CS218607B1 - Low melting polyetheramides - Google Patents

Abstract

The invention relates to low-melting polyetheramides, with a melting point below 120 °C and a content of more than 85-97 wt. % diaminopolyglycol component. The purpose of the invention is the development of easily applicable modifiers for polyamides and polyamide fibers. The solution consists in adjusting the quantitative representation of the starting components, thereby achieving a reduction in melting temperatures and the possibility of applying the modifier to the monomer.

Description

3 218607

The present invention relates to low melting polyetheramides having a high diamine polyglycol component content.

Polyetheramides are generally proposed as effective polyamide modifiers. Compared with polyglycols, or their simple derivatives, the compatibility with the polymer has a substantial higher stability of the modifying effect. They are prepared by poly-condensation of a mixture composed of diamine derivatives of polyglycols, dicarboxylic acids, polyamido-forming monomers and other impurities. With regard to their properties and their current use by adding to the finished polyamide, the previously claimed and protected polyetheramides with a lower content of the diamino polyglycol base component than 80-85% in the mass modifier. Such modifiers have good dispersion effects, are wash-resistant. Disadvantages are the problems associated with their incorporation into the polymer. This can be accomplished by reshaping the mechanical mixture of the granulated modifier with the polymer granulate, or by mixing their hot melt with the polymer melt for modification.

Both of these techniques are technically challenging to implement. The first method requires a modifier with relatively high melting temperatures. to a diamino polyglycol content in the diffiner below 80-85%. Converting the granulator to the modifier is also a serious problem due to its stickiness.

On the other hand, for the second mode of incorporation of the dopolyamide modifier, i.e. for the mixing of the melts of both components, the necessity of working at relatively high temperatures at which the already technically complex mixing equipment is needed. A more preferred process of modification by adding a modifier to the monomer at low temperatures, once claimed polyetheramides, does not allow for their relative high melting temperatures.

These problems can be solved by the development of new types of polyetheramides with low melting temperatures and this requirement by correspondingly altered compositions. Preferred modifiers applicable to doamide-forming monomers have been shown to be low melting polyetheramides having a melting point below 120 ° C, consisting of a polycondensate mixture of diamino-polyethylene glycol, dicarboxylic acids having 5-8 carbon atoms, or their esters, ε-caprolactam or ε-aminocaproic acid, and optionally stabilizers and branching agents, characterized in that their molecular chains contain more than 85 to 97 wt. α, ω-diamino-polyethylene glycol having an average molecular weight of 800-4000 and 1 - 1.2 equivalents of carboxylic acid or its ester to the diamino polyethylene glycol used.

The proposed low-melting polyether amide has the function of a modifier over the prior art more advantages. The demands for quality, especially purity of the starting diaminoopolyalkylene glycols are lower. Its main advantage is its application properties and the possibility to use it in a mono next. α-, ω-Diamino-polyethylene glycol for a suitable polyether amide according to the invention, similar to the preparation of branched polyether amides, an average relative mol. weight'800—4000 preferably 1000—2000. Lower molar mass no longer makes it possible to prepare a product with the desired composition. Higher does not provide high productive, long-lasting antistatic effects.

The high α-, ω-diamino-polyglycol modifier is preferably applied to the polyamide monomer, e.g., caprolactam, or its polymerization mixture with other additives prior to polymerization, or during polymerization. The use of the high diamine polyglycol modifier of the present invention in a finished polymer processed by conventional means is less preferred.

However, if the polymer, after addition of the modifier, undergoes a prolonged heating above the melting temperature while mixing, then the modifier can also be applied to the finished polymer. It is believed that upon application of the domonomer modifier, this is subject to changes during polymerization, mainly due to preamidation of functional groups. As a result, the scaling resistance of the modifier is increased. On the other hand, the fact that the modifier does not lose its anti-static efficiency even when incorporated into the polymer indicates that it is not completely blocked in the polymer, as is the case when the modifier is added to the monomer instead of the modifier.

The technical advantages of the polyether amide modifier of the proposed type over the current modifiers are the lower quality of the raw materials, the simpler composition and the method of its preparation, the easier handling of it due to the relatively low dipping temperature and simpler application of the polymer, or in this case more correct to the monomer resp. A further technical advantage is that the modifier of the higher concentration of the active ingredient can be added to the polymerization mixture to a lesser extent and thus less affecting the course of the polymerization itself and some utility properties of the modified polymer.

The modifiers of the present invention and the method for their preparation demonstrate, without limiting the scope of the invention, the following examples. Example 1

A mixture of 161 g of α-, ω-diamino polyglycol with a relative average molecular weight of 1610, 16 g of adipic acid, 10 g of caprolactam, 0.5 g

Claims (3)

4 triphenyl phosphite was heated to 25 ° C for 6 hours. The reaction product was suitable as an antistatic modifier for polyamide and polyamide products useful in the monomer. Example 2 Mixture of 161 g of α-, ω-diamine polyglycol by relative diameter. mol. 1610, 16 g of adipic acid, 5 g of caprolactam and 0.5 g of triphenylphosphite were sapolycondensed as in Example 1. The resulting modifier had a reduced melting point compared to the prior art, the modifying properties and application being the same as those of the modifier Example 3 Example 3 A mixture of 161 g of α-, ω-diamino polyglycol, 16 g of adipic acid and 0.5 g of triphenyl phosphite was condensed by heating at 253 ° C for 6 hours in an autoclave. The prepared modifier had a lower melting point as in previous cases. The mode of use and the modifying effect are similar to those of the previous cases. Example 4 A modifier was prepared similar to Example 1 except that the addition of triphenyl phosphite was omitted in its composition. The degree of polycondensation was about to be lower than in Example 1. Modification effects SUBSTITUTE Low-melt polyetheramides with a melting point of 120 ° C, prepared by polycondensation of a mixture of diamino-polyethylene glycol, 4-8-carbon dicarboxylic acids or esters thereof, ε-caprolactam or ε-aminocaponic acid and optionally stabilizers and reagents cause 218607, but its utility was similar to Example 1. Example 5 A modifier was prepared similar to the Example 3. In the composition, however, the addition of triphenylphosphine was omitted. The modifying effects and application possibilities are similar to those in Example 3. Example 6 A mixture of 15 g of α-, ω-diamino-polyethylene glycol 3000, 0.8 g of adipic acid and 0.05 g of triphenylphosphine was polycondensed as in the previous example. The modifier was good processable above 100 ° C liquid. Example 7 A mixture of 16.1 g of α-, ω-diamino-polyethylene glycol, 2 g of diethyl acid, adipic acid was condensed at 250 ° C for 4 hours. The condensate was used as a modifier. Example 8 Mixture of 16.1 g of α-, ω-diamino-polyethylene glycol diam. mol. 1610.2 g of dimethylphthalate and 0.05 g of triphenylphosphite were polycondensated at 255 ° C for 4 hours. The modifier was liquid at a temperature above 100 ° C and a good workable. However, the increased content of the modified fibers has partly exacerbated the increased content. THE INVENTION. their branching molecules whose molecular chains contain more than 85-97% wt. α-, ω-diamino-polyethylene glycol of the average relat. mol. 800 to 4000 and 1 to 1.2 equivalents of dicarboxylic acid or ester thereof to the diamino-polyethylene glycol used. Price: 2,40 Kčs Printed by Moravské tiskařské závody, operation 12, Leninova 21, Olomouc