DE1520367A1 - Process for the production of linear polyamides from caprolactam in the presence of alpha-amino acids - Google Patents

Description

Hitherto, mixed polyamides containing <JL-amino acids prepared with good lösliohkeitseigenschaften by copolymerization of N-Oarboxyanhydride or other derivatives such as the esters, the primary (£ -Aminooarbonsäuren with at least one hydrogen on the FLL-carbon. This (ü -Aminaeäurepolyamide however, they are unsatisfactory in the manufacture of pores and threads because they are generally poor in response to aqueous machining treatments and to most

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commonly used dyes are very resistant.

Many of -Aninosäuremischpolyaraide been made without sufficient YJasserempfindlichkeit and dyeability d _o h _e a relatively easy ".Yasserabsorption and the ability dyes hold back, reducing their technical usefulness is greatly reduced. For maximum technical usability, it is essential that a film- or fiber-forming material can be well and easily dyed with a variety of dyes. Further, in order to process the fibers or threads into woven fabrics, including finishing, weaving, etc., a certain water absorbency is required when the material is to be processed on existing systems

So far it has been assumed in the production of -amino acid mixed polyamides that it is impossible to incorporate the high polymers oC-amino acids as such. Caprolactam has already been polymerized in the presence of oC -aminocaproic acid. However, the product obtained was polyoaprolactam; there was no modification of the polymer. (X-amino acids cannot be polymerized with themselves, because they do not directly degrade to polyamides.

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hydrate, but rather have a tendency to dimerize; as a result, diketopiperazines are formed

It is known to produce linear polyamides by condensing oil amino acids, preferably not as such but rather in the form of their N-carboxylic acid anhydrides for use arrive with amino acids that have at least 5 carbon atoms in a linear chain between the amino group and the carboxyl group contain, for example a corresponding amino acid with 11 carbon atoms can be used, the proportions of the two Components are completely free.

Furthermore, a process for the production of hydrophilic superpolyamides is known in which £ O-aminocarboxylic acids with at least 4 carbon atoms between the amino and carbony groups or their lactams with hydroxides of aminocarboxylic acids with at most 3 carbon atoms between the amino and carboxyl groups are heated. eno The ( according to this process, to be used as a derivative of the amino acid) brings foreign constituents into the reaction mixture in an undesired manner.

It is also known to produce polycondensation products from lactams with more than six members in the core, in particular: -Caprolactam. These products are by heating the lactams with the addition of aminocarboxylic acids, preferably those which promote the formation of the

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Polyamide · favorable ^ obtained so can ζ · Β. By heating oraprolactam with 10 » aminoaproic acid for 5 hours between 180 ° and 320 ° 0 polycondensates can be obtained from which strings can be drawn Should be used in order to obtain condensation times for a mustache · There is no foreign body introduced into the reaction, which has an effect on the behavior of the filaments obtained from the polycondensates. In the known process, the amino acids can be used as catalysts for the dissociation of the tea-camouflaged application.The amino acids used in the known process are aminocaproic acid, aminooctanoic acid, aminoundecanoic acid, 1,12-aminostearic acid, leucine or serine.The amount of amino acids added

. can vary considerably and is advantageously 1 - 15 #. When using aminocaproic acid, more than 15 i can be »used«

The object of the invention is to create a method for the production of linear mixed polyamides with improved color and moisture absorption capacity

According to the invention, a mixture of 90-99 Gew.jC i -Oaprolaotam and 30-1 Gew.jfS Alaain in a known manner at a temperature between 100 and 250 ⁰ C,

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preferably 150 and 225 ⁰ O, polycondensed

The use of alanine in polycondensation achieves a special technical effect with regard to the dye absorption capacity and the increase in the moisture retention capacity or moisture absorption Use of the amino acids in the described known Process is not achievable. ^

The reaction mixture should contain at least 70% of the mixture of caprolaotam. Unless a large excess of oaprolaotam is used, it is not possible to use alanine as such. The reaction temperature is critical and is in the range from 100 to 250 ⁰ O, preferably in the range from 150 to 225 ⁰ C, especially if fiber-forming copolyamides are to be produced. You mixed polyamides can be conveniently prepared by the / "- Caprolaotarn and the alanine in an inert atmosphere, such as nitrogen, with"

or polymerized without the use of a polymerization catalyst · Sas alanine is only weak in the £ -0aprolaotam Löalioh, but a solution occurs as the reaction progresses · a complete solution usually takes place after 1/2 to 5 hours) then the heating continued, over polymers of high molecular

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weight to form which for the manufacture of piping and charging are desired. In general, a total reaction time of 3 to 6 hours is sufficient. It can however, times of less than 3 hours and more than 6 hours depending on the. desired final molecular weights are applied «

The production of the copolyamides according to the invention takes place practically in two stages, although the isolation of a product other than the final desired mixed polyamide is not required · In the first stage, reacts the -Caprolaotam with the alanine to form a polyamide with an average Molejfalirgewioht, the least equal to the sum of the molecular weights of the acid · and d «* Caprolaotarne is · Then in the second stage · the Heating continued, resulting in conversion of the first-stage misohypolyamides, which are not fiber-forming, into the high molecular weight fiber-forming misoh polyamide · The heating is continued at the temperatures mentioned above until the polymerization reaction occurs has progressed to a point at which the desired molecular weight in the product is obtained by conventional Oil viscosity measurements can be determined "

In the method according to the invention, the In question, the reaction at atmospheric pressure is satisfactory, but sub- or over-atmospheric

druok be used In many cases it is not necessary to 909847/1077

the hot reaction mass during at least a part, usually in the last stages of subjecting the polymerization to a reduced pressure · This allows Water and other volatile low molecular weight reaction byproducts, if any, as well as unreacted Monomers, such as excess CaprοIactarn, can be largely removed · Pressures in the range of 10 to 100 mm Hg are sufficient for this purpose · Additional a stream of inert gas can be passed through the reaction mass while it is under reduced pressure Pressure to facilitate the removal of volatile matter

The method according to the invention is preferably carried out in an inert atmosphere, since when working at high temperatures and in particular at about 200 ° C or more, the polymerizing mixture is susceptible to oxidation by air or even traces of oxygen Deterioration of the polymer, and accordingly it is essential to exclude oxygen from the reaction vessel if any coloration of the end product is harmful, such as in the production of fiber-forming copolymers other inert G _H s before initiating the reaction

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purged and the oxygen-free atmosphere is maintained by passing a continuous stream of inert gas through the reaction chamber during the polymerization. Ea can be any inert (Yes, like helium or argon, can be used, for economic reasons, Stiokatoff is preferably used

turns. Common technical stiokatoff, however, is in general not satisfactory since he has traces of

* Contains oxygen, which can interfere. The nitrogen should therefore be up to a content of not more than o, oo5 i "oxygen cleaned.

After completion of the polymerization, the mixed polyamide formed can be drawn into threads immediately, or it can be cooled down and on some twofold Greetings to be ground for storage · The geschftoLient polymer can be cooled by quenching in water and the resulting product to the desired size

. grind and dry

The mixed polyamides produced according to the process of the invention have repeating structural units, dl · by the formula below can be shown!

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in which x and y are the average number of such groups mean in the polymer chain. Generally includes the group χ, which is derived from the oaprolactam, " 7o to 99 wt. # Of the polymeric molecule and the group y, which is derived from alanine, 1 to 3o wt. ',' Of the polymeric Molecule.

The mixed polyamides according to the invention can according to the conventional solution or smelting spinning process continuous threads are processed from which, if necessary Staple fibers can be produced.

Threads obtained from the isohpolyamides produced by a method according to the invention have the ability to assume a very high degree of permanent orientation under tensile stress. The threads can be stretched or cold-drawn at once by applying a moderate pull with ordinary repair work. They can be cold drawn to a multiple of their original length. This Kaltaiehvorgänge can be performed (with threads which have been completely brought to the * cooling and solidifying, or cold drawing may be followed as part of a continuous process immediately the formation of the load. Bs can thereby by any means known for this purpose devices and cold drawing process

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can be used, for example using vehicles with different speeds, of different speeds Temperatures and under LIitver..sung v / poor or hot water or steam.

The invention is explained below using an exemplary embodiment explained in more detail.

example

A mixture of 1 part of dl-oC-alanine and 9 parts of £ ~ Oaprolactati was heated at 222 ° C with introduction of nitrogen. The dl-ßl-alanine dissolved in 1 hour. The mixture was heated for a further 5 hours at 222 ⁰ G, was obtained whereupon a polymer had a melt viscosity of dc.s 2oo Poisen. After the melt had cooled, a light yellow crystalline polymer was obtained which had a melting point of 180 ° C. Soft, pliable threads were obtained from the melt by pulling it with a glass rod.

The products produced in accordance with the invention can be used in the manufacture of tapes and threads Used in the textile sector, e.g. for the production of knitted and woven textiles and pile products will. The products have both improved coloring properties

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as well as an increased moisture absorption capacity and an increased ability to retain moisture. The latter property is particularly important in clothing are desirable, in which, in general, the comfort in wearing the garment is closely related to the moisture absorbency. Also have threads and Fibers from the LIi a ohpo Iy amid β η according to the invention are generated, compared to an increased absorption capacity Wool dyes, which is very beneficial when mixed with wool fibers. After all, the fibers did and filaments also have improved tensile strength and elongation properties and are therefore more pliable.

Mixed polyamides produced according to the process of the invention are also used to produce Suitable for films or foils. Solutions can be drawn through an elongated slot into an ICoagulierbad that contains a Contains non-solvents for the mixed polyamide will. Duron appropriate choice of the size and shape of the opening through which the polymer is expelled rods, sheets, plates, ribbons, and other shaped articles can be made.

The polymers or mixed polyamides, which according to the Invention can be obtained »under heat and baw. or pressure deformed or otherwise in certain

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Be brought into shape. For example, the polymer can be exposed to thin webs or sheets that are useful as wrapping material. Products of irregular shape can be cast in suitable shapes or pressed. The mixed polyamides that are obtainable according to the invention are also used for the production of Suitable for coating compounds or lacquers.

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Claims (1)

DM. E. WIEGAND '· MONKS DIPL-ING. W. NIEMANN HAMBURG PATENT ANWXLTE JB Monks 15, ²⁶ February 1964 NUSSBAUMSTRASSE 11 W < 11 490/63 7 / Bn G 12-791 IVb / 39c Tr.A. Claim Process for the production of linear polyamides from oaprolactam in the presence of ^ -amino acids, characterized in that a mixture of 70-99 wt. ^ C -oaprolactam and 30-1 wt. $ Alanine in a manner known per se at a temperature between 100 and 25O ⁰ O, preferably 150 and 225 ⁰ O, is polycondensed. $ 01847/1077 ORtQiNAL