DE1495930C3 - Polyamides - Google Patents

Description

Make up half of the polyamine used; in particular, the ethylene or propylenediamine content should represent ³ A of the amine groups present.

There is essentially one equivalent of carboxyl groups for one equivalent of the amino groups used. Small excesses of about up to 10% of either the carboxyl groups or amino groups however, are still viewed as "essentially equivalent".

For the polyamides obtained according to the invention are used polymeric fatty acids, which by Polymerization of drying or semi-drying oils or free fatty acids or simple ones Alcohol esters of these fatty acids are formed. The term fatty acids refers to saturated, ethylenic unsaturated and acetylenically unsaturated, naturally occurring and synthetic monovalent aliphatic Acids with 8 to 24 carbon atoms.

Due to their ready availability and their relatively easy polymerization are oil and Linseed oleic acid is the common starting material for the production of polymeric fatty acids.

Commercially available polymeric fatty acids made from unsaturated Cie fatty acids have the following typical composition:

Ci8 monovalent acids 5 to 15 percent by weight,

C36 dibasic acids 60 to 80 percent by weight,

Cm (and higher) trivalent acids 10 to 35 percent by weight.

These mixtures can be used in a suitable manner, e.g. B. by distillation in a high vacuum or solvent extraction, fractionate so that, if necessary, polymeric fatty acids with a high concentration of can win dimeric fatty acids. In the polymeric fatty acids that are obtained according to the invention for the Polyamides are used, the content of the monomeric fatty acids can be within a fairly wide range Range, namely between 1 and 5% and 15 to 20%, fluctuate.

The solubility properties of the polyamides obtained according to the invention were determined by that 35% solid solutions in denatured ethanol (ethyl alcohol, 81.5%; isopropyl alcohol, 9.0%; methyl alcohol, 4.3%; Water, 4.3%; Methyl isobutyl ketone, 0.9%). The solutions were made observed immediately, sealed and stored at room temperature (about 23 ° C) for several weeks. While Observations were made of this storage and the day on which the solution gelled was noted was observed first.

The blocking properties were measured by TAPPI method D477. The polyamides obtained according to the invention were applied from the solution to label paper so that the film thickness after drying was about 0.00127 cm. The two coated surfaces were brought into contact with each other at a relative humidity of about 95% under a pressure of 0.07 kg / cm ² and at temperatures of 54 to 71 ° C, and the area sticking together as an average block was blocked. The blocking was tested by either eating one coated side on another coated side or surface on surface, and one coated side on an uncoated side or surface on back. The melting points (softening points) of the polyamides obtained according to the invention were measured by conventional melting point determinations with “ball and ring” according to ASTM E 2858T.

In the following examples, the polymeric fatty acids are derived from tall oil fatty acids; all parts and Percentages mean parts and percentages by weight, unless stated otherwise.

example 1

0.777 gram equivalent (717 g) polymeric fatty acid, 0.223 gram equivalent (13.4 g) acetic acid, 0.90 Gram equivalent (27.0 g) ethylenediamine and 0.10 gram equivalent (3.4 g) diethylenetriamine were in a three-necked round bottom flask equipped with a thermometer, mechanical stirrer, distillation column and helmet was introduced. The mixture was stirred and heated to 100 ° C, 15 Maintained at this temperature for minutes and then heated to 140 ° C; at this point water started to distill off. The temperature was gradually increased to 200 ° C and, while the water continued distilled off, held at 200 ° C. for a further 4 hours; the last hour under reduced pressure of about 15 up to 20 torr. The vacuum was released and the product removed from the flask and cooled. An amber-colored, hard, solid polyamide was obtained.

Example 2

A series of polyamides were prepared by following the procedure of Example 1, with those shown in FIG The following table mentioned monomer compositions were used.

Equivalents Monocarboxylic acid Equivalents Equivalents Equivalents Equivalents polymers Ethylenediamine Diethylene Azelaic acid fatty acid - triamine Comparison 0.167 attempt 1.0 - 0.223 1.0 - - IN THE 0.833 acetic acid 0.223 0.90 0.10 - II-2 0.777 acetic acid 0.223 0.90 0.10 - II-3 ^v 0 _A 77-7 acetic acid 0.223 1.00 - - 11-4 0.777 acetic acid 0.22 0.80 0.20 - II-5 0.777 acetic acid 0.25 0.85 0.15 - II-6 0.75 acetic acid 0.25 0.90 0.10 0.03 II-7 0.75 acetic acid 0.90 0.10 - II-8 0.75 Propionic acid 1.00 - -

Continuation .

Equivalents

polymers

fatty acid

Monocarboxylic acid

Equivalents.

Equivalents
Ethylenediamine

Equivalents

Diethylene

triamine

Equivalents of azelaic acid

II-9 0.75 Formic acid 0.22 0.90 0.10 0.03 H-IO 0.777 Butyric acid 0.223 0.90 0.10 - 11-11 0.70 acetic acid 0.223 0.90 0.10 0.077 11-12 0.777 Propionic acid 0.223 0.90 0.10 ■

The polyamides obtained had the following properties:

Softening point Amine number Acid number Solubility at 35% solids content and 23 ° C Days to in denatured ethanol Gelation at the start ■ - ■ (° C) - ■ _ ·. · - ■ Comparison ι attempt 110 4.1 3.9 . insoluble > 39 II-l 120 4.4 3.7 Completely*) II-2 127.5 8.6 5.0 Completely*) ■> 38 II-3 131.2 2.8 3.2 Completely*) > 33 II-4 120.8 9.1 6.0 Completely*) > 24 -. ·· H-5; 121.5 7.4 ::. 6.0 ■ complete *) > 24 II-6: · .. ·.; - 126.5: .- ■ 6.4 ■ 4,3 ■: ^; Completely*) 1 II-7 128.8 6.3 4.9 Completely*) 1 H-8 144.2 3.9 ■ 3.4 Completely*) 1 ■ II-9 99.8 8.4 2.1 cloudy 24 11-10 134.1 6.6 3.3 Completely 2 H-Il 131.4 6.4 5.7 Completely H-12 136.8 6.0 3.7 Completely

*) Clear solution at room temperature.

The polyamide of the comparative experiment was made from 90% denatured ethanol and 10% n-propanol existing solvent mixture insoluble. The polyamide according to Example H-I was completely soluble in this solvent mixture at 35% solids content. The polyamide according to Example 11-12 proved to be very readily soluble in at a solids content of 35% a solvent mixture which consisted of 1 part of n-propanol and 2 parts of denatured ethanol.

A solution of the polyamide according to Example II-2 with 35% solids content in denatured ethanol was used with regard to the properties that are important for flexographic ink binders.

% Block at 54 ° C, 0.07 kg / cm ² , 95% relative humidity:

24 hours - surface to surface none

Top to back none

% Extensibility, G. E. Impact Flexibility Tester 5 to 10%

Compatibility test, 70:30 weight ratio; SS ¹ A second,

Nitro cellulose compatible

Example 3

Sward hardness 21 The following table shows the influence

Tack-free time, 0.00381 cm wet film 3 minutes 55 moderately small amounts of lactic acid on the

Gloss on label paper, 0.00381 cm shafts according to the invention with and without lactic acid

wet film 74 obtained polyamides.

Equivalent Others

polymers

fatty acid

Equivalents equivalents carboxylic ethylenic acid diamine

Equivalent Er solubility at 35% solids

Diethylene softener content and 24 ° C in vertriamine point ethanol

at the beginning days up

for gelation ( ⁰ C)

II-2
IU-I

0.777
0.77

acetic acid
acetic acid
Lactic acid

0.223

0.18

0.05

0.90 0.90

127.5 complete 39

119.6 complete 42

continuation

Equivalent Others Equivalents Equivalents Equivalents He Solubility at 35% solids polymers Carbon Ethylene Diethylene softening substance content and 24 ° C in ver fatty acid acid diamine tnamin Point quenched ethanol at the beginning days until ' to Ge Γ C) lation

11-12 III-2

0.777 0.77

Propionic acid propionic acid lactic acid

0.223

0.18

0.05

0.90 0.90

0.10 0.10

136.8 complete 2

130.2 complete 20

Claims (4)

Patent claims: 1. Polyamides, obtained by condensation at 150 to 250 ° C of polyamines of the general formula H2N (R'NH) "H where R 'is an alkylene radical having 2 to 3 carbon atoms and π is an integer from 1 to 4, ι ο where at least half of the polyamines used are η-Λ , with lower aliphatic monobasic acids of the general formula "■." RCOOH> 5 wherein R is a hydrogen atom or an aliphatic radical having 1 to 4 carbon atoms, and with polymeric fatty acids, optionally with lactic acid or azelaic acid, the equivalents the amino groups used are essentially the equivalents of the carboxyl groups used correspond, at least 90 equivalent percent of the carboxylic acid groups used from the polymeric fatty acids and the lower monobasic aliphatic acids and the remainder of lactic acid or azelaic acid and wherein the equivalent ratio of the polymeric fatty acids to the lower aliphatic monobasic acids in the range from 90:10 to 65:35. 2. Polyamides according to claim 1, obtained using acetic acid or propionic acid as lower aliphatic monobasic acid. 3. Polyamides according to claim 2, obtained using a mixture of ethylenediamine and diethylenetriamine in the equivalent ratio of 90: 10 as polyamine. 4. Process for the preparation of the polyamides according to claim 1 by condensation of polymers Fatty acids with polyamines of the general formula wherein R 'is an alkylene radical having 2 to 3 carbon atoms _; men and π is an integer from 1 to 4, wherein at least half of the used polyamines η = 1 and · equivalents of amino groups used correspond essentially to the equivalents of carboxyl groups used in usual Amidierungstemperaturen of 150 to 25O ⁰ C , characterized in that in addition to the polymeric fatty acids, lower aliphatic monobasic acids of the general formula RCOOH 55 used in which R is a hydrogen atom or an aliphatic radical having 1 to 4 carbon atoms, wherein at least 90 equivalent percent of the carboxylic acid groups used are from the polymers Fatty acids and the lower aliphatic monobasic acids and the remainder of lactic acid or Azelaic acid and the equivalent ratio of the "" polymeric fatty acids to the lower aliphatic monobasic acids in the range of 90:10 to 65:35. Flexographic inks are colors that are produced by rollers or pillows on flexible sheets of plastic film and have paper applied. Since the replacement of the previously widespread polyethylene films with new ones Plastic films, such as polypropylene films, for heat sealing the new plastic films at higher temperatures are required, the binders for flexographic inks must not only be soluble in alcoholic Solvents, but also be resistant to these higher temperatures and also the associated sticking together or the blocking brought about by the high temperatures resist. Solubility in alcohols used as solvents must be achieved without the Adversely affect the toughness, adhesion, gloss and chemical resistance of the paints. According to GB-PS 8 85 614 by reacting an alkylenediamine with 2 to 6 carbon atoms 150 to 300 ° C with a mixture of polymeric fatty acids and dimerized resin acids Polyamides are said to be useful as binders for flexographic inks. More detailed investigations however, have found that these polyamides in denatured ethanol, the ideal solvent for flexographic inks, are not soluble. The polyamides described in GB-PS 8 45 560, which by condensation of polymeric fatty acids with dibasic acids with 5 to 10 carbon atoms, alkylenediamines with 2 to 6 carbon atoms, Polyalkylenepolyamines with 3 to 5 amino groups and their alkylene groups with 2 to 3 carbon atoms contain, and optionally monomeric fatty acids with 8 to 22 carbon atoms are formed in denatured Ethanol is insoluble and is therefore not suitable as a binder for flexographic inks. The polyamides obtained according to the invention, on the other hand, are used as binders for flexographic inks particularly suitable because they advantageously have high melting points, the required non-blocking Show properties and a greatly improved solubility in alcohols, especially in ethanol, have that compared to the solubility of conventional polyamides made from polymeric fatty acids and ethylenediamine is markedly improved without the addition of a lower aliphatic acid. Most of the polyamides obtained according to the invention show excellent solubility in denatured Ethanol. Certain polyamides with a higher melting point are less in denatured ethanol soluble, but their solubility is sufficient for most purposes. Also supply other small additions Solvents, e.g. B. n-propanol, isopropanol, heptane or aliphatic hydrocarbon mixtures, dye binder solutions with satisfactory properties. Examples of lower aliphatic monobasic acids using the polyamides according to the invention are formic acid, acetic acid, propionic acid and butyric acid. From the point of view of physical properties, from the point of view of availability and economy, are acetic acid and Propionic acid the preferred acids. The polyamines with the use of which the polyamides are obtained according to the invention include including ethylenediamine, propylenediamine, diethylenetriamine and triethylenetetramine. These polyamines can be used individually or in a mixture with one another, but the ethylene or propylene diamine content must such a mixture at least the