 2.1; saponification value:
168; Iodine value: 83; OH value: 8) 674 females remained. The turbidity point was -2°C. Example 2 At a reaction temperature of 100 °C to 200 °C (increased within 6 hours), a mixture of tall olein and distillate fatty acids from rapeseed oil in a ratio of 1:1 (acid number: 192: saponification number: 195: iodine Value: 1.15; resin acid; 0.6%)
Addition product of 2 moles of ethylene oxide to crabmeat fatty acid (acid value: 0.3; saponification value: 155; iodine value: 1 bulb: OH value: 161) from 50 female and menhaden oil 6
0 females were esterified in a vacuum of 4 Yanagi Hg in the presence of tin powder.

After distilling off 3 layers of reaction water and filtering the catalyst, 106 pieces of light brown liquid ester (acid value: 1.9; saponification value: 176; iodine value: 1 powder; OH value: 17) remained. . The turbidity point was approximately 0°C. Example 3 As described in Example 2, industrial palm oil (acid number: 20
1: Saponification value: 203; Iodine value: 94: Turbidity point 65°C
), up to 30% of which consists of distillate fatty acids from menhaden oil and up to 70% of industrial olein (acid number: 1.4; saponification number: 117; iodine number:
92; OH value: 157) was esterified with the addition product 39 acid of 2 moles of propylene oxide per mole of fatty acid mixture consisting of 39 acids in the presence of zinc oxide.

After distilling off one batch of reaction water, liquid ester (acid value: 0.7
; Saponification value: 163; Iodine value: 92) About 67 females were obtained. The turbidity point was about -10°C. Example 4 The ester mixture prepared according to Example 1 was sulphitized in a known manner at 70 DEG C. and 80 DEG C. with 14% by weight of sodium bisulfite under air blowing until a water emulsion was formed.

The degree of sulfite reached approximately 25%. Suede leather, simulated with chromium and post-selected in the usual manner with synthetic retainers, is subjected to the addition of 8 moles of ethylene oxide to a fatty alcohol mixture of 95% chain length C,2 to C,8 sulfite products. A mixture of 5% 6-8% was fatliquored in the usual manner at 60 DEG C. for 48 minutes at 100% yield, dried and finished.

Clothing leather was obtained that was as supple and perfect as cloth, and had a pleasant feel.

Example 5 The ester mixture prepared according to Example 2 was sulfated in the usual manner with 18% oleum and neutralized with 5% aqueous ammonia.

After separation of the brine, a fatliquoring substance content of approximately 8% by weight was adjusted with water. The epithelial leather subjected to the traditional chrome method and finished by the phytofacial method was treated with 70% of the sulfated product and the corresponding unsulfated ester 3.
10% using 5 to 6% fatliquor substances in a mixture with 0%
Fatliquing was carried out at 50-60° C. for 4 minutes at a bath ratio of 0% and dried and finished in the usual manner.

A supple epithelial leather with good texture was obtained.

Example 6 The esterification product produced according to Example 3 was sulphated as described in Example 5, neutralized in ammonia and adjusted to a fatliquoring mass of about 8% by weight.

The epithelial leather, which has been subjected to the chroming process and after-refined by the synthetic oxidation process, is treated with a fatliquoring substance 5 to 6 of a mixture of 70% of the above-mentioned sulfated product and 30% of the corresponding unsulfated ester. Using %, 60 qo at 100% yield
Fatliquor was carried out for 45 minutes, dried and finished.

A perfect, tactile and supple epithelial leather was obtained. Example 7 Distilled fish oil - fatty acids (acid number: 1) as described in Example 1
97: saponification value: 200; iodine value: 140) 56 females were treated with peanut oil-distillation-fatty acid (acid value: 0; saponification value: 12)
1 of the liquid part of 0; iodine value: 59; OH value: 131)
Addition product of 3 moles of propylene oxide per mole 85
Esterification was carried out in the presence of tin(0) chloride using a female.

After distilling off 37 g of reaction water, liquid ester (acid value: 1.2
; Saponification value: 155; Iodine value: 71; OH value: 19)
1370 g were obtained, which still did not separate out the solid fraction even at 0°C. The gist of the present invention is the method described in the claims, and includes the following matters as embodiments thereof.

Process according to claim 1 or 2, using adducts with 2 and 4 moles of '1' ethylene oxide and/or propylene oxide.

'21 Higher unsaturated fish oil fatty acids average 2.1 to 5.0% per fatty acid chain. The method according to claims 1 and 2 and the above [11], which contains a milky double bond.

'2} In addition to higher unsaturated fatty acids having a chain length of C2o to C24, fish oil and fatty acids have an additional portion of mono- or polyunsaturated fatty acids with a chain length of C, 4 or 8, and a chain length of C.

Claims 1 and 2 and supra' containing at most 35% by weight of saturated fatty acids of C22 to C22.
11-(2}'Process according to.'41 The liquid fatty acid or fatty acid mixture contains a major amount of oil acid, linoleic acid, gadoleic acid and/or erucic acid, Claims I and 2 and the method according to the above documents 1' to '3}.

'5) 2% by weight of liquid fatty acid or fatty acid mixture
The following chain length C, Claims 1 and 2 and the above '1} to { containing saturated fatty acids of C22 to C22.
Method according to 4. (6' 0.8:1 None, 1.2:1
, preferably using a molar ratio of the esterification components of about 1:1.
'5} method.

Claims (1)

[Scope of Claims] 1. Fish oil fatty acids or higher unsaturated fatty acids having a content of 10 to 60% by weight of chain length C_2_0 to C_2_4 and having on average 2.1 to 5.3 double bonds per fatty acid chain. An adduct of 1 to 10 moles of ethylene oxide and/or propylene oxide to a liquid fatty acid mixture containing fish oil fatty acids with one or two unsaturated bonds of chain length C_1_0 to C_2_2 that do not substantially contain higher unsaturated fish oil fatty acids. A method for producing a cold-resistant liquid fatty acid ester, which comprises esterifying it with a liquid fatty acid or a fatty acid mixture containing 75% by weight or more of unsaturated fatty acids. 2 Adding ethylene oxide and/or fatty acid to a liquid fatty acid or fatty acid mixture containing 75% by weight or more of an unsaturated fatty acid with one or two unsaturated bonds of chain length C_1_0 to C_2_2 that does not substantially contain higher unsaturated fish oil fatty acids.
or by esterifying an adduct of 1 to 10 mol of propylene oxide with a fish oil fatty acid or a mixture containing fish oil fatty acids having a content of 10 to 60% by weight of higher unsaturated fatty acids with a chain length of C_2_0 to C_2_4. , a method for producing cold-resistant liquid fatty acid ester.