DE926758C - Process for the preparation of condensation polymers - Google Patents

Description

Process for the production of condensation polymers It has been found that the structure is new, technically versatile, branched or networked Condensation polymers are obtained when one leads to the formation of linear polycondensation products capable amino and / or oxy or. Mercaptocarboxylic acids or their functional ones Derivatives, such as esters, amides, lactams, lactones, nitriles, optionally in a temporary manner Presence of water and / or in the presence of inert solvents with relatively small amounts of resinous polycarboxylic acids, especially polyvinyl carboxylic acids, or their functional derivatives, on their own or in the presence of water for amide or ester formation with the bifunctional acids or acid derivatives mentioned are capable of being heated to reaction temperature until the desired degree of polycondensation achieved or implementation has come to an end.

Free aminocarboxylic acids or their polymerizable ones are preferably used Lactams on the one hand and oxycarboxylic acids or their polymerizable lactones or Mercaptocarboxylic acids on the other hand. Aminocarboxonitriles, oxy- and mercaptocarboxonitriles usually require the presence of water. In the case of the esters, one can also do so in the absence of water in the presence of transesterification catalysts, e.g. B. Alkali alcoholates, for Goal come. Working in the presence of water generally sets the use of pressure in the first stage of the reaction, at least as far as it is concerned Esters or nitriles. That required for the cleavage of nitriles or esters Water can also consist entirely or partially of substances that form water in the heat, such as Amino acids or oxy acids, arise in the reaction mixture. Functional derivatives of the resinous polycarboxylic acids, if necessary in the presence of water or water-supplying substances with amino, oxy or mercapto groups in reaction occur, contain z. B. anhydride, ester, amide or nitrile groups.

Polycarboxylic acids or polycarboxylic acid compounds necessary for the process The invention come into consideration, for example, the following: Polyvinylcarboxylic acids, such as polyacrylic acid, polyfumaric acid, polyitaconic acid, copolymers of acrylic acid, Crotonic acid, maleic acid, maleic acid half esters and other relatively indifferent ones Vinyl compounds such as styrene, acrylic acid dimethylamide, vinyl butyl ether, vinyl sulfonamide, Copolymers of maleic anhydride and vinyl compounds, such as. B. styrene, Polyacrylic acid amides, e.g. B. Polyacrylsäuremonomethylamid, addition products of Maleic anhydride on rubber, copolymers of acrylic acid amide and acrylic acid methyl ester, novolaks and resols reacted with halogen fatty acids such as 5-bromovaleric acid.

For condensation with these polycarboxylic acids or polycarboxylic acid derivatives For example, the following aminocarboxylic acids, oxycarboxylic acids or mercaptocarboxylic acids are suitable or their amide-forming derivatives: Firstly, aminocarboxylic acids and derivatives with at least five carbon atoms between the amino and carboxyl groups: s-aminocaproic acid, e-aminocaproic acid methyl ester, e-caprolactam, N-formyl-e-aminocaproic acid, y-methyl-e-aminocaproic acid, N-Cax'bomethoxy-e-aminocaproic acid, N, N'-carbonyl-bis- [e-aminocaproic acid], 7-aminheptanoic acid and its lactams, 9-aminononanoic acid, 9-aminononanoic acid nitrile, ii-aminoundecanoic acid, i2-aminostearic acid, co - aminohexylthioundecanoic acid; -secondly, oxycarboxylic acids with at least q. C atoms between hydroxyl and carboxyl group: 7-oxyheptanoic acid, io-oxydecanoic acid, i-oxyundecanoic acid, i2-oxystearic acid, ricinoleic acid, α-valerolactone, e-caprolactone; thirdly, mercaptocarboxylic acids: 7 - mercaptoheptanoic acid, i i-mercaptoundecanoic acid, i i-mercaptoundecanoic acid amide.

In addition, accelerating or the Polycondensation regulating substances should be present, e.g. B. acidic substances such as hydrogen chloride, Phosphoric acid, zinc chloride, alkaline transesterification catalysts, such as alkali alcoholates the oxycarboxylic acid ester, or monofunctional end-group-forming substances, e.g. B. Amines, such as N-butylamine, dicyclohexylamine, 6-pyrrolidinohexylamine-i, monohydric Alcohols such as dodecyl alcohol and dihydroabietinol. Also small to moderate amounts in diaruins and dicarboxylic acids, the latter is expedient. in excess, can be present. The additional use of diamines of the 6-pyrrolidinohexylamine-i is of particular importance because with such polyvalent amines the loss in color affinity, which occurs through the acylation of the terminal amino groups, can be balanced again.

Most uniform, i.e. H. only under lateral branching and without crosslinking, the reaction with resinous polycarboxylic acids proceeds if one only aminocarboxylic acids and their functional derivatives (lactams, formyl compounds, Urethanes, esters, nitriles) and / or oxycarboxylic acids or polymerizable lactones used by such. It is surprising, however, that small amounts of diamines are also used and dicarboxylic acids or glycols and dicarboxylic acids in the reaction mixture; for modification the process products can incorporate without extensive, the deformation mechanically exclusive networking occurs, especially if one is in favor of it ensures that there is no excess diamine present. On the other hand, you can go through carefully dosed excesses of diamine adjust the degree of crosslinking as required, if necessary, z. B. by excesses in amounts of 1 / 2oo to 12o mol, based on the dicarboxylic acid.

As a rule, the networking should only be carried out so far that the polymers formed still remain thermoplastically deformable. This area is particularly easily exceeded if networking starts too early. The presence water has an inhibiting effect in this regard. So it is when using for Formation of intermediate bridges capable substances expedient, these only later and gradually incorporated into the reaction mixture and / or initially in the presence to condense of water. One can advantageously proceed in such a way that one first Stage produces a relatively low molecular weight condensation product, this then with the substances causing the networking, which of course are also more polyfunctional Can be nature, mixed and now post-condensed. In this case, too, it can It may be expedient to add any excess diamine used only at the end.

Acylated polyamino compounds have been used to regulate the degree of crosslinking proved to be particularly useful, probably because the acyl groups facilitate the incorporation is delayed. Suitable are e.g. B. diformylated diamines, such as N, N'-diformylhexamethylenediamine, N, N'-Diformyl-tetramethylene - bis - [y - aminopropyl ether], urethane compounds, such as hexamethylene bis [isopropyl carbamate], polyvalent urea compounds, especially those with terminally strongly negatively substituted amide groups, such as Hexamethylene-bis- [o), «) '* - diphenylurea], reaction products from one mole of one Diisocyanate and 2 moles of a lactam, e.g. B. α-pyrrolidone. Neutral connections of this type are also very suitable for post-condensing little or not branched, previously isolated precondensates. Are especially beneficial for this purpose long-chain compounds with functional groups of the aforementioned type, e.g. B. linear polymers Compounds of diformylated diamines and dicarboxylic acids or diurethanes and Dicarboxylic acids. Also linear polymeric polycondensation products with free amino end groups are well suited. When such polycondensates are used, the reaction becomes the last The stage is expediently carried out in the absence of water in order to prevent the splitting of the to keep added crosslinking agent as far as possible.

Particularly interesting substances emerge, if at least partially bifunctional compounds are condensed in, the basic tertiary nitrogen contained in the molecule, in particular oxy-, amino- and mercaptocarboxylic acids, their Chain one or more times through an N R group (R is preferably a monovalent unsubstituted hydrocarbon radical) is interrupted. Substances of this type are z. B. the following: N-ethyl-N-y-oxypropyl-aminoundecanoic acid (from (v-bromundecanoic acid methyl ester by reacting with ethylamine, allowing 3-bromopropanol-i to act on the free Amino compound and saponification), V - methyl - N- «o -oxyamylaminocaproic acid (from 8-oxyvaleraldehyde and methyl N-methyl-aminocaproate by joint reduction on Raney nickel and saponification); N-methyl-N-aminopropylaminocaproic acid (available by adding acrylonitrile to e-caprolactam in the presence of alkali, reduction to the 1 \ T-aminopropyl-e-caprolactam, splitting to the amino acid and alkylation with Dimethyl sulfate after formylation of the terminal amino nitrogen); i i -piperazine undecanoic acid (from i-bromundecanoic acid nitrile and excess piperazine with subsequent saponification).

The condensation is carried out in the usual manner. In most cases it is advisable to start with for a while, preferably until it is stopped of equilibrium to work under pressure at temperatures between about i8o and 250 ° - and then the reaction under atmospheric pressure or reduced pressure to end. The reaction can also be carried out in a flow process, namely if the starting materials are predominantly low-melting substances, such as lactams, oxycarboxylic acids or lactones can be used. If polyesters are formed, it is recommended that to greatly reduce the pressure towards the end of the implementation (to about 10 to 1 mm) and to provide as large a surface as possible, e.g. By stirring or flowing the melt over hot surfaces in the absence of oxygen for removal to facilitate the volatile by-products. Can accelerate implementation the released water is also chemically carried out by passing carbon oxysulfide over it decompose.

The equivalent ratio between polycarboxylic acids or polycarboxylic acid derivatives and aminocarboxylic acids, oxycarboxylic acids or mercaptocarboxylic acids or their derivatives can vary within considerable limits depending on the intended use. Do you want z. B. Polymers for processing on fibers or films or others shaped structures in which a relatively high mechanical strength is required is to produce, the proportion of polycarboxylic acid is expediently about 1 / 2oo up to 1/10 equivalent, based on amino, hydroxyl or sulfhydryl groups. Let it be z. B. polyamides from 5o moles of e-caprolactam or g-aminonanoic acid and one equivalent Polyacrylic acid can be orientated quite well according to the usual melt spinning process Process threads, although one should have expected the multiple branching would abolish spinnability or at least significantly impede it.

If one starts from very high polymer polycarboxylic acids, difficulties in the homogenization can arise if the reaction is not initiated in the presence of a relatively large amount of water. It is best to use medium-high polymer materials, especially since the extremely high polymer materials suffer from degradation due to scratching anyway at the required condensation temperatures. With increasing amounts. Polycarboxylic acid gives brittle structures with a higher acid number and increasing swellability or solubility in aqueous alcohol, especially in the presence of alkaline agents such as ammonia or alkali hydroxide. These solutions gel in the cold. Solubility and swellability are particularly promoted if different aminocarboxylic acids and / or oxycarboxylic acids or mercaptocarboxylic acids are used or compounds are used that are interrupted in the chain by hetero groups such as O, S, S 02 NH, S 02 NR, or finally those which are substituted by alkyl side chains. Particularly favorable solubility properties result from the use, if appropriate, of a proportion of bifunctional substances with tertiary amino groups. The proportion of tertiary nitrogen is expediently dimensioned so that the uncrosslinked polyamides in warm, aqueous, z. B. two to three times normal acetic acid are still soluble. Such solutions gel when they cool to form gelatine-like gels which, with a sufficient degree of polycondensation, can have high gel strength and elasticity. The gel melting points of these jellies can, depending on the constitutional hydrophilicity of the polyamides, in particular on the average number of basic nitrogen atoms in the molecule, be significantly higher than in the case of gelatin, e.g. B. between 30 and 85 °, based on about 100% solutions in 2-n-acetic acid.

The polymers made by the process of the invention contain as end groups predominantly or exclusively carboxyl groups. In proportion to that the dyeing behavior of the process products corresponds to a high alkali binding capacity. The affinity for dyes with acidic groups is opposite to analog Polyamides without condensed polycarboxylic acid are reduced, while the basic ones Dyes are absorbed more strongly. The same applies to dyes or dye components, whose uptake requires a certain degree of swelling in an alkaline medium, e.g. B. naphthols or indanthrenes. When dyeing the polyamide compounds according to the invention with acidic Dyes can be removed by adding strong acids, e.g. B. sulfuric acid, to the dye liquor a compensation can be brought about.

The presence of several carboxyl groups in the molecule enables valuable ones Finishing effects, e.g. B. subsequent crosslinking with responsive to carboxyl groups polyvalent compounds, such as polyvalent isocyanates, mustard oils, 1, 2 - alkyleneimine compounds, Carbodiimides, carbamic acid chlorides, alkylene oxides, epihalohydrins. Particularly In this regard, the alcohol-soluble mixed polyamides, which are valuable. Condensation of the polycarboxylic acid with mixtures of polyamide-forming aminocarboxylic acids different molecular weight can be obtained, e.g. B. from mixtures of s-aminocarboxylic acids or their lactam and i2-aminostearic acid.

High molecular weight products with a particularly high alkali binding capacity are created, if you use relatively large amounts of polycarboxylic acid, some of the carboxyl groups but by an indifferent, non-volatile base, e.g. B. lithium hydroxide or sodium hydroxide, neutralized or if one of amino carboxylic acids or their lactams and polymers Esters or ester acids runs out and the remaining ester groups by aftertreatment the polyamides with alkalis, e.g. B. in methanol-water solution 85:15, saponified. Particularly are suitable in this case polyearboxylic acid esters of secondary alcohols, for. B. Isopropyl polyacrylate or copolymers of those which still contain free carboxyl groups.

EXAMPLE I 150 mol of medium viscosity polyacrylic acid are dissolved in ten times the amount of water and mixed with 1 mol of E-caprolactam. The mixture is first heated to 220 ° for 4 hours in a closed vessel, then, after the pressure has been released, post-condensed for a further 3 hours at 240 °, avoiding the ingress of oxygen. The colorless, very tough polyamide obtained melts without decomposition at 207 to 208 ° and can be spun from the highly viscous melt into solid threads which can be stretched by three times their length. The polyamide shows a relative viscosity of 2.0 g in 0.5% cresol solution; There are characteristic differences compared to a similar polyamide which was produced without polyacrylic acid. While in normal unbranched polyamide the specific viscosity in 85% formic acid is constant at a lower concentration regardless of the concentration, such an area is completely absent in the case of the branched products. Differences can also be seen in appearance. The structures made from the branched polyamide are glossier and more transparent. Relatively strong structures such as bristles are characterized by a particularly high resistance to buckling, without the stiffness being reduced.

Example e 1/5 mol of medium viscosity polyacrylic acid is condensed in three times the amount of water with 1 mole of e-caprolactam among those given in Example i Conditions. The result is a relatively brittle product that differs from that prepared according to example i also by solubility in warm alcoholic Lye differs. This product can be easily removed by heating with diisocyanates transform into an insoluble and infusible polyamide. Instead of the diisocyanates you can also use shipping bases, z. B. the reaction product of 2 moles Use salicylaldehyde and 1 mole of hexaethylene diamine. Networking can too in connection with a deformation. Example 3 2 mol of i2-aminostearic acid are condensed, 3 moles of e-caprolactam and 1/10 mole of polyacrylic acid in the presence of water at Zoo up to 2i0 ° without pressure. The polyamide obtained dissolves in hot alcohol and can processed from alcoholic solution onto foils. They are called alcoholic Solutions solidify to form a stiff jelly on cooling. The melting point of the Polyamide is at i55 °. In addition to its excellent mechanical properties, the polyamide is also characterized by its high water resistance. It is also suitable for ' Deformation on leather-like products. Example 1 mole of f-caprolactam and 1 / 5o mole Medium-viscosity polyacrylic acid are initially mixed with 100% water, based on lactam 4 hours under pressure to 220 °, then heated to 2q.00 'for 3 hours without pressure. The polyamide obtained in this way melts at 204 to 2o60 'and has a relative Viscosity of 1.72. The alkali binding capacity became 0.013, the acid binding capacity found to be 0.0014. Example s i mole of e-caprolactam is mixed with 1/25 mole of methyl polyacrylate and 10 ° / o of water heated first for 4 hours to 220 °, then for 6 hours to 2 ° 0 °. That The resulting polyamide melts at 2o5 to 2o6 'and can be stretched from the melt Spin threads. The relative viscosity is 1.5.

Example 6 8 moles of caprolactam and 2 moles of i: 2-amill, ostearic acid are with 1/25 mol of polyacrylic acid, the amount of the latter based on i gram atom Nitrogen in the mixture of the starting materials, with the addition of 10 1 / o water 4 Hours on 22o0 under pressure and then for a further 3 hours in a stream of nitrogen heated to 2q.0 ° under atmospheric pressure. A translucent, at 174 is obtained Up to 175 "'melting polyamide, which dissolves in 85% alcohol in the heat. The hot 150% solution gelatinizes in the cold.

The polyamide can be spun from the melt into stretchable threads, that have a strong tendency to curl. Without the addition of polyacrylic acid, the melting point is at 18o to r81 °.

If the ratio of lactam to amino acid 8: 1 is chosen, the result is an opaque polyamide with a melting point of igo to 1g1 °, which is found in alcohol only is soluble to a small extent. The polyamide can be easily extracted from the melt well spun into firm, stretchable threads.

Claims (5)

PATENT CLAIMS: 1. Process for the preparation of condensation polymers with amide and / or ester bonds, characterized in that one for the formation linear polycondensation products capable of amino and / or oxy or. Mercaptocarboxylic acids or their functional derivatives, such as esters, amides, lactams, lactones, nitriles, if appropriate in the temporary presence of water and / or in the presence of inert solvents with relatively small amounts of resinous polycarboxylic acids, in particular Polyvinylcarboxylic acids, or their functional derivatives, which by themselves or in Presence of water for amide or ester formation with the mentioned bifunctional Acids or their functional derivatives are capable of operating at elevated temperature converts to polymeric products and these polymeric products possibly also with bifunctional compounds capable of reacting with carboxyl groups, such as isecyanaites " Alky lenimines, alkylene oxides, aftertreated. 2. The method according to claim 1, characterized characterized in that amines which form end groups, especially in the case of amidation, are monofunctional effective, polyvalent amines of the 6-pyrrolidinohexylamine-r type, added will. 3. The method according to claim 1 and 2, characterized in that low Amounts of diamines or glycols and dicarboxylic acids are added to the reaction mixture will. . 4. The method according to claim i to 3, characterized in that in place of diamines whose derivatives acylated by carboxyl compounds are used. 5. The method according to claim 1 to q., Characterized in that such bifunctional Starting materials are used, the at least partially basic tertiary nitrogen contained in the molecule.