CS245540B1 - Fatty acid bisaminoamides - Google Patents

Abstract

The solution describes bis-aminoamides based on fatty acids, suitable as lubricants for the surface treatment of glass fibers. The preparation of these compounds can be carried out by amidation of fatty acids with diethylenetriamine in a molar ratio of 1:1. The prepared amino amide is allowed to react with phthalic anhydride or violet, isophthalic, terephthalic acid or their esters in a molar ratio of 2:1. By neutralizing with acids, they can be converted into appropriate salts, for example with acetic acid.

Description

(54) Fatty acid-based bisaminoamides

2

The solution describes bis-aminoamides based on fatty acids, suitable as lubricants for the surface treatment of glass fibers. The preparation of these compounds can be carried out by amidation of fatty acids with diethylenetriamine in a molar ratio of 1:1. The prepared amino amide is allowed to react with phthalic anhydride or violet, isophthalic, terephthalic acid or their esters in a molar ratio of 2:1. By neutralizing with acids, they can be converted into appropriate salts, for example with acetic acid.

The invention relates to bis-aminoamides based on fatty acids and their ammonium salts.

To treat glass and mineral fibers, spit lubricants are used (Czech Republic Auth. Osv. No. 185 291, 185 293). They are usually amphipathic compounds from which it is possible to prepare either aqueous solutions or emulsions.

For these purposes, alkylolamides prepared by the reaction of higher fatty acids with alkylolamines and aminoamides based on aliphatic polyamines and fatty acids have found significant application for these purposes (US Pat. No. 3-108,891, 3,167,483, 3,265,516, 3,284,179 and 3,461,090).

Various amino amides are known, the preparation and modification of which are carried out with various compounds in view of their application. Basic amino amides are most often prepared by condensation, mainly of fatty acids with aliphatic polyamines. (Cs. aut. osv. no. 169 045, 169 047, 170 697, 170698.)

For special applications, mainly as hardeners of epoxy resins, aminoamides are modified with, for example, acrylic acid or its esters (Czech Republic Patent No. 162 137 and 163 890), epoxy elements or epoxy fatty acids (Czech Patent No. 151073, 152 353 and Patent No. 187 162).

When using aminoamides based on fatty acids and diethylenetriamine or dipropylenetriamine solubilized with, for example, acetic acid, we found that there is a significant deterioration of the mechanical properties of polyester fiberglass, mainly the bending strength. Due to the fact that the mentioned compounds are characterized by good sliding properties for glass fibers, their modifications were made, which do not deteriorate their mechanical properties, but on the other hand, remove their influence on the deterioration of mechanical properties. During applied research, we found that these properties make them! compounds according to the invention.

The invention describes bis-aminoamides based on fatty acids of the general formula

R1CNH (CH2 )2NH (CH2 )2NHCR3CNH (CH2 )2NH (CH2 )2NHCR2

O 0 0 o where represents

R1, R2 alkyl or alkenyl radical with 7 to 22 carbon atoms,

R3 phenylene and their ammonium salts.

The preparation of these compounds can be carried out as follows. The corresponding amino amides are prepared by condensation of fatty acids at a temperature of 140 to 220 °C with diethylenetriamine in a 1:1 molar ratio. Fatty acids are used either individually, but more often in mixtures than fatty acids isolated from various oils and fats.

Aminoamides prepared in this way are subjected to a reaction with phthalic anhydride or violet, isophthalic, terephthalic acid or their esters, or with technical mixtures based on them. Neutralization with organic or inorganic acids such as formic, acetic, propionic, hydrochloric, phosphoric, etc. it is possible to convert the reaction products into the corresponding ammonium salts. In this way, it is possible to regulate a whole range of properties of bisaminoamides, such as hydrophilicity, consistency, melting point, etc. due to the required properties.

The invention is further clarified in the form of examples, the composition of which is given in weight and concentration.

Example 1

The appropriate fatty acid, 10 ml of benzene and 10 g of diethylenetriamine were introduced into a sulfonation flask with an azeotropic attachment. The batch was kept at the reflux temperature until the evolution of the reaction water was complete. After this time, 8 g of (1,2:), (1,3) and (1,4) benzenedicarboxylic acid (BDK) were added to the batch, and the batch was kept at reflux temperature until the evolution of reaction water stopped. After cooling, it was washed with aqueous, sodium hydroxide solution, water and the volatile fractions were removed under vacuum. The amount of individual fatty acids and the properties of bis-aminoamides are listed in Table 1.

TABLE 1

Acid Weight g BDK Melting point °C

stearic 27.5 1.2 70 to 73 stearic 27.5 1.3 71 to 74 stearic 27.5 1.4 74 to 77 oil 27.4 1.2 38 to 40 oil 27.4 1.3 40 to 42 oil 27.4 1.4 41 to 44 caprylic 14.0 1.2 31 to 33 caprylic 14.0 1.3 32 to 35 caprylic 14.0 1.4 36 to 39 palmitic 24.8 1.2 58 to 61 laurel 19.4 1.2 37 to 40 myristic 22.1 1.2 42 to 45 geranium 15.3 1.2 34 to 37

Example 2

TABLE 4

500 g of a technical mixture of fatty acids with the composition listed in Table 2 was placed in a sulfonation flask equipped with a stirrer, a contact thermometer, a nitrogen supply and an azeotropic attachment.

TABLE 2

Acid % stearic 52.4 palmitic 42.3 lauric 1.9 arachic 0.7 caprylic 0.1 pentadecanoic 0.3 heptadecano 1.7 capric 0.3 unidentified 0.3

100 g of xylene and 180 g of technical diethylenetriamine with an amine number of 1,638 mg KOH/g were added to the fatty acid melt. The mixture was heated to boiling temperature and condensation was allowed to proceed until the evolution of water ceased. After this time, 129 g of phthalic anhydride were added and the reaction was allowed to proceed until the evolution of water ceased. The prepared bis-aminoamide has the appearance of a waxy substance with a melting point of 65 to 67 °C at 20 °C.

Example 3

An aminoamide was prepared by condensing 400 g of a technical mixture of liquid fatty acids with the composition listed in Table 3 with 145 g of diethylenetriamine according to the procedure of Example 1.

TABLE 3

Acids % oleic 83.4 linoleic 10.4 linolenic 3.6 stearic 1.2 unidentified 1.4

70 g of the prepared amino amide, 15.5 g of acid and 10 ml of toluene were introduced into the apparatus with an azeotropic attachment. The stock was heated to boiling temperature, at which it was maintained until the evolution of water stopped. The properties of bis-aminoamides based on various acids are listed in Table 4.

Acid

Melting point °C violet isophthalic terephthalic

Example 4 to 46 57 to 60 69 to 72

100 g of a technical mixture of fatty acids with the composition listed in Table 5, 49 g of diethylenetriamine and 10 ml of toluene were introduced into the apparatus.

TABLE 5

Lauric acid 50.8 Myristic acid 13.8 Palmitic acid 11.6 Capric acid 8.1 Caprylic acid 7.8 Oleic acid 3.7 Stearic acid 1.2 Unidentified 3.0

The stock was heated to boiling temperature, at which it was maintained until the evolution of water stopped. After this time, 35 g of phthalic anhydride was added and the reaction was again allowed to proceed until the evolution of water ceased. The prepared bis-aminoamide has a melting point of 39 to 42° Celsius. Water-dilutable salts can be prepared by neutralizing with strong acids. The prepared bis-aminoamide with an average molecular weight of 700 in an amount of 5 g was melted and neutralized with acid while stirring and dissolved in 500 ml of water to form opalescent solutions. The acid and its amount are listed in Table 6.

TABLE 6

Acid g

anthill 0.7 acetic 0.9 hydrochloric acid (37%) 1.3

Example 5

Bis-aminoamide based on fatty acids and phthalic acid with an average molecular weight of 850, prepared according to Example 2, was used in the form of a salt with acetic acid to treat glass fibers. Rov2 4 5 5 41 was evaluated using the same method as the basic amino amide based on the listed fatty acids and diethylenetriamine. 3-methacryloxypropyltrimethoxysilane was used as a coupling agent. The treated fibers were used as reinforcement for polyester resin. The evaluation of fiberglass was done by bending strength test and the results achieved are shown in table 7.

TABLE 7

Lubricant Aminoamide Bis-aminoamide flexural strength limit dry MPa 990 1,260 coefficient of variation (%) 6.7 5.6 flexural strength limit after welding MPa 890 1108 coefficient of variation (%) 6.4 5.9 glass content (%) 65.6 65.5

Claims (1)

OBJECT OF THE INVENTION Fatty acid bis-amine amides of general formula R1CNH (CH2) 2NH (CH2) 2NHCR3CNH (CH2) 2NH (CH2) 2NHCR2 Where R 3 is phenylene, R 1, R 2 is an alkyl or alkenyl radical and their ammonium salts. of 7 to 22 carbon atoms,