CS218608B1 - Concentrates of antistatic modifiers in liquid form for polyamides and methods for their preparation - Google Patents

Abstract

Concentrates of antistatic modifiers in liquid form for the modification of polyamides consist of 5 to 60% by mass. polyetheramides or their prepolymers, prepared by polycondensation of a mixture of 50 to 95 wt.%. diaminopolyethyleneglycols with an average mol. weight 800 to 4000, from dicarboxylic acids with 4 to 8 carbon atoms, or their esters, in the amount of 1 to 1.2 equivalents per diaminopolyethylene glycol used, or allowance up to 100% wt. epsilon-caprolactams or epsilon-aminocaproic acid and from 40 to 99.5% water, or organic polar solvents or their mixture. The method consists in dispersing the polyetheramides in the solvent by heating the mixture to boiling point for 2 to 6 hours.

Description

It is an object of the present invention to provide concentrates of antistatic modifiers in liquid form and processes for their preparation.

Antistatic modifiers are generally polar-containing substances that reduce the surface static charge of polymers and polymer products.

Effective antistatic modifiers for polyamides, especially for polyamide fibers, are polyetheramides. Polyetheramides are substances of a macromolecular nature, generally with the character of a block copolymer. They are usually prepared by polycondensation or copolycondensation of substances with polyamide-forming functional groups, of which, as a rule, one or rarely more, contain a polyether, usually polyglycol ether chain, in the molecule.

Their advantage is good antistatic efficiency and resistance to scrubbing. On the other hand, the methods of their processing are complex and technically demanding.

The polyetheramides described above are generally added to the polyamide mass in various ways. Their properties correspond to such applications. A more technically preferred method of application would be to add them to the monomer prior to the preparation of the polyamide, or topically to the finished fibers. This is, of course, possible only if the requirement that the physical and chemical properties of the modifier correspond to such uses is met.

In particular, the physical properties require that the polyetheramide used be melted at relatively low temperatures not exceeding the substantial melting point of the monomer or, in terms of handling, even better to be liquid at normal temperature or to be applied to the fiber surface.

The properties of the polyether amides described above, and hence their melting points, can be varied within a relatively wide range by the method of preparation, in particular by the nature and relative proportions of the amounts of their starting components. However, these possibilities are not unlimited, since the polyether amides prepared must meet the requirement of scrub resistance on the one hand, and on the other hand their composition must not allow complete, immovable incorporation of the individual modifier molecules into the resulting polyamide macromolecules.

We have found that the possibilities of lowering the melting point of polyether amides, without neglecting its influence on the starting composition, can be further expanded by the addition of suitable solvents.

This possibility has not been pursued so far because it has not been up-to-date with regard to the use of polyetheramides to date, and because liquefaction of polyetheramides encounters some implementation problems. In particular, polyether amides dissolve into false solutions only to a limited extent in the composition. By a more complicated process, it is possible to prepare liquid permanent dispersions of polyether amides of a composition which does not allow the formation of liquid metals. Such dispersions have very good and versatile application properties while maintaining the modifying effects.

Concentrates of antistatic modifiers for polyamides and a process for their preparation according to the invention consisting of (A) 0.5 to 60 wt. % polyetheramides or prepolycondensates thereof, obtained by polycondensation of a mixture of 50 to 95 wt. diamino polyethylene glycols with diam. mol. % by weight of 800 to 4000, dicarboxylic acids of 4 to 8 carbon atoms, or esters thereof in an amount of 1 to 1.2 equivalents per diamine polyethylene glycol used and, optionally, up to 100 wt. ε-caprolactam or ε-aminocaproic acid and from (B) 40 to 99.5 wt. water or organic polar solvents or mixtures thereof.

The organic polar solvents may be glycol, oligomers thereof, ethanol or mixtures thereof. The polyether amides of the present invention are prepared in the form of a liquid dispersion or solution by heating the polyether amides with solvents to the boiling point of their mixture for a long time.

The practical preparation of the polyetheramide modifier in the form of a liquid concentrate or solution may advantageously be carried out in such a way that the polyetheramide, or its prepolycondensate of suitable composition, is added to the polyetheramide modifier. by performing the polycondensation, it is allowed to cool partially and is added to the required amount of selected solvents, or the cold, solidified modifier is mixed with the solvent and its dispersion is ensured by heating the mixture. For the preparation of the modifier in liquid form according to the invention, it is advantageous to use a polyetheramide with a higher content of the polyether component above 50%.

Such polyetheramide disperses relatively readily, forms a stable emulsion and has many technical advantages in applications related to its liquid form. They are mainly as follows: the liquid modifier can be stocked, can be manufactured for commercial purposes because it is technically applicable without prior treatment, its application is simple and does not require special manufacturing equipment.

Its other advantage is its versatility in a variety of ways and techniques of use. However, it is expedient to choose the appropriate concentration of polyetheramide for each mode of use.

For the preparation of dilute concentrates, it is possible to start from concentrates with a higher content of polyetheramide. Their concentration can be easily adjusted by the addition of a solvent.

Example 1

Polyetheramide having a starting content of 60 wt. diaminopolyethylene glycol of relative mol. The weight of 1600 was allowed to cool to about 180 ° C just after the polycondensation preparation and then extruded as a string into water heated to 70 ° C so that the final mixture contained 40% by weight of polyetheramide.

The extruded strings swell very rapidly in contact with water and gradually melted away. The dispersion of the modifier was completed by heating to the boiling point of the mixture for two hours.

Example 2 A polyetheramide identical to Example 1 was cooled and allowed to solidify. After cutting to water, water was added at a ratio of 40:60. The mixture was heated to boiling for four hours to give a liquid dispersion.

Example 3 l

The polyetheramide pre-polycondensate prepared by polycondensation of a mixture of 100 g of diamino-polyethylene glycol, 10 g of adipic acid by heating to 253 ° C for three hours was allowed to cool to 120 ° C. Then 10 g of ε-caprolactam was added with stirring. After further cooling to 70 ° C, the mixture was mixed with an equal amount of 70 ° C warm water. The mixture was then converted to an opalescent solution by heating for half an hour. j

Example 4 218608

The modifier concentrate was prepared similar to Example 1. However, the polyetheramide used varied in composition and represented the polycondensate of a mixture of 32 g of diamino polyethylene glycol with mol. weight. 1600.4 g of dimethyl phthalate and 5 g of ε-aminocaproic acid.

Example 5

The procedure for preparing the modifier concentrate was identical to Example 1. However, the polyetheramide was a polycondensate of a mixture of 30 g of diamino-polyethylene glycol 3000, 2 g of diethyl adipate and 5 g of ε-aminocaproic acid.

Example 6

The polyetheramides used in the previous examples were liquefied similar to Example 2. except that a mixture of 70% water and 30% diglycol was used as the solvent instead of water.

Claims (3)

OBJECT OF THE INVENTION Concentrates of antistatic modifiers, even in liquid form, for polyamides, characterized in that they consist of 0.5-60 wt. % polyether amides or prepolycondensates thereof, obtainable by polycondensation of a mixture of 50 to 95 wt. diamine-; nopolyethylene glycols having an average molecular weight of 800 to 4000, dicarboxylic acids having 4 to 8 carbon atoms, or esters thereof, in an amount of 1 to 1.2 equivalents per diamine polyethylene glycol used and, optionally, addition I to 100 wt. % of ε-caprolactam, or ε-aminocaproic acid I, and from 40 to 99.5 wt. water and / or organic polar solvents. 2. Liquid concentrates according to claim 1, characterized in that the organic solvents are glycol and its glycol ^. oligomers, ethanol, or mixtures thereof. 3. Preparation of liquid concentrates after! 2. The process according to claim 1, wherein the polyether amides are dispersed in the solvent by heating to the boiling point of the mixture for 2 to 6 hours.