CS215439B1 - A method for preparing polyether amide antistatic polyamides - Google Patents

Abstract

The method of preparation of polyetheramide antistatic modifiers for polyamides, in which, in the first stage, a polycondensate is prepared from an incompletely reacted mixture, consisting of alpha-omega-diamino derivatives of polyethylene glycol, dicarboxylic acid or its ester and part of other components in an amount of up to 8% by weight. and the second stage of polycondensation is carried out after the completion of the reaction mixture so that the diamino derivative of polyalkylene glycol used in the first stage constitutes 40 to 80% by weight. from the total amount of modifier, while the second stage can also be carried out in the presence of modified polyamide or its monomer or their mixture.

Description

A process for the preparation of polyetheramide antistatic modifiers for polyamides by preparing in the first step a polycondensate from an incomplete reaction mixture composed of alpha-omega-diaminoderivatives of polyethylene glycol, dicarboxylic acid or an ester thereof and part of the other components in an amount of up to 8% by weight. and the second stage of polycondensation is carried out after completion of the reaction mixture such that the diaminoderivative of the polyalkylene glycol used in the first stage is 40 to 80% by weight. % of the total amount of modifier, wherein the second step may also be carried out in the presence of the modified polyamide or monomer thereof or a mixture thereof.

It is an object of the present invention to provide polyetheramide modifiers for polyether polyamide. amides.

The polyetheramides described to date as antistatic polyamide modifiers are prepared by polycondensation of a multi-component reaction mixture composed of the respective α-, ω-diamino polyglycol. or dicarboxylic acids, or functional derivatives thereof, polyamide-forming bifunctional substances, and other admixtures e.g. antioxidants, partial chain branching agents of the resulting polycondensate; and i. Such polyether amides i are macromolecular substances having the character of a block copolymer in which the polyether and polyamide segments are present in a statistically alternating arrangement. The polyether component bears the antistatic properties of the modifier, and the polyamide component, chemically identical to the modified polymer, provides the scrub resistance of the modifier and hence the stability of the antistatic effect. The scrub resistance is increased by the use of a partially branched product. These properties make polyetheramides among the best antistatic polyamide modifiers. In addition to the aforementioned advantages, the polyether amides described above also have some disadvantageous properties, in particular in the claims for their preparation conditions in a usable form and in the claims for their technical application. Of the commonly used methods of incorporating modifiers into polymers, the polyether amides so far prepared with the most desirable composition can be applied practically only by using the polyether amide melt immediately after preparation by polycondensation, without allowing it to cool and solidify by mixing with the melt % of the polymer in a suitable mixing device. This is because the modifier, due to its non-crystalline nature and tackiness, cannot be practically prepared in powder form and that its preparation in granular form is also a serious, technologically unsolved problem. Likewise, the preparation and use of the chilled and solidified modifier has no chance of success, since in this case there are serious difficulties in re-melting the bulk polymer material, meltable over a wide range of about 150 ° C. The technical application of the above method of applying polyetheramide by mixing its melt with the polymer melt following its preparation is associated with claims for special devices to maintain the modifier, after its preparation, in the molten state, for its transport and melt dosage at relatively high melt temperatures. Long-term exposure to higher temperatures translates into a deterioration in the properties of the modifier, in particular a reduction in its whiteness. In addition, we introduce this procedure eliminating the possibility of making a modifier as a commercial product. The requirement to simplify the technical and technological application of polyether amides as modifiers can be partially addressed in the field of their properties by adjusting their composition, namely by changing the melting temperatures and other physical properties of the modifiers. However, such a solution results in a deterioration of other desirable properties of the modifiers.

Starting from these contradictory problems and requirements, it has been shown to change the procedure for preparing the modifier so that its preparation is carried out in a two-step process. The novel process according to the invention makes it possible to prepare a modifier in Tahko-applicable form without increasing the quality requirements of the starting materials.

It has been shown that a suitable method for preparing polyetheramide polyamide modifiers by polycondensation at temperatures of about 255 ° C is a mixture of diamino polyethylene glycols of relative humidity. mol. weight of 600-4000 dicarboxylic acids having 4-12 carbon atoms or their esters and other components such as caprolactam or ε-amino-caproic acid, stabilizers, branching agents of modifier molecules, is a two-stage polycondensation, in which a pre-polycondensate of incomplete reaction mixture is prepared composed of an α, ω-diamine derivative of polyethylene glycol and dicarboxylic acid, or an ester thereof in an amount of 1-1.2 equivalents per polyglycol diamine derivative used, and part of the other components in an amount of up to 8% of the total reaction mixture for modifier production.

The second stage of polycondensation is then carried out after completion of the reaction mixture such that the diamine derivative of the polyalkylene glycol used in the first stage is 40-85% by weight. to the total amount of modifier.

Composition of the reaction mixture for the first stage of the reaction t. j. For the preparation of the prepolycondensate, which is an intermediate for the preparation of the modifier, it is preferably chosen that the intermediate has a low melting point. In particular, the composition comprises a major part or all of the corresponding diamino polyglycol used for the preparation of the modifier and a major part of the dicarboxylic acid. Other ingredients may also be added to the mixture at this stage. However, there is a strict limitation that it cannot be substances which substantially increase the melting point of the prepolycondensate in the amount added. This limitation applies in particular to polyamide-forming monomers which are not to be added at this stage, or at all, or only a small fraction of the proportion in which they are represented in the second stage of the reaction and thus also in the final modifier composition is added.

For the second stage of polycondensation, the reaction mixture is assembled so that all of the components needed to produce the modifier with the desired properties can be used in the polycondensation. This second stage of the reaction can also be carried out in the presence of a modified polymer, or a monomer thereof, or a mixture thereof.

Both stages of the reaction are carried out approximately under the conditions used in the preparation of polyamide - 6. However, if polycondensation is to be discontinued after the first stage and some manipulation needs to be done with the prepolymer, it is preferable to cool the pre-polycondensate reaction mixture to near melting point. , or below this temperature if necessary.

The proposed method allows the use of a modifier in the form of a mixture in which some of the components already act as products of mutual reaction - prepolycondensate, other than the starting chemical indi- viduals, and only in the second stage, by reacting all the components, is the final modifier.

The advantage of said process is that a substantially lower melting point of the reaction mixture is used before the second stage of the polycondensation reaction than the melting point of the finished modifier.

The melting point of the mixture is mainly determined by the properties and composition of the prepolycondensate, the nature and the relative amount of impurities. By their suitable choice it is possible to achieve that the pre-polycondensate or the starting mixture for the second stage - modifier preparation has a melting point well below 100 ° C. This greatly simplifies the manipulation of the modifier and the technical possibilities of its application in the form of a complete or incomplete reaction mixture prior to carrying out the second stage of polycondensation.

Pre-polycondensate resp. its mixture with other substances prepared in the first step according to the invention can easily be applied in the form of a melt immediately after its preparation, or after it has cooled down, respectively. solidification and re-melting. Here, the melting of the prepolycondensates resp. their mixture with other substances is, as a result of their low melting points, technically and technologically possible. This eliminates the need to use and process the modifier at its production site and allows it to be commercialized.

In addition to the aforementioned main advantages, the preparation process of the present invention has a lesser advantage in that the transport and further handling of the prepolycondensate melt can be carried out without the strict exclusion of air oxygen due to the low melting temperatures. In addition, even if it is maintained for a long time at a temperature above the melting point, its thermal destruction and deterioration do not occur.

A further advantage is that the second phase of polycondensation can also be carried out in the presence of modified polymers or polymers. their monomers, or mixtures thereof.

The process of preparing the polyetheramides and intermediates thereof according to the present invention is demonstrated without limitation by the following examples.

Example 1

Mixture of 24 g of a polyethylene glycol α-, ω-diamine derivative with relative mol. weight of 1610, 2.5 g of adipic acid and 0.06 g of triphenyl phosphite were heated - polycondensed - for 2.5 hours in an inert atmosphere, and then 90 min. under vacuum at 254 ° C. After cooling to 100 ° C, the resulting polycon215439 densate was added with stirring to the epsilonamino caproic acid ligands. The total mixture - suspension - was allowed to cool to normal temperature. The mixture could be used as a modifier that reduced the elstat at 3%. charge of modified PAD fibers by more than 60% compared to unmodified fibers.

Example 2

The modifier was prepared as in Example 1, except that epsilon-caprolactam was used instead of epsilon-aminocaproic acid for the initial polycondensate. The mixture is liquid at a temperature above 60 ° C. Its application and modification properties coincide with the properties of the modifier of Example 1.

Example 3

The starting mixture had the initial composition and the treatment method as in Example 2. However, triphenylphosphite was added to the mixture only after the first stage - stage - polycondensation, together with the addition of epsilon caprolactam. The mixture had identical physical properties to the intermediate of Example 2. and the polycondensation properties provided the same options for the second stage of polycondensation.

Example 4

The starting mixture of all components for the preparation of the modifier in the composition according to Example 1 was subjected to a single-stage polycondensation. A modifier with melting points of 150-160 ° C, identical to the method of preparation and properties with modifiers according to CS, was formed. AO 170 627. This had good modifying properties, but could only be incorporated into the polymer by processing them at temperatures above 220 ° C in a more complicated manner than by using the modifiers of the present invention.

Example 5

A mixture of 20 g of a polyalkylene glycol diamine derivative having an approximate molecular weight of 1000.3.2 g of adipic acid and 0.06 g of triphenylphosphite was polycondensed as described in Example 1. After cooling to 100 ° C, 9 g of epsilon-aminocaproic acid were added to the polycondensate. The mixture was used as a modifier.

Example 6

A mixture of 20 g of a polyalkylene glycol diamine derivative of approximately mol. weight 4000, 0.8 g adipic acid and 0.06 g triphenyl phosphite were subjected to polycondensation according to Example 1.

9 g of epsilon-capro-, lactam were added to the prepolymer and a second polycondene- step was carried out; fixed. The mixture of prepolymer with caprolactan and the product of the second stage of condensation were used as modifiers. However, in the preparation of both the prepolycondensate and the end product, the mixing problems of the individual components had to be separately addressed.

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Example 7

The composition and procedure for preparing the modifier are identical to those of Example 2, except that triphenylphosphite, a branching agent for the modifier molecules, is omitted in the preparation of the mixture. The absence of the branching agent reduces the polycondensation degree of the modifier, but does not impair the possibilities for its use to the extent that it is in a one-step preparation process analogous to Example 4.

Example 8

The preparation of the modifier is carried out in such a way that only the first stage of polycondensation is carried out separately and only by reaction of the basic components i.e. α-, ω-diamino polyglycol, adipic acid and triphenyl phosphite in amounts according to Example 2. The mixture at a temperature above 50 ° C forms a liquid substance. The mixture was added to the polymerization mixture caprolactam in an amount of 3%, and sapolycondensated with it. During this process, the basic prepolycondensate of the modifier reacts with an appropriate portion of the monomer - caprolactam - to the polyetheramide incorporated in the polymer.

Example 9

Similar to Example 2, a larger scale modifier sample was prepared. A mixture of 2400 g of α-, ω-diamino polyglycol, 250 g of adipic acid, 5 g of triphenylphosphite was polycondensed at 254 ° C under a nitrogen atmosphere and for 1.5 hours. in a vacuum. 1000 g of caprolactam was added to the mixture after partial cooling to 100 ° C. The mixture was used as a PAD modifier with good results.

Example 215439

A pre-polycondensate of a mixture of 2400 g of α-, ω-diamino-polyethylene glycol, 250 g of adipic acid and 6 g of triphenyl phosphite was used as modifier. It can be used as a modifying additive to caprolactam, or other polyamide-forming monomer supplementing its composition, prior to transferring polycondensation.

Example 11

The modifier was prepared similar to the example

8. except that the addition of triphenylphosphite has been omitted from its composition. It could be used as in the previous example.

Example 12

Mixture of 24 g of a α, ω-diamine derivative of polyethylene glycol with relative mol. 1610.3.3 g of dimethyl terephthalic acid ester was polycondensed in an inert atmosphere at 250 ° C for 2.5 h. per norm. pressure and then 1.5 h. under vacuum. The resulting condensate was admixed to caprolactam in an amount of 4% and subjected to post-polycondensation.

Example 13

The preparation of the modifier was similar to Example 1. However, instead of adding triphenylphosphite, 0.05 g of trimezinic acid was used. The properties of the polycondensate coincided with Example 1.

Claims (1)

EXAMPLE 7 Composition and procedure for the preparation of a modifier, according to the procedure of Example 2, with the exception that the triphenylphosphite - a branching agent of the modifier modifier - is omitted in the preparation of the mixture. The absence of branching agent reduces the polycondensation degree of the modifier, and does not impair its use as much as in the one-step preparation process analogous to Example 4. EXAMPLE 8 The preparation of the modifier is carried out so that only the first stage of the polycondensation is converted and only by the reaction of the base. of the components ie α-, ω-diamino polyglycol, adipic acid and triphenylphosphite in the amounts of Example 2. The mixture of priteplote above 50 ° C forms a liquid substance. The 3% mixture was added to the polymerization mixture of caprolactam and subjected to a polyol density. In its course, the basic prepolycondenation of the modifier reacts with the appropriate caprolactam monomer moiety on a polyether amide incorporated in the polymer. Example 9 Similar to Example 2, a larger scale sampler was prepared. A mixture of 2400 g of α-, ω-diamino polyglycol, 250 g of adipic acid, 5 g of triphenyl phosphite was polycondensed at 254 ° C under nitrogen and 1.5 hours in vacuo. 1000 g of caprolactam was added to the mixture after partial cooling to 100 ° C. The mixture was used with a PAD modifier with good results. EXAMPLE 215439 Pre-polycondensate mixtures of 2400 g of α-, ω-diamino-polyethylene glycol, 250 g of adipic acid and 6 g of triphenyl phosphite were used as modifiers. It may be used as a modifying additive to caprolactam or other polyamide-forming monomer in addition to its composition prior to conversion of the polycondensation. Example 11 A modifier was prepared similar to Example 8 except that the addition of triphenyl phosphite was omitted from its composition. It can be used as in the previous example. Example 12 A mixture of 24 g of α-, ω-diamine derivative of polyethylene glycol by relative. mol. the weight of 1610.3.3 gdimethyl esters of terephthalic acid was polycondensated with an inert atmosphere at 250 ° C for 2.5 hours in a normal atmosphere. pressure and then 1.5 hours under vacuum. The resulting condensate was 4% of the admixture of caprolactam and was co-condensed with it. EXAMPLE 13 Similar to Example 1 was followed in the preparation of the modifier. Instead of adding triphenylphosphite, 0.05 g of trimesic acid was used. The properties of polycondensate were as described in Example 1. METHOD FOR THE PREPARATION OF POLYETERIDE ANTISTATIC MODERATORS FOR POLYMAMIDE by polycondensation in an inert atmosphere at temperatures of about 255 ° C of a mixture of diamino-polyethylene glycol with relat.mol. the weight of 600-4000, dicarboxylic acids containing 4-12 carbon atoms, or their esters and other components such as ε-caprolactam, or ε-aminocaproic acid as polyamide-forming monomers, stabilizers, branching agents of the modifier molecules, and the like in that the preparation of the modifier is effected as a two-stage polycondensation, wherein in the first stage, the polycondensate from the incomplete reaction mixture is added in the course of 6-12 hours, of the invention consisting of α-, ω-diamine derivatives of polyethylene glycol, dicarboxylic acid or its ester 1 to 1.2 equivalents to the diamino-polyethylene glycol used and up to 8% by weight of other components. for the total modifier reaction mixture and the second polycondensation stage, after completion of the reaction mixture, the diethylamine derivative of polyalkylene glycol is used, the first stage being 40-80% by weight. the total amount of the modifier, wherein the second stage of polycondensation is optionally carried out also in the presence of a modified polyamide, or a monomer thereof, or a mixture thereof. Price: 2,40 Kčs Printed by Moravské tiskařské závody, operation 12, Leninova 21, Olomouc