CS227286B1 - Amphoteric esteramines on the fatty acid basis - Google Patents

Description

The invention relates to novel amphoteric fatty acid ester amines and their salts.

For the treatment of glass fibers and mineral fibers, whether intended for reinforcement of plastics and rubbers or for technical purposes, a variety of lubricants is used which, in their composition, contain various greases, usually amphipathic compounds. Industrially, the most widely used method is to apply lubricants from aqueous systems mainly because the use of organic solvents is limited, either because of their toxicity, flammability and, last but not least, for economic reasons. For these reasons, the compounds must be useful as lubricants for lubricating compositions! switch multiple conditions. A prerequisite is that they are soluble or emulsifiable in water. Mainly for these reasons, various nonionic alkylene oxide compounds such as alkyl polyglycol ethers and the like are used as lubricants. Although the use of these compounds as lubricants is sufficient for a variety of glass fiber applications, they have proven to be poorly effective in formulating so-called " of hard direct lubricants. In this case, increased concentrations of film-forming substances, mainly polyvinyl acetate dispersions, are used to achieve a lubricating deposit of over 1% by weight. This measure causes considerable problems in textile processing, mainly due to poor unwinding and processing of glass fibers. An increase in lubricant concentration to improve textile processing has proved to be ineffective. In analyzing this problem, we have found that the main reason for the poor performance of conventional lubricants is that the polymer film has enclosed them in its structure.

By application research, we have found that the problems are substantially eliminated by using the compounds of the invention as lubricants in lubricating compositions.

The present invention provides novel fatty acid esteramines of the general formula

CH2CH2OOC-R2-COOH

From (R 3 ~ COOCH2CH2) _x N (CH ₂ CHzORi) ₂ _ _x wherein x is an integer of or 2,

R1 is a hydrogen atom or a moiety having the structure —OC — R2 — COOH,

R2 is a divalent radical, 1,2-phenylene or vinylene,

R 8 is an alkyl or alkenyl radical of 8 to 18 carbon atoms and their salts with bases such as sodium, potassium, ammonium and quaternary ammonium salts with mono-, di-, tri (2-hydroxyethyl) amine or with acids such as formic, acetic, propionic acid .

The preparation of these compounds can be carried out as follows. Condensation of triethanolamine with fatty acids at 150 to 200 ° C affords the corresponding esteramines. The esterification takes place without the use of catalysts and can be monitored by changing the acid number of the batch.

R 3 COOH + N (CH 2 CH 2 OH) 3 R 3 COOCH 3 · CH 2 N (CH 2 CH 2 OH) 2 + H 2 O

The corresponding diesteramines can also be prepared in the same manner, whereby the fatty acids used are used either individually but most often in mixtures as fatty acids isolated from various oils and fats.

R3COOH + N (CH2CH2OH) 3 -> (R3C00CH2CH2) 2NCH2CH2OH + 2 H2O

The thus prepared esteramines and diester- or maleic anhydride in the melt of tepamines are subjected to addition with phthalic anhydride to a temperature of 70 to 150 ° C (R 3 COOC 2 H 4) 2NC 2 H 4 OH + R 2 (CO) 2 O -> (R 3 COOC 2 H 4) 2NC 2 H 4 OOCR 2 COOH

In the case of esteramines, the addition may be performed in an esteramine: anhydride molar ratio of 1: 1 to 2.

R3COOC2H4N (C2H4OH) 2 + 2Rz (eO) 2O-> R3COOC2H4N (C2H4OOCR2COOH) 2

By neutralization with sodium, potassium, ammonium carbonate or hydroxide, monoethanolamine, diethanolamine, triethanolamine, they can be converted to the corresponding anionic salts. When used to neutralize acids such as formic, acetic and propionic, they can be converted to the corresponding cationic salts.

The presence of polar groups in the lubricant structure results in improved wetting of the treated fibers with polar plastics in the production of fiberglass. From the technological point of view, the production of the derivatives according to the invention consists mainly in that they can be prepared from commercially available raw materials by a simple and unpretentious process for the equipment.

The invention is further elucidated by way of examples in which the composition is given in weight concentration.

Example 1

Preparation of esteramine

TABLE 1

Maleic anhydride Acid number Viscosity Melting point (g) (mg KOH / g) (mPa.s / 20 ° C) (° C)

To a sulfonation flask equipped with a contact thermometer, stirrer, nitrogen inlet and distillation head was added 200 g of triethanolamine, which was heated to 170 ° C. From the separating funnel, 379 g of oleic acid were added slowly, according to the rate of condensation water release. After distilling about 80% of the stoichiometric amount of water, the reaction was terminated under vacuum at 180 ° C until completion of water evolution. The esteramine has a viscosity of 210 mPa at 20 ° C. . with.

Preparation of ester amine maleate

100 g of esteramine, maleic anhydride were charged to the flask and the addition was carried out in the melt at 110 ° C for 2 hours. The amount of maleic anhydride and the properties of the maleate are shown in Table 1.

23.7

47.4

107

178 to 55

5108

WITH

Preparation of cationic salts

ChLCH.Ol · / '0

CH '(CH ACHICH (CHi / GCCH / H ^ N © ^C0 ° ^ CHAHAOCCH ^ CHCOOH)

The salts were prepared by homogenizing 10 g of esteramine maleate having an acid number of 103 mg KOH / g with the appropriate acid at 35 ° C and 5 g of the corresponding salt was dissolved in water and made up to 500 ml with water. The amount of acid, the refractive index of the salts and the effect of the salt solutions on the reduction of the surface tension of the water are shown in Table 2.

TABLE 2

M acid Infill (G) H formic 0.9 CH ₃ acid 1.2 CzH5 propionic acid 1.4 Example 2

Preparation of diesteramine

The flask was charged with 200 g of triethanolamine, which was heated to 170 ° C. 757 g of oleic acid were added from the separatory funnel. The condensation was carried out according to the procedure of Example 1. The diesteramine had a viscosity of 107 mPa at 20 ° C. with.

Preparation of anionic salts

n _D ²⁰ Surface tension (mN. M ^_1 ) 1.4794 43 1.4748 35 1.4728 34

Preparation of diesteramine phthalate

200 g of diesteramine, 43.7 g of phthalic anhydride were charged to the flask and the addition was carried out in the melt at 125 ° C for 1.5 hours. The prepared phthalate has no. acidity 69 mg KOH / g and viscosity at 20 ° C 13 544 mPa. with.

COOX

CH3CH4 / CH-CH (CH3COOCH3CH3)

NCH2CH2OOC-, ~

The salts were prepared by neutralizing 10 g of diesteramine phthalate with the appropriate base. In the case of solid sodium and potassium hydroxides, these were used in the form of 50% aqueous solutions. The base used, the amount thereof and the effect of salts on reducing the surface water drift are shown in Table 3. Aqueous salt solutions were prepared by dissolving 5 g of salt in water, which was made up to 500 ml with water.

TABLE 3

principle Infill (G) n _D ²⁰ Surface tension (mN. M ¹ ) ammonium hydroxide (26%) 1.80 1.4743 42 sodium hydroxide (55 ° / o) 1.00 1.4828 35 Potassium hydroxide (50%) 1.50 1.4803 34 monoethanolamine 0.80 1.4931 35 diethanolamine 1.30 1.4930 35 triethanolamine 1.90 1.4933 35

Example 3

275 g of triethanolamine and 500 g of a technical mixture of fatty acids of the composition shown in Table 4 were introduced into the flask.

TABLE 4

Stearic acid (%) 52.4 Palmitic 42.3 Lauric 1.9 Arachic 0.7 Caprylic 0.1 Pentadecanoic 0.3 Heptadecanoic 1.7 Caprenic 0.3 Unidentified 0.3

The condensation was carried out according to the procedure of Example 1. After reaching an acid number of 1.8 mg KOH / g, 175 g of maleic anhydride was added to the melt at 110 ° C and the addition was accomplished with an acid number of 125 mg KOH / g. The prepared technical mixture of ester amine maleate has an appearance of a waxy mass with a melting point of 42 to 43 ° C.

Example 4

To the flask was charged 106 g of triethanolamine, which was heated to 170 ^° C. 200 g of the technical mixture of liquid fatty acids of the composition given in Table 5 was slowly added from the separatory funnel according to the water release rate.

TABLE 5

Oleic acid (%) 83.4 Linoleic 10.4 Linoleic 3.6 Stearic 1.2 Not identified 1.4

Condensation was carried out according to the procedure of Example 1. At 100 ° C, 210 g of phthalic anhydride was added to the melt and after dissolution the temperature was raised to 130 ° C and held there for 2 hours. The prepared technical mixture of ester phthalates has a melting point of 80-82 ° C and an acid number of 161 mg KOH / g.

Example 5

Following the procedure of Example 1, the corresponding N-bis (2-hydroxyethyl) aminoethyl esters of fatty acids (HEMK) were prepared by reacting triethanolamine with fatty acids. 100 g of HEMK, phthalic anhydride were added to the flask and addition was performed at 125 ° C for 2 hours. Phthalic anhydride amounts and properties of individual phthalates of structural formula

CO OH 2 CH 2 CH 2 OOC

R.COOCH.CH.N * CH3 OH where

R 3 is the remainder of the fatty acid used shown in Table 6.

TABLE 6

HEMK phthalic anhydride (G) Acid number (mg KOH / g) Melting point (° C) stearic 35.6 100.1 51 palmitic 38.2 106.0 43 myristic 41.2 113.1 36 lauric 44.7 118.2 27

Example ₆ rjs' · stearic acid with acetic acid in hmotnostβ '' nominal ratio of 2: 1, a paste that from the ester amine of Example 3 was decanted Ip ^ was used as a 1 ° / o aqueous solution of _t to adjust the optical fiber directly after leaving the Pt oven. The paste consisting of 50% esteramine and 50% esteramine phthalate according to Example 5 based on stearic acid was evaluated in the same manner. The migration coefficient, which indicates the ratio of lubricant content on the outside of the coil to the inside of the coil, is 1.8 in the case of esteramine alone and has been reduced to a minimum of 1.2 by addition of esteramine phthalate. In this way, an even coating of the fibers with a lubricant is achieved, which is positively manifested in various textile operations.

a cylinder which was used to lubricate glass fiber of E-glass with a diameter of 6 μπι. 34 tex when weaving on a pneumatic loom. Paraffin, which is commonly used for weaving lubrication, was evaluated in the same manner. When using esteramine, a higher performance of 6-10% was achieved over paraffin.

Example 7

Melting and homogenizing the N-bis (2-hydroxyethyl) aminoethyl ester

Claims (1)

OBJECT OF INVENTION Fatty acid amphoteric esteramines of the formula CH2CH2OOC-R2-COOH Z (R 3 - COOCH 2 CH 2) _x N \ (CH ₂ CH ₂ OR 12) _x wherein R 3 is an alkyl or alkenyl radical x is an integer of 1 or 2, having from 8 to 18 carbon atoms, and their salts with R 1 are hydrogen or struc- tures such as sodium, potassium, ammonium and Quaternary ammonium with mono-, di-, tri (2-hydR2 is a divalent group of 1,2-phenylene or oxyethyl ethyl amine or with acids such as vinylene, formic acid, acetic acid, propionic acid.