DE897625C - Process for the production of high molecular weight polycondensation products - Google Patents

Description

Process for the production of high molecular weight polycondensation products. B. co, co'-diamines and «), co'-dicarboxylic acids and combinations which, in addition to diamines or dicarboxylic acids, are functional derivatives of dicarboxylic acids or diamines, such as esters, amides, nitriles, formyl compounds, capable of polyamide formation in the presence of supplementary components , Urethanes, diamine salts of volatile acids, e.g. B, carbonic acid and formic acid, diisoeyanates and substances that form in the heat, furthermore (o-aminocarboxylic acids and their polyamide-containing functional derivatives, such as formyl compounds, urethanes, esters, amides, nitriles, lactams, and combinations of glycols and diisocyanates or such If the correct proportions are chosen, the substances emitting generally readily and quickly deliver high-polymer products, there are considerable difficulties in obtaining high-polymer polyesters, especially stringy polyesters, so-called super polyesters, by simple condensation (cf. G. V. Schulz, Zeitschrift für physicalische Chemie, 1938 [A] Vol. 18? "S.I27).

It has now been found that it can be carried out in a relatively easy manner to high-polymer linear polycondensation products that also contain amide groups, if you first of all use components suitable for polyester formation, e.g. B. oxycarboxylic acids, equimolecular mixtures of glycols and dicarboxylic acids, a) amino alcohols and dicarboxylic acids, to moderately high polymer substances precondensed and then these substances after the addition of a appropriate amount of a diisocyanate or a diisocyanate that splits off in the heat The material is heated until the desired degree of polymerisation is reached. The addition of the diisocyanate can be used all at once or, in most cases more expediently, be done gradually, e.g. B. by introducing diisocyanate vapor into the liquid Reaction mixture, optionally under pressure.

The use of solvents for the polyesters is common here advantageous, since the reaction then takes place under particularly mild and uniform conditions can be carried out. It is not necessary that the method of the invention takes place immediately after the primary condensation. Rather, the post-condensation can optionally up to the super polymeric state at any later point in time and can be carried out at any point. For example, the post-condensation in connection with a deformation process on z. B. fibers, films or three-dimensional Shaped bodies are made. You can z. B. the prepolymer with the required Melt together the amount of diisocyanate and this has not yet condensed out Mixture until processing on z. B. Injection molded articles -storage, or you can use hard, precondensed, powdered plastics with a powdery reactant, z. B. hexamethylene bis-carbamic acid di-p-chlorophenyl ester or hexamethylene bis-2-oxydiphenylcarbamic acid ester (from the chloroformic acid ester of phenol with hexamethylene diamine or from hexamethylene diisocyanate and the corresponding phenol) -, mix and store the dry or dry one Heat mixture to reaction temperature during processing.

The process of the invention is not limited to starting materials of uniform structure. Equally useful are mixed products, in addition to appropriate for polyester formation materials still Beirn heating under - polyamide formation reactive components such. B. aminocarboxylic acids, combinations of diamines and dicarboxylic acids, incorporated or disintegrate into such substances during hydrolysis, among other things.

Products of this type are e.g. B. the condensation products of any mixtures of e-aminocaproic acid and its lactam and ii-oxyundecausal acid, the condensation product of 1 mole of hexamethylene diamine, 2 moles of adipic acid and 1 mole of tetramethylene glycol, the mixed condensate of 1 mole of sebacic acid, oß moles of tetramethylene diamine and 0.2 moles of decamethylene glycol and the copolymer of 1 mole of adipic acid, 0.5 moles of a), co'-dioxydibutyl ether, 0.5 moles of hexamethylenediarrün. Includes products that contain components with basic nitrogen atoms, e.g. B. polyamides, N-methyl diethanolamine or N - Di -a), o.) '- diaminodibutyl - N-methylamine (from ö-bromobutylbenzamide and methylamine) as a component.

The process products can be made up like the known high polymers Polyester and polyester amides with a sufficiently high degree of polymerisation on fibers, Process foils and three-dimensional moldings. They are particularly suitable for the production of pliable films and coatings on flat structures, e.g. B. Papers and fabrics. Also as textile auxiliaries, e.g. B. as a sizing agent some of the products obtainable by the process are valuable.

For the production of fibers and flat structures, coatings and the like, the process products cannot usually be processed from the melt flow, but in many cases also from solutions, e.g. B. in esters, halogenated hydrocarbons, their mixtures with alcohols. Some are also soluble in saturated or unsaturated alcohols and araliphatic alcohols and even in alcohol-water mixtures, especially if the starting materials in the chain are interrupted by amide, ether or sulfonamide groups. The presence of residues of relatively short chain amino acids, e.g. B. the aminocaproic acid, particularly favors the solubility. Example ii moles of aminonanoic acid, 1 mole of adipic acid, 1 mole of decamethylene glycol are heated to 225 ° for 4 hours under nitrogen in an autoclave. The water formed is then carefully blown off and heated, further in vacuo to 23 ° for 4 hours. The waxy product, which solidifies when it cools, shows only very little thread-pulling power. When the composition is fused with 1/1 mole of octamethylene diisocyanate to 1 mole of bifunctional starting material in the original mixture at 2oo ', a high polymer product is obtained which can be drawn out from the melt to form stretchable threads. Example 2 1 mole of adipic acid and 1 mole of 3-aminopropanol are heated in the autoclave Rising from 150 'to 200' in 4 hours and now obtained at this temperature for 1 hour. The water formed is then allowed to escape and, after its removal, heated to 220 'for 3 hours. 0 mole of hexamethylene diisocyanate is then introduced into the melt in vapor form and heating continued for an hour at 2oo '. The product obtained can be processed onto threads and foils. EXAMPLE 3 A polyurethane made from 1 mole of 1,4-butylene glycol and 0.95 mole of hexamethylene diisocyanate is added in a completely dry state 4.5 MOI octamethylene diisocyanate is mixed and heated in a melt flow for 1 hour.You can also mix the product with an equivalent amount of diphenyl-4,4-diiso Mix the cyanate, melt the mass together and then shape it. Since the substance has a low viscosity at the beginning, the mixture is very easy to process.

The correct dosage of the additional amount is for a given and approximate the same starting material can easily be determined empirically. But you can also the reactive end groups by determining the hydroxyl number and the Record the acid number quantitatively and the equivalent values of the calculation based on the additional amount. Particularly simple and clear relationships arise when the two end groups consist of carboxyl groups. It will therefore preferred starting materials are those products which have an excess are made of carboxyl component. In principle, however, you can also use products work, which preferably have terminal hydroxyl groups. This is special then advantageous if the formation of gaseous by-products (carbonic acid) is avoided should be, z. B. during post-condensation in connection with a sensitive deformation process, like a spinning vanguard.

For example, the following diisocyanates are suitable for the process: tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene, m-phenylene, p-phenylene diisocyanate , 4,4'-diphenyl diisocyanate, diisocyanates from y, y'-diaminodipropyl ether, y, y'-Diaminodipropyl sulfide, aryl carbamate from diamines such as hexamethylenediamine, benzidine, di- (δ-aminobutyl) -methylamine, the aryl tricarbamate from di- (b-aminobutyl) amine.

Claims (1)

PATENT CLAIM: Process for the production of high molecular weight polycondensation products, characterized in that moderately high polymer polyesters which also already have amide groups may contain, in the presence or absence of solvents with Diisoeyanaten or with substances which form diisocyanates at elevated temperatures.