DEF0010582MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: December 10, 1952 Bekanirtgematiht on August 23, 1956

GERMAN PATENT OFFICE

PA TENTAN REGISTRATION

CLASS 39c GROUP 10 INTERNAT. CLASS C 08 g

F 10582 IVbI'39 c

Dr. Max Coenen, Krefeld-Uerdingen, Dr. Conrad Nagel and Dr. Wilhelm Hechelhammer, Krefeld

have been named as inventors

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk

Process for the production of a polyester amide ..

; It is known that polyester amides can be prepared from mixtures of the most varied proportions of polyester and polyamide-forming compounds, such as dicarboxylic acids, dialcohols, diamines, aminocarboxylic acids, Oxycarboxylic acids or amino alcohols, pick up and optionally diisocyanates ^ in one Production process or in stages.

It is also known to produce polyester amide-like condensation products by condensing ίο lactones of oxyalkoxyacetic acids with primary or secondary diamines and heating the glycols containing carboxamido groups with bifunctional ester-forming compounds to temperatures between 150 and 300 ⁰ until high-polymer condensation products are formed. The condensation products obtained thereafter are solid, waxy substances in the cold, which after several hours of heating in a vacuum can be spun from the melt flow into threads.

None of the polyester amides obtainable by these known processes combines all of them for one high-quality plastic required properties in itself, e.g. high temperature resistance, high tensile, kink and abrasion resistance and

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Elasticity and good processability, e.g. B. to injection molded parts, but especially to cold stretchable Films, threads, or bristles, but all but one was found Polyester amide, which stands out from all others due to the sum of its properties. the Production of this, relatively high-melting, temperature-resistant and easily stretchable, Polyester amide is the solid and elastic film, thread or bristle that can be processed Subject of the present invention.

The · inventive method consists in terephthalic acid diamide-N, N'-dicaproic acid or their functional derivatives, namely their desters with lower alcohols, in particular their Dimethyl ester, with the addition of polycondensation catalysts with ethylene glycol, the latter preferably in excess, among polyester-forming Polycondensing conditions.

In addition to the terephthalic acid diamide-N, N'-dicaproic acid, z. B. their dichloride, in particular but, as already mentioned, their diesters with lower alcohols, e.g. B. with methyl, ethyl, Propyl, butyl and amyl alcohol, as well as corresponding mixed esters, can be used. The preferably to be used terephthalic acid-N, N'-dieapronic acid dimethyl ester can, for. B. by Esterification of terephthalic acid diamide-N, N'-dicaproic acid or its dilactams with methanol with the addition of a catalyst, e.g. B. concentrated sulfuric acid, with particularly good prey and in the high purity required for the process, most advantageous) but through Alcoholysis of 2 mol by Beckmann rearrangement from cyclohexanone oxime to sulfuric acid Solution of the resulting Caprolaetam with methanol and subsequent reaction of the resulting s-aminocaproic acid methyl ester obtained with 1 mole of terephthalyl dichloride will. Finally, the dicarboxylic acid mentioned can also be mixed with glycol or its alkali salt with ethylene chlorohydrin reacted to the diglycol ester and this then, optionally with the addition of an excess Ethylene glycol, polycondensed.

A process for the preparation of such terephthalic acid diamide-N, N'-dicaproic acid ester is to here, however, are not placed under patent protection. As polycondensation catalysts are, for. B. suitable: sodium, lithium, magnesium, boron, manganese, lead, zinc oxide, calcium oxide, lead oxide, Boron oxide, sodium alcoholate, sodium carbonate, magnesium alcoholate, zinc borate or mixtures such catalysts.

The polycondensation of the starting materials is carried out in a manner known per se by heating the mixture to temperatures between about 150 and 300 ^° , preferably between about 200 and 250 ^° , with the exclusion of oxygen. If you go z. B. from the dimethyl ester of terephthalic acid diamide-N, N'-dicaproic acid, it recommends. to let the transesterification with -dem glycol initially go on at temperatures of about 190 to 200 ⁰ under normal pressure. The temperature is then increased to about 230 to 240 ° and the pressure is gradually reduced to 0.5 to 0.1 mm. It is advisable to stir the mass thoroughly while it is being heated. After a reaction time of about 3 to 6 hours, a light-colored, tough polycondensation product is obtained which has a polyamide-like break and excellent fiber-forming properties. Films, threads or bristles made from them can be cold-stretched by 300 to 500%. The product has a melting point of about 210 to 220 ° and an inherent viscosity in a 0.5% solution in cresol of about 1.1 to 1.2.

example 1

35 parts by weight of terephthalic acid diamide-N, N'-ddcapronsäuredimeithylester (melting point 165 °), 15 parts by weight of ethylene glycol and 0.2 parts by weight of yellow lead oxide are ^{heated to 190 to 200 0} , with stirring and passing over nitrogen, until the transesterification is complete. This generally takes about an hour ^Z U. Then, ^1, the reaction mixture is brought to 230 to 240 and ⁰ is applied after reaching this temperature, vacuum, which is increased gradually from 0.3 to 0.1 mm. The condensation is continued for 4 1/2 hours with stirring.

The end product is ivory in color, exhibits a polyamide break and excellent fiber properties. Thin structures made from it, such as threads, bristles, films or foils, can be cold-stretched in a ratio of 1: 4 to 1: 5. The polycondensation product has a melting point of 213 to 26 °. The relative viscosity η _{Γ of} a 0.5% solution in cresol is 1.75, corresponding to an η ₀ value of 1.12.

A mixture of dimethyl terephthalate, aminocaproic acid or caprolaetam is condensed and ethylene glycol in any order in one or two stages below those listed above Conditions, a low melting point resin is obtained.

If terephthalic acid diamide-N, N'-diacetic acid ^{dimethyl ester (mp. 158 0} ) is polycondensed with ethylene glycol under the same conditions ^ as described above, a low molecular weight, powdery product is also obtained, which ^{decomposes at temperatures above 200 0} with discoloration and no solid ones Structure results.

Example 2

40 parts by weight of TerephthalsäuredliamidrN, N'-dicapronsäurediäthylenglykolester (mp. 131 °), which z. B. from the sodium salt of terephthalic acid diamide-N, N'-dicaproic acid and ethylene chlorohydrin can be obtained, 5 parts by weight of ethylene glycol and 0.02 parts by weight of yellow lead oxide are stirred in the course of; ^{Heated from 190 to 200 0} to 230 to 240 ^{0 for} 1 hour in the absence of oxygen. When a temperature of 220 ^{0 is} reached, the reaction vessel is slowly evacuated until a pressure of 0.5 to 0.2 mm is reached. The polycondensation takes place after about 4 hours

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completed. The reaction product has approximately the same properties as that described in Example ι.

Claims (1)

PATENT CLAIM: Process for the preparation of a polyester amide, characterized in that one Terephthalic acid diainide-N ^ N'-dicaproic acid or their functional derivatives, namely their diesters with lower alcohols, preferably their dimethyl esters, with the addition of Polycondensationskatarysatoren with ethylene glycol, the latter preferably in excess, under polyester-forming conditions, polycondensed. Considered publications:
Belgian Patent No. 506816;
German patent application D 4385 IVc / 39 c (patent 869867).