MXPA00007730A - Method for producing polymer mixtures comprised of amino nitriles and thermoplastic polymers - Google Patents

Abstract

The invention relates to a method for producing polymer mixtures by reacting at least one amino nitrile with water in the presence of thermoplastic polymers and optional additional monomers which form polyamide. The inventive method comprises the following steps:(1) reacting at least one amino nitrile with water at a temperature ranging from 90 to 400°C and under a pressure ranging from 0.1 to 35 x 106 Pa, whereby a reaction mixture is obtained;(2) additional reaction of the reaction mixture at a temperature ranging from 150 to 400°C and under a pressure which is lower than the pressure in step 1, whereby the temperature and pressure are selected in such a way that a first gas phase and a first liquid or a first solid phase or a mixture comprised of the first solid and first liquid phases are obtained, and the first gas phase is separated off from the first liquid or the first solid phase or from the mixture comprised of the first liquid and first solid phases;and (3) mixing the first liquid or the first solid phase or the mixture comprised of the first liquid and first solid phases with a gaseous or liquid phase which contains water and which can contain thermoplastic polymers and optional additional monomers which form polyamide. Said mixing occurs at a temperature ranging from 150 to 370°C and under a pressure ranging from 0.1 to 30 x 106 Pa, whereby the polymer mixture is obtained and whereby the thermoplastic polymers and optional additional monomers which form polyamide are added in one or more of the steps.

Description

PROCEDURE FOR THE PREPARATION OF MIXTURES OF POLYMERS FROM AMINONITRILS AND THERMOPLASTIC POLYMERS The present invention relates to a novel process for the preparation of polymer mixtures in which aminonitriles are transformed in the presence of water, thermoplastic polyamides and optionally other monomers forming polyamides. The homogeneously prepared synthetic materials have disadvantages that limit the possibilities of use. By means of polymer blends, the different properties of the parts of the mixture can be combined and thus the profiles of the properties of the plastics can be improved. For this reason, for example, mixtures of polyamides with amorphous plastic materials such as polyaplene ether sulfones or polyetherimides are prepared. The polyamides can be prepared in different ways in this way. Among the most important methods for the preparation of polyamides is the hydrolytic polymerization with ring opening of the lactams. A variant of this process, which can also be carried out on an industrial scale, is described, for example, in DE-A 43 21 683. The preparation of polyamides from aminonitriles presents an alternative preparation route and makes possible the use of other raw Materials. This is described in the unpublished DE-A 197 09 390, oldest priority, continuous discontinuous procedures for the preparation of polyamides from aminonitriles and water at increased temperature and increased pressure. To prepare mixtures containing polyamide, e-caprolactam is polymerized, inter alia, in the presence of polyarylene ether sulfone, according to U.S. Patent No. 3,729,527. In DE-A 41 02 996 it is also proposed to polymerize lactams in the presence of amorphous polymers such as polysulfones, polyphenylene ethers, polyetherimides, polyamideimides or styrene copolymers, to prepare polymer alloys. The polymerization is initiated by means of strong bases. If the polymeric components of the mixtures are mixed in the melt, for example, in an extruder, they are added in general means that provide tolerance. In accordance with EP-A 0 374 988, McGrath et al., Polym. Prepr. 14, 1032 (1973) or Corning et al., Makromol. Chem. Macromol. Symp. 75, 15-9 (1993) are suitable as means for granting tolerance to copolymers of segments of polyamide and polyarylene ether sulfones, which can be prepared by dissolving the polyarylene ether sulfone in a lactam melt and the lactam being polymerized in the presence of a strong base with exclusion of water.

Studies on anionic polymerization of lactams in the presence of polyetherimides or polysulfones in an extruder have also been examined, e.g. , by Van Buskirk et al., Polym. Prepr. 29 (1), 557 (1988). All the processes mentioned above use lactams or polyamides, prepared from lactams, for the preparation of mixtures of polyamides and thermoplastic polymers. The mentioned processes have the disadvantage that the polymer chains of the thermoplastic polymers are degraded by the attack of the anions present in the reaction mixture. In addition, the anionic polymerization requires special technical measures for the control of the degree of polymerization, since the reaction develops in general very fast and in a very short time there is a strong increase in viscosity. Consequently, only products of defined structure can be obtained, that is to say of chain length and / or defined viscosity with difficulty, if it is achieved. In addition, the products contain catalyst residues and degradation products or byproducts, which frequently can not be eliminated. If the polymerization is carried out in an extruder, often a complete transformation can not be achieved, and the final product still contains residual monomers. In addition, usually only dark products are obtained, eg. , brown.

Schnablegger et al., Act Polym. 46, 307 (1995), describe the transformation of e-caprolactam with polyarylene ether sulfones, which contain terminal groups to inophenyl. The amino groups react there with the e-caprslactam with ring opening and thus initiate the polymerization reaction. The reaction is carried out in the absence of water, and phosphoric acid can be used as a catalyst. The disadvantage of this process is that the polyarylene ether sulfones with two aminophenyl end groups per polymer chain can only be prepared in pure form at high cost. The object of the present invention was to provide an improved process for the preparation of compositions based on different thermoplastic synthetic materials and polyamides (polymer blends), which does not have the disadvantages of the known processes. The object is achieved according to the invention by means of a preferably continuous process for the preparation of a polyamide by transformation of at least one aminonitrile with water in the presence of thermoplastic polymers and optionally other monomers forming polyamides, comprising the following steps (1) Transformation of at least one aminonitrile with water at a temperature of 90 to 400 ° C and a pressure of 0.1 to 35 x 10e Pa, preferably in the presence of a Brdnsted acid catalyst, selected from a catalyst of beta-zeolite, layered silicate or titanium dioxide of 70 to 100% by weight of anatase and 0 to 30% by weight of rutile, in which up to 40% by weight of titanium dioxide can be replaced by tungsten oxide, obtaining a reaction mixture, (2) further transformation of the reaction mixture at a temperature of 150 to 400 ° C and a pressure that is lower than the pressure of Step 1, which can be Presence of a Bronsted acid catalyst, chosen from a catalyst of beta-zeolite, layered silicate or titanium dioxide of 70 to 100% by weight of anatase and 0 to 30% by weight of rutile, in which up to 40% can be replaced % by weight of the titanium dioxide by tungsten oxide, the temperature and pressure being chosen in such a way that a first gas phase and a first liquid phase or a first solid phase or a mixture of a first solid phase and a first solid phase can be obtained. liquid phase, and the first gas phase is separated from the first liquid phase or the first solid phase or from the mixture of the first liquid phase and the first solid phase, and (3) mixture of the first liquid phase or the first solid phase or the mixture of a first liquid phase and a first solid phase with a liquid phase containing water and which may contain the aforementioned catalyst, at a temperature of 150 to 370 ° C, and at a pressure of 0.1 at 30 x 106 Pa, The polymer mixture is obtained by adding the thermoplastic polymers and optionally other polyamide-forming monomers in one or more steps. Preferably the aforementioned process further comprises the following step: (4) Subsequent condensation of the polymer mixture at a temperature of 200 to 350 ° C and a pressure that is lower than the pressure of step 3, the temperature and pressure being chosen such that a second gaseous phase containing water and ammonia and a second liquid phase or a second solid phase or a mixture of a second liquid phase and a second solid phase / containing the polymer mixture are obtained. The object is furthermore achieved by means of a preferably continuous process for the preparation of polymer mixtures by means of the transformation of at least one aminonitrile with water in the presence of thermoplastic polymers and optionally other monomers forming polyamides, comprising the following steps (1) Transformation of at least one aminonitrile with water at a temperature of 90 to 400 ° C and a pressure of 0.1 to 35 x 106 Pa, preferably in the presence of a Bronsted acid catalyst, chosen from a beta-zeolite catalyst, layered silicate or "titanium dioxide" of 70 to 100% by weight anatase and 0 to 30% by weight rutile, in which up to 40% by weight of the dioxide can be replaced titanium by tungsten oxide, obtaining a reaction mixture, (2) further transformation of the reaction mixture at a temperature of 150 to 400 ° C and a pressure that is lower than the pressure of Step 1, which can be carried out in presence of a Bronsted acid catalyst, chosen from a catalyst of beta-zeolite, layered silicate or titanium dioxide of 70 to 100% by weight of anatase and 0 to 30% by weight of rutile, in which up to 40% can be replaced % by weight of the titanium dioxide by tungsten oxide, the temperature and pressure being chosen in such a way that a first gas phase and a first liquid phase or a first solid phase or a mixture of a first solid phase and a first solid phase can be obtained. liquid phase, and the pri mere gaseous phase is separated from the first liquid phase or from the first solid phase or from the mixture of the first liquid phase and the first solid phase, and (3) subsequent condensation of the first liquid phase or the first solid phase or from mixing a first liquid phase and a first solid phase, which can be carried out in the presence of a Brdnsted acid catalyst, selected from a catalyst of beta-zeolite, layered silicate or titanium dioxide of 70 to 100% by weight of anatase and 0 to 30 wt% of rutile, in which up to 40 wt% of the titanium dioxide can be replaced by tungsten oxide, at a temperature of 200 to 350 ° C and a pressure that is lower than the step pressure 2, the temperature and pressure being chosen such that a second gaseous phase containing water and ammonia can be obtained, and a second liquid phase or a second solid phase or a mixture of a second solid phase and a second liquid phase, which contains the polymer mixture, adding the thermoplastic polymers and optionally other polyamide-forming monomers in one or several steps. According to the present invention, aminonitriles, water, thermoplastic polymers and optionally other polyamide-forming monomers are used as educts. Apart from the use of aminonitriles as polyamide educts, the invention has the advantage that the polymer blends are not generated after the preparation of the polyamides but in the course of the transformation of the aminonitriles, which makes the preparation more economical of finely dispersed mixtures with better product properties. The thermoplastic polymer is preferably added in steps 3 and / or 4. Preferably there are no other monomers.

The basic procedure for the preparation of the pure polyamide is described in the prior published patent application, unpublished, DE-A-197 09 390.

As aminonitrile, basically all aminonitriles, ie compounds having at least one amino group as well as at least one nitrile group, can be used in the mixture. Among these, the α-ammonitriles are preferred, among which the α-aminoalkyl nitriles having 4 to 12 carbon atoms, more preferably 4 to 9 carbon atoms in the alkylene radical, or an aminoalkylaryl nitrile having 8 to 13 carbon atoms may be used. C, those which have between the aromatic unit and the amino and nitrile group an alkylene group with at least one C atom being preferred. Among the aminoalkylaryl nitriles, those having the amino and nitrile group in the 1,4-position one with respect to the other. As α-aminoalkyl nitrile, preferably also α-aminoalkyl nitriles are used, the alkylene moiety (-CH 2 -) preferably containing 4 to 12 C atoms, more preferably 4 to 9 C atoms, such as 6-amino-1-cyanopentane (6-) aminocapronitrile), 7-amino-1-cyanohexane, 8-amino-1-cyanoheptane, 9-amino-1-cyanooctane, 10-amino-1-cyanononane, more preferably 6-aminocapronitrile. 6-aminocapronitrile is commonly obtained by hydration of adiponitrile by means of known processes, described for example, in DE-A 836 938, DE-A 848 654 or US 5,151,543.

Of course, mixtures of several aminonitriles or mixtures of an aminonitrile with other comonomers can also be used, such as caprolactam or the mixture which is defined in more detail below. Polyamide-forming monomers As other polyamide-forming monomers, for example, carboxylic acids such as alkanedicarboxylic acids with 6 to 12 carbon atoms, especially 6 to 10 carbon atoms, such as adipic acid, pimelic acid, suberinic acid, acid, can be used. azelaic or sebacic acid as well as terephthalic acid and isophthalic acid, diamines such as C4_12 alkyldiamine, especially with 4 to 8 carbon atoms such as hexamethyldiamine, tetramethylenediamine or octamethylenediamine, furthermore m-xylylenediamine, bis- (4-aminophenyl) methane, bis- ( 4-aminophenyl) -propane, 2, 2 or bis- (4-aminocyclohexyl) methane, bis- (4-aminophenyl) -propane-2, 2 or bis- (aminocyclohexyl) methane, as well as mixtures of dicarboxylic acids and diamines each in any combination, but in the relation to each other advantageously in an equivalent ratio as hexamethylene diammonium adipate, hexamethylene diammonium terephthalate or adipate d and tetramethylene diammonium, preferably hexamethylene diammonium adipate and hexamethylene diammonium terephthalate. Polycaprolactam and polyamides which are prepared from caprolactam, hexamethylenediamine as well as adipic acid, isophthalic acid and / or terephthalic acid have a special technical significance. In a preferred embodiment, e-caprolactam and hexamethylene diammonium adipate ("AH" salt) are used. In a special embodiment, especially when it is desired to prepare branched or extended-chain copolyamides or polyamides, the following mixture is used in place of pure 6-aminocapronitrile: 50 to 99.99, preferably 80 to 90% by weight of 6 aminocapronitrile, 0.01 to 50, preferably 1 to 30% by weight of at least one dicarboxylic acid, selected from the group consisting of aliphatic C4-C10 α-dicarboxylic acids, aromatic CB-C12 dicarboxylic acids and cycloalkanedicarboxylic acids C3-C8, 0 to 50, preferably 0.1 to 30% by weight of a,? -diamine with 4 to 10 carbon atoms, 0 to 50, preferably 0 to 30% by weight of a,? -dinitrile C2 -C12, as well as, 0 to 50, preferably 0 to 30% by weight of a C, -C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C, C2. inorganic or its salt, reaching the sum of the individual weight percentage data 100%.

As the dicarboxylic acids, aliphatic C 4 -C 10 α-dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberinal acid, azelaic acid, sebacic acid, preferably adipic acid and sebacic acid, more preferably adipic acid can be used and aromatic C8-C12 dicarboxylic acids such as terephthalic acid as well as C-C3 cycloalkanedicarboxylic acids such as cyclohexanedicarboxylic acid. As a, β-diamine having 4 to 10 carbon atoms, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine and decamethylenediamine, preferably hexamethylenediamine can be used. It is also possible to use salts of the aforementioned dicarboxylic acids and diamines, especially the salt of adipic acid and hexamethylenediamine, the so-called AH salt. As α, β-dinitrile C2C12, aliphatic dinitriles are preferably used, such as 1-dicyanobutane (adiponitrile), 1,5-dicyanopentane, 1,6-dicyanohexane, 1,7-dicyanoheptane, 1,8-dicyanoctane, 1, 9- dicyanononane, 1,10-dicyanodecane, more preferably adiponitrile. If desired, diamines, dinitriles and aminonitriles, which are derived from branched alkylene or arylene or alkylarylene, can also be used.

As C 5 -C 12 -aminocarboxylic acids, there can be used 5-aminopentanoic acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminohexanoic acid. -aminododecanoic, preferably 6-aminohexanoic acid. The preceding compounds can also be used as mixtures. Thermoplastic polymers The thermoplastic polymers are all polymers which are dissolved in aminonitriles, in their mixtures with other polyamide-forming monomers or in their reaction mixtures and which do not impair their polymerization. Under the term "dissolution" is understood according to the invention the preparation of a melt that has a clear appearance for the observer, that is, the thermoplastic polymers A can be dissolved physically dispersed in fine form.

Suitable amorphous polymers include polyarylene ethers such as polyarylene ether sulfone or polyphenylene ether, polyether ether, polyamideimide, polystyrene or styrene copolymers such as styrene / acrylonitrile copolymers, styrene / diene copolymers, elastic graft copolymers such as rubber based on diene rubbers or acrylate as the. so-called ABS (acrylonitrile / butadiene / styrene), ASA (acrylonitrile / styrene / acrylate) or AES (acrylonitrile / ethylene / styrene) or other ethylene copolymers. It is also possible to dissolve mixtures of different polymers A. Polyarylene ethers are, in particular, the compounds of the general formula (I).

The variables t and q mentioned in General Formula I can adopt the value 0, 1, 2 or 3. T, Q and Z can be the same or different, independently of each other. They can represent a chemical ligation or a group chosen between. -OR-, -S02-, -S-, C = 0, -N = N- and S = 0. In addition, T, Q and Z can also represent a group of the general formula -RaC = CRb-or -CRcRd-, where Ba and Rb in each case mean hydrogen or Cx to C10 alkyl groups, Rc and Rd in each case hydrogen , alkyl groups Cj. to C10, such as methyl, ethyl, n-propyl, i-propyl, t-butyl, n-hexyl, Cx to C10 alkoxy such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy or aryl groups C6 to C18 as phenyl or naphthyl. Rc and Rd can also be attached together with the carbon atom, to which they are linked, forming a cycloalkyl ring with 4 to 7 carbon atoms. Cyclopentyl or cyclohexyl are preferred among them. The cycloalkyl rings can be unsubstituted or substituted with one or more, preferably two or three, CS to C6 alkyl groups. Among the preferred substituents of the cycloalkyl rings is methyl. Preferably, polyarylene ethers are used, in which T, Q and Z mean -O-, -S02-, C = 0, a chemical ligation or a group of the formula -CRcRd. Among the preferred residues Rc and Rd are hydrogen and methyl. Of the groups T, Q and Z at least one means -S02- or C = 0. If both variables t and q are 0, then Z is either -S02- or C = 0, preferably -S02-. Ar and Ar1 represent C6 to C18 aryl groups, such as 1,5-naphthyl, 1,6-naphthyl, 2,7-naphthyl, 1,5-anthryl, 9,10-anthryl, 2,6-anthryl, 2,7 -anthyl or biphenyl, especially phenyl. Preferably, these aryl groups are unsubstituted. They may, however, have one or more substituents, for example, two. Examples of substituents which can be used are C.sub.1 -C.sub.1 -C.sub.12 alkyl radicals, such as methyl, ethyl, n-propyl, i-propyl, t-butyl, n-hexyl, aryl, C6 to C18, such as phenyl or naphthyl, alkoxy Ct to C1Q, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy and halogen atoms. Preferred substituents include methyl, phenyl, methoxy and chloro. Some suitable repeating units are indicated below: so \ // -, -J (ID Polyarylene ethers with repeating units (II), (12) or (18) are especially preferred. Among them are, for example, polyarylene ethers with 0 to 100 moles% repeating units (II) and 0 to 100 moles% repeating units (12). The polyarylene ethers can also be block co-copolymers or copolymers, in which segments of polyarylene ethers and segments of other thermoplastic polymers are found such as polyesters, aromatic polycarbonates, polyester carbonates, polysiloxanes, polyimides or polyetherimides. The molecular weights (number average) of the branches of the blocks and / or of the grafts in the copolymers are generally in the range of 1000 to 30000 g / mol. The blocks of different structure can be ordered alternately or statistically. The weight part of the polyarylene ether in co-copolymers or block copolymers is generally at least 10% by weight. The weight part of the polyarylene ether can be up to 97% by weight. Co-copolymers or block copolymers with one part by weight of polyarylene ether with up to 90% by weight are preferred. Especially preferred are co-copolymers or block copolymers with 20 to 80% by weight of polyarylene ether. Suitable polyarylene ethers are also those which are modified with monomers containing acid or anhydride groups. Such polyarylene ethers can be prepared, e.g. , starting from the monomers containing corresponding acid and / or anhydride groups. They can also be obtained by means of grafting these monomers onto the polyarylene ether chain. Among the suitable acid groups are the carboxylic acid, sulfonic acid and phosphonic acid groups. Especially preferred are polyarylene ether sulfones, which contain acid groups, distributed sequentially or statistically in the polymer chain, the acid groups can be linked, eg. , to the arylene residues or to the intermediate alkylene members. For example, polyarylene ether sulfones which are modified with fumaric acid, maleic acid, maleic acid anhydride or more especially 4,4'-dihydroxyvaleric acid are suitable. Examples of such polyarylene ether sulfones can be found in, e.g. , EP-A-0185237. Mixtures of two or more different polyarylene ether sulfones can also be used.

In general, the polyarylene ethers have average molecular weights Mn (number average) in the range of 5000 to 60000 g / mol and relative viscosities of 0.20 to 0.95 dl / g. The relative viscosities are measured according to the solubility of the polyarylene ethers either in a 1% by weight solution of N-methylpyrrolidone, in mixtures of phenol and dichlorobenzene or in 96% sulfuric acid at 20 ° C or 25 ° C. Polyarylene ethers with repeating units I are known and can be prepared according to known methods.

They are formed, eg. , by condensation of aromatic bishalogenated compounds and the alkaline double salts of aromatic bisphenols. They can also be prepared, for example, by autocondensation of alkali salts of aromatic halogenols in the presence of a catalyst. Polyarylene ethers, which contain carbonyl functions, can also be obtained by electrophilic polycondensation (Friedel-Crafts). In the electrophilic polycondensation, carbonyl bridges or dicarboxylic acid chlorides or phosgene with aromatic compounds, which contain two hydrogen atoms - which can be exchanged for electrophilic substituents, or an aromatic carboxylic acid chloride, are also converted for the formation of carbonyl bridges or which contains both an acid chloride group and a substitutable hydrogen atom, is self-polycondensed. Preferred process conditions for the synthesis of polyarylene ethers are described, for example, in EP-A-0 113 112 and EP-A-0 135 130. Transformation of the monomers into aprotic solvents is particularly suitable., especially N-methylpyrrolidone, in the presence of anhydrous alkali carbonate, especially potassium carbonate. The transformation of the monomers into the melt has proven to be advantageous in many cases. The polyarylene ethers of the general Formula I can have as terminal groups, e.g. , hydroxy, chloro, alkoxy, among them preferably methoxy, phenoxy, amino or anhydride or mixtures of the mentioned terminal groups. The thermoplastic polymers A can also be compounds based on substituted polyphenylene ethers, especially disubstituted, the oxygen of the ether of a unit being linked to the benzene nucleus of the neighboring unit. Preferably, polyphenylene ethers substituted in position 2 and / or 6 with respect to the oxygen atom are used. Examples of substituents which may be mentioned are halogen atoms, such as chlorine or bromine, long-chain alkyl radicals with up to 20 carbon atoms, such as lauryl and stearyl, and also short-chain alkyl radicals having 1 to 4 hydrocarbon atoms, they do not preferably have a tertiary hydrogen atom in the OI position, eg. , methyl, ethyl, propyl or butyl radicals. The alkyl radicals can in turn be replaced one or more times by halogen atoms, such as chlorine or bromine, or by a hydroxyl group. Other examples of possible substituents are alkoxy radicals, preferably with 1 to 4 carbon atoms or optionally phenyl radicals substituted one or more times by halogen atoms and / or Cx-C4 alkyl groups according to the preceding definition. Also suitable are copolymers of various phenols, such as copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol. Of course, mixtures of various polyphenylene ethers can also be used. Examples of the polyphenylene ethers which can be used according to the invention are: Poly (2,6-dilauryl-1, 4-phenylene ether), Poly (2,6-diphenyl-1,4-phenylene ether), Poly (2, 6) -dimethoxy-l, 4-phenylene ether), Poly (2,6-diethoxy-l, 4-phenylene ether), Poly (2-methoxy-β-ethoxy-1, 4-phenylene ether), Poly (2-ethyl-6-) stearyloxy-1, 4-phenylene ether), Poly (2,6-dichloro-l, 4-phenylene ether), Poly (2-methyl-6-phenyl-1, 4-phenylene ether), Poly (2,6-dibenzyl) , 4-phenylene ether), Poly (2-ethoxy-1, 4-phenylene ether), Poly (2-chloro-l, 4-phenylene ether), Poly (2,6-dibromo-1,4-phenylene ether), are preferably used polyphenylene ethers having alkyl radicals having 1 to 4 carbon atoms as substituents, such as: Poly (2,6-dimethyl-1,4-phenylene ether), Poly (2,6-diethyl-1, 4-phenylene ether), Poly (2) methyl-6-ethyl-1, 4-phenylene ether), Poly (2-methyl-6-propyl-1, 4-phenylene ether), Poly (2,6-dipropyl-1, 4-phenylene ether) and Poly (2-methyl) ethyl-6-propyl-l, 4-phenylene ether). Polyphenylene ethers in the sense of the invention are also to be understood as those modified with monomers, such as fumaric acid, maleic acid or maleic anhydride. Such polyphenylene ethers are described, inter alia, in WO 87/00540. Especially used in polyphenylene ether compositions are such that they have an average molecular weight M w (weight average) of ca. 8000 to 70000, preferably approx. 12000 to 50000 and especially approx. 20000 to 49000. This corresponds to a limit viscosity of approx. 0.18 to 0.7, preferably of approx. 0.25 to 0.55, and especially of approx. 0.30 to 0.50 dl / g, measured in chloroform at 25 ° C. The determination of the molecular weights of the polyphenylene ethers is generally carried out by means of gel permeation chromatography (ShodexIR separation columns) 0.8 x 50 cm of type A 803, A 804 and A 805 with THF as elution medium. room temperature) . Dilution of polyphenylene ether samples in THF is carried out under pressure at 110 ° C, injecting 0.16 ml of a 0.25% solution. The detection is generally carried out with a UV detector. The calibration of the columns was carried out with polyphenylene ether samples, whose absolute molecular weight distribution is determined by means of a combination of light-laser-GPC dispersion. hermore, polyetherimides or mixtures of various polyetherimides are suitable as thermoplastic polymers. As polyetherimides, aliphatic as well as aromatic polyetherimides can be used in principle. Also suitable are polyetherimides containing both aliphatic and aromatic groups in the main chain. For example, polyetherimides containing repeating units of the general Formula II can be used: choosing Q ', for example, between: wherein Z 'and R' independently of one another may be the same or different. Z 'and R' can mean, for example. , an alkylene group C to C30. The alkylene group can be either linear or branched or also be closed as a ring. Among them may be mentioned methylene, ethylene, n-propylene, i-propylene, cyclohexylene or n-decylene. But Z 'and R' may also represent a C7 to C30 alkylarylene moiety. Examples thereof are diphenylenemethane, diphenylene ethane or 2,2-diphenylenepropane. In addition Z 'and R' can mean a C6 to Cl8 arylene moiety such as phenylene or biphenylene. The aforementioned groups may be substituted in turn with one or more substituents, or interrupted by heteroatoms and / or groups. Especially preferred substituents are halogen atoms, preferably chlorine or bromine or C restos alkyl radicals. to C10, especially methyl or ethyl. Among the preferred heteroatoms and / or groups are -S02-, -0- or -S-. The following are presented as an example some suitable residues Z 'and R': where Q "can mean -CyH2y-, -CO-, -S02-, -O- or -S-, q is 0 or 1, p means 0 or 1 and y represents an integer from 1 to 5. R" can means CL to C10 alkyl or Cx to Cio alkoxy, and r may be zero or 1. In addition the polyetherimides may contain other imide units apart from the units of the general Formula II. Suitable, for example, units of Formulas III or 112 or their mixtures are: (III) (H2) Preference is given to using polyetherimides containing repeating units of the general Formula III: where Z "and R" have the same meaning as Z 'and R'.

Especially preferred polyetherimides contain repeating units where Z "means: and R "is chosen from: '/ Especially preferred polyetherimides contain repeating units of Formula (III1): (H? L) The polyetherimides generally have average molecular weights (average value in number Mn) of from 5000 to 50000, preferably from 8000 to 40000. They are known or can be obtained according to known methods. Thus the corresponding dianhydrides can be transformed with diamines corresponding to the polyetherimides. In general, this transformation is carried out in a substance or in an inert solvent at temperatures of 100 to 150 ° C. As a solvent, o-dichlorobenzene or m-cresol are particularly suitable. The polyetherimides can also be prepared in the melt at temperatures of 200 to 400 ° C, preferably 230 to 300 ° C. For the preparation of the polyetherimides, the dianhydrides are generally converted to the diamines in an equi-olar ratio. However, some molar excesses are also possible, eg. , 0, 1 to 5 mol% of dianhydride or diamine. Polystyrenes can also be used as polymers according to the invention. Suitable monomers are styrenes, and also styrenes alkylated in the nucleus or in the side chain. As examples, mention may be made of chlorostyrene, α-ethylstyrene, styrene, p-methylstyrene, vinyltoluene and p-tert-butylstyrene. Preferably, however, only styrene is used. ~~~~ Homopolymers are generally prepared according to known procedures in bulk, solution or suspension (see Ullmanns Enzyklopadie der technischen Chemie, Volume 19, pages 265 to 272, Verlag Chemie, Weinheim 1980). The homopolymers can have a weight average molecular weight Mw of from 100 to 300,000, which can be determined according to the usual methods. In addition, the thermoplastic polymers can be styrene-based copolymers, among which copolymers based on other vinylaromatic monomers, such as α-methylstyrene or substituted styrenes, can also be understood according to the invention. , alkylstyrenes CX-C-LO such as methylstyrene or mixtures of different vinylaromatic monomers. Suitable are, for example, styrene copolymers of: 50 to 95% by weight, preferably 60 to 80% by weight of styrene, α-methylstyrene or substituted styrenes, N-phenylmaleimide or their mixtures, and 5 to 50% by weight, preferably 20 to 40% by weight of acrylonitrile, methacrylonitrile, methylmethacrylate, acid anhydride Maleic or its mixtures. The styrene copolymers are resinous, thermoplastic and rubber-free. The styrene copolymers which are especially preferred are those of styrene with acrylonitrile and optionally with methyl methacrylate, of a-methylstyrene with acrylonitrile and optionally with methylmethacrylate or of styrene and α-methylstyrene with acrylonitrile and optionally with methylmethacrylate and of styrene and maleic anhydride . Various of the described styrene copolymers can also be used at the same time. These styrene copolymers are known and can be prepared by radical polymerization, especially by emulsion, suspension, solution and bulk polymerization. They generally have viscosity values in the range of approx. 40 to 160, which corresponds to molecular weights Mw average (average in weight) of approx. 40000 to 2000000. In the process according to the invention, styrene copolymers of vinylaromatic monomers can also be used, for example, styrene or α-methylstyrene and conjugated dienes. A particularly suitable vinylaromatic monomer is styrene. Conjugated dienes are used, inter alia, butadiene or isoprene, butadiene being preferably used. The copolymers obtainable by first polymerizing the vinylaromatic monomers with conjugated dienes and then subjecting them to a hydration reaction can also be used as styrene copolymers. Such styrene copolymers can be obtained in particular by anionic polymerization of vinylaromatic monomers and conjugated dienes. Thus, block copolymers of these comonomers are mainly generated. The methods for the preparation of such styrene copolymers are known in general, e.g. , of US-A 3,595,942. The styrene copolymers used can have any structure, block copolymers with a three-block structure are especially preferred, as well as branched structures, so-called star-shaped, with multi-block structure. The synthesis of star-shaped block copolymers from vinylaromatic monomers and diene monomers is described in DE-A 19 59 922, the synthesis of block copolymers prepared in the form of a star with multiple initiation in DE-A- 25 50 226 as well as in US 3,639,517. Suitable monomers as well as initiators can be found in the mentioned writings. Particular preference is given to block copolymers based on styrene as vixarylaromatic monomer as well as butadiene and / or isoprene as conjugated diene monomers. The part of the vinylaromatic monomer in the styrene copolymers used is generally from 25 to 95, preferably 40 to 90% by weight. Thermoplastic polymers can also be graft copolymers, which are preferably prepared from: a) ca. 40 to 80% by weight, preferably 50 to 70% by weight of a graft base from a rubber elastic polymer with a glass transition temperature of less than 0 ° C, a2) approx. 20 to 60% by weight, preferably 30 to 50% by weight of a grafted aggregate of: a21) approx. 50 to 95% by weight, preferably 60 to 80% by weight of styrene or substituted styrenes of the above-mentioned general Formula III or methylmethacrylate or mixtures thereof a22) approx. 5 to 50% by weight, preferably approx. 20 to 40% by weight of acrylonitrile, methacrylonitrile, methylmethacrylate, maleic anhydride or mixtures thereof. For the graft base a) polymers whose glass transition temperature is below 10 ° C, preferably below 0 ° C, especially -20 ° C, come into consideration. These are, for ex. , natural rubber, synthetic rubber based on conjugated dienes or their mixtures with other copolymers, as well as elastomers based on C1-8 alkyl esters of acrylic acid, which may contain other comonomers. Preferably, polybutadiene or copolymers of butadiene and styrene are considered as the graft base. Further preferred are graft bases (a), which are composed of: all) 70 to 99.9% by weight, preferably 66 to 79% by weight of at least one alkyl acrylate with 1 to 8 C atoms in the alkyl radical, preferably n-butylacrylate and / or 2-ethylhexylacrylate, especially n-butylacrylate as the only alkyl acrylate. al2) 0 to 30% by weight, preferably 20 to 30% by weight of another copolymerizable, monoethylenically unsaturated monomer, such as butadiene, isoprene, styrene, acrylonitrile, methylmethacrylate and / or vinylmethylether. al3) 0.1 to 5% by weight, preferably 1 to 4% by weight of a copolymerizable, polyfunctional, preferably bi-or trifunctional monomer, which causes crosslinking. Suitable such bi- or polyunitic crosslinking monomers al3) are monomers preferably containing two, optionally also three or more, ethylenic double bonds capable of copolymerization, which are not conjugated in the 1,3-positions. Suitable crosslinking monomers are, for example, divinylbenzene, diallylmaleate, diallyl fumarate, diallyl phthalate, triallylcyanurate or triallylisocyanurate. The acrylic acid ester of the tricyclodecenyl alcohol has proved to be an especially suitable crosslinking monomer (see DE-A-12 60 135). This type of graft base is also known and described in the literature.

Of the grafted aggregates a2) those in which a21) means styrene or α-methylstyrene are preferred. Preferred monomer mixtures are, in particular, styrene and acrylonitrile, α-methylstyrene and acrylonitrile, styrene, acrylonitrile and methyl methacrylate, styrene, N-phenylmaleimide and maleic anhydride. The grafted aggregates can be obtained by copolymerization of components a21) and a22). For the case that the graft copolymer contains a graft base a), composed of polybutadiene polymers, there is talk of an ABS rubber. The graft copolymerization can be carried out, as is known, in solution, suspension or preferably in emulsion. In the preparation of the ABS rubber and the emulsion graft, the soft phase of the graft copolymer preferably has an average particle diameter (d.sub.50 value of the integral mass distribution) of 0.08 mm. By increase of the particles, eg. , by agglomeration or by obtaining the emulsion by means of the sowing latex method, the d50 value is adjusted in the range of 0.2 to 0.5 mm. In such graft copolymerizations, at least partially chemical bonding of the monomers which polymerize with the already polymerized rubber is carried out, the connection probably taking place in the double bonds contained in the rubber. At least a part of the monomers is then grafted to the rubber, ie it is ligated to the rubber macromolecules by means of covalent bonds. The grafting can also be carried out in several steps, a part of the monomers forming the graft cover and then the rest being grafted in first. If the graft base a) of the graft co-polymers is composed of the components all), possibly al2) and al3), we speak of ASA rubbers. Its preparation is known or can be carried out by known methods. The preparation of the grafted aggregate of the grafted copolymers can be carried out in one step or in two steps. In the case of Z the preparation of the grafted aggregate in a single step polymerizes a mixture of the monomers a21) and a22) in the desired weight ratio in the range of 95: 5 to 50:50, preferably 90:10 to 65:35 in the presence of the elastomer al, in a known manner, preferably in emulsion. In the case of a preparation of the grafted aggregate a2) in two steps, the first step generally comprises 20 to 70% by weight, preferably 25 to 50% by weight with respect to a2). For their preparation, only monoethylenically unsaturated aromatic hydrocarbons (a21) are preferably used. The second step of the grafted aggregate generally comprises 30 to 80% by weight, especially 50 to 75% by weight, referred in each case to a2). For its preparation, mixtures of monoethylenically unsaturated aromatic hydrocarbons a21) and monoethylenically unsaturated monomers a22) are used in the weight ratio a21) / a22) of in general 90:10 to 60:40, especially 80:20 to 70:30. The graft copolymerization conditions are preferably chosen in such a way that particle sizes of 50 to 700 nm result (d50 value of the integral mass distribution). The measures for this are known. By means of the seed latex process, a rubber dispersion with large particles can be prepared directly. To obtain as viscous products as possible, it is often advantageous to use a mixture of at least two graft copolymers with different particle size. To achieve this the rubber particles are enlarged in a known manner, eg. , by agglomeration, so that the latex is bimodally composed (eg, 50 to 180 nm and 200 to 700 nm). In addition, thermoplastic polymers A of grafted α-olefins should be mentioned as copolymers. The α-olefins are generally monomers with 2 to 8 C atoms, preferably ethylene and propylene. Suitable as comonomers are alkyl acrylates or alkyl methacrylates which can be derived from alcohols having 1 to 8 Cr atoms, preferably ethanol., butanol or ethylhexanol, as well as reactive comonomers such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride or glycidyl (meth) acrylate and also vinyl esters, especially vinyl acetate. Mixtures of various comonomers can also be used. Copolymers of ethylene with ethyl or butyl acrylate and acrylic acid and / or maleic anhydride have proven to be particularly suitable as comonomers. The copolymers can be prepared in a high pressure process at a pressure of 4Q0 to 4500 bar or by grafting the comonomers onto the poly-α-olefin. The part of the α-olefin in the copolymers is, in general, in the range of 99.95 to 55% by weight. Polyamides as thermoplastic polymers Preferably, in the second, third and fourth steps of the process, polyamides are added as thermoplastic polymers, prepared from polyamide-forming monomers, such as dicarboxylic acids, such as alkanedicarboxylic acids with polycarboxylic acids. to 12 carbon atoms, especially 6 to 10 carbon atoms, such as adipic acid, pimelic acid, suberinal acid, azelaic acid or sebacic acid, as well as terephthalic acid and isophthalic acid, diamines such as C4_12 alkyldiamines, especially with 4 to 8 atoms of carbon such as hexamethylenediamine, tetramethylenediamine or octamethylenediamine, in addition m-xylylenediamine, bis- (4-aminophenyl) methane, bis- (4-aminophenyl) -? ropano-2,2 or bis- (4-aminociclohexyl) methane, as well as mixtures of dicarboxylic acids and diamines, each in any combination, in relation to each other nevertheless advantageously in a to an equivalent ratio as hexamethylene diamine adipate, hexamethylene diamine terephthalate or tetramethylene diammonium adipate, preferably hexamethylene diammonium adipate and hexamethylene diammonium terephthalate. Especially preferred are polyamides which are composed of caprolactam, hexamethylenediamine, as well as adipic acid, isophthalic acid and / or terephthalic acid. The process according to the invention comprises 3 or 4 steps, the thermoplastic polymers can be added to the reaction mixture in all process steps, while other polyamide-forming monomers are preferably added in process steps 1 to 3. In addition other polyamides can be added to the polymer mixture preferably in the third and fourth steps of the process. In general, 30 to 100, preferably 35 to 100% by weight, based on the total amount of monomers (monomers b for forming polyamides and aminonitriles), for aminonitriles and from 0 to 70, preferably 0 to 65% by weight, are used. referred to the total amount of monomers, of the other monomers forming polyamides. The salt AH is commonly used as an aqueous solution, the concentration of which is generally 30 to 75, preferably 35 to 70% by weight, based on the aqueous solution. In general, the weight ratio between aminonitriles and salt AH is chosen in the range of 4: 1 to 20: 1, preferably in the range of 5: 1 to 15: 1. The part of the thermoplastic polymers in the reaction mixture in the solution is in general from 1 to 75% by weight. Correspondingly the part of the sum of aminonitriles and polyamide-forming msnomers is from 25 to 99% by weight. Preferably, the mixture contains from 2 to 75, especially from 3 to 70% by weight of the thermoplastic polymers and from 25 to 98, especially from 30 to 97% by weight of the total amount of aminonitriles and monomers forming polyamides. According to the invention, in the first step (Step 1) at least one aminonitrile is heated with water, at a temperature of approx. 90 up to approx. 400 ° C, preferably approx. 180 to approx. 310 ° C and especially at approx. 220 up to approx. 270 ° C, regulating a pressure of approx. 0.1 to approx. 15 x 10e Pa, preferably approx. 1 to approx. 10 x 106 Pa and especially approx. 4 to approx. 9 x 106 Pa. The pressure and the temperature can be regulated one with respect to another in this step in such a way that a liquid phase or a solid phase and a mixture of a liquid phase or a solid phase and a gas phase can be obtained. According to the melting point of the polyamide-forming monomers, the thermoplastic polymers are dissolved at temperatures in the range of 50 to 300 ° C, preferably in the range of 80 to 290 ° C in aminonitrile and other monomers forming polyamide. In order to obtain a good possible mixture of the components of the solution, the mixtures are advantageously stirred. For this they are suitable, eg. , stirring vessels. The water is then added in general in one go, in portions or continuously. The temperature of the solution is increased either simultaneously or subsequently in general at 180 to 330 ° C., preferably at 220 ° C. to 310 ° C. The solution can remain in the equipment in which it was prepared or - especially in the case of continuous transformation - it can be transferred to another reaction vessel before or after the temperature rise or before or after the addition of water. According to the invention water is added in a molar ratio between aminoalkylnitrile and water in the range of 1: 1 to 1:30, more preferably 1: 2 to 1: 8, more preferably still 1: 2 to 1: 6. , preferring the use of excess water, referred to the aminoalkyl nitrile used. In this embodiment, the liquid phase or the solid phase or the mixture of liquid phase and solid phase corresponds to the reaction mixture, while the gas phase is separated. Within the framework of this step the gaseous phase can be separated immediately from the liquid phase or from the solid phase or from the solid phase or liquid phase mixture, or the reaction mixture that is formed within this step can be present in two. liquid-gaseous phases, solid-gas or liquid / solid-gaseous. Of course the pressure and the temperature can also be regulated one with respect to the other in such a way that the reaction mixture is in the form of a single solid or liquid phase. The separation of the gas phase can be carried out using stirred or unstirred separating vessels or cascades of containers as well as using evaporation apparatuses, e.g. , by means of rotary evaporators or thin film evaporators, as for example. , by film extruders or by ring disk reactors, which guarantee an increased surface area between phases. It is optionally required to pump the reaction mixture to another container and / or the use of a recirculation reactor to increase the surface between phases. In addition, the separation of the gas phase can be stimulated by the addition of water vapor or inert gas to the liquid phase. Preferably, the pressure is regulated to a pre-set temperature such that it is lower than the equilibrium vapor pressure of ammonia, however, greater than the equilibrium vapor pressure of the remaining components in the reaction mixture at the temperature prefixed In this way, the separation of the ammonia can be particularly favored and thus the hydrolysis of the acidic amide groups can be accelerated. Preferably, in the two-phase process, a pressure is chosen which is greater than the pure water vapor pressure corresponding to the mass temperature of the reaction mixture, but lower than the equilibrium vapor pressure of ammonia. In Step 1, stirring vessels, circulation tubes or container cascades can be used. In a two-step process, the use of containers or a reaction column is preferred, while in the single-phase liquid process, as a preferred embodiment, a circulation tube provided with filling bodies is preferably used. It is also possible to use a tube bundle reactor, optionally equipped with filler bodies, in the first step of the process and it is especially advantageous in a two-stage process to improve the heat exchange and further reduce a new one. axial mixing of the reagents. As filler bodies can be used, eg. , Raschig rings or mixed elements of Sulzer, to ensure a tight time distribution of time and to limit a new mixing. In another embodiment, circulation in the reactor of the first step from top to bottom is carried out, it being preferably provided in turn with filling bodies that limit a new axial mixture of the reactants. In this way, the ammonia gas released into the reactor, which is formed mainly directly after entry into the reactor, reaches the gas phase in the reactor head by the shortest path. Therefore, the disturbance of the circulation profile in the further development of the reactor is reduced by gas bubbles and / or by convection. In a more preferred embodiment of the two-stage process, a vertical circulation tube is placed which circulates from bottom to top and has a further opening for the separation of the gas phase from above the outlet of the product. This tube reactor can be filled completely or partially with a catalyst granulate. In a preferred embodiment, the vertical reactor in the two-phase process is filled up to the limit of the phases with catalyst material at most. In another preferred embodiment of the first step, the pressure is chosen in such a way that the reaction mixture is in a single liquid phase, that is, a gas phase is not present in the reactor. In this single-stage process, the preferred embodiment is a circulation tube filled exclusively with catalyst material. In a further preferred embodiment, the aminonitrile / water mixture is heated continuously with the aid of a heat exchanger and the mixture thus heated is introduced together with thermoplastic polymers and polyamide-forming monomers into a reaction vessel regulated thereto. temperature, preferably a tube, which may optionally contain incorporated elements such as Sulzer's mixed elements, to avoid further mixing. Of course, the aminonitrile / water mixture can also be heated separately from the thermoplastic polymers and other monomers and then mixed in the reactor. With respect to the residence time of the reaction mixture in the first step there are no limitations; it is chosen, however, in general in the range of approx. 10 minutes to approx. 10 hours, preferably between approx. 10 minutes and approx. 6 hours. Although there are no limitations with respect to the transformation of nitrile groups in Step 1, the transformation of nitrile groups in Step 1 is in general, especially for economic reasons, of not less than approx. 70 mol%, preferably at least 95 mol% and especially approx. 97 to approx. 99 mol%, referred in each case to the number of moles of aminonitrile used. The transformation of nitrile groups is commonly calculated by means of IR spectroscopy (CN valence oscillation at 2247 wave numbers), Raman, NMR or HPLC spectroscopy, preferably by IR spectroscopy. Furthermore, according to the invention it is not excluded that the transformation in Step 1 (and in the other steps, especially steps 2 and / or 3) can also be carried out in the presence of phosphorus compounds containing oxygen, especially phosphoric acid phosphorous acid and hypophosphorous acid as well as its alkali metal and alkaline earth metal salts and ammonium salts such as Na3P04, NaH2P04, Na2HP04, NaH2P03, Na2HP03, NaH2P02, K3P04, KH2HP04, KH2P03, K2HP03, KH2P02, the molar ratio being chosen ? -aminonitrile and phosphorus compounds in the range of 0.01: 1 to 1: 1, preferably 0.01: 1 to 0.1: 1. In addition, a catalyst can be used as described below. The transformation can be carried out in Step 1 in a circulation tube, containing a Bronsted acid catalyst, selected from a catalyst of beta-zeolite, layered silicate or titanium dioxide from 70 to 100% by weight of anatase and 0 to 30% by weight of rutile, in which up to 40% by weight of the titanium dioxide can be replaced by tungsten oxide. If a very pure aminonitrile is used, then the anatase part in the titanium dioxide catalyst should be as high as possible. Preferably, a pure anatase catalyst is used. If the aminonitrile used contains impurities, for example 1 to 3% by weight of impurities, a titanium dioxide catalyst containing a mixture of anatase and rutile is preferably used. Preferably, the anatase part is 70 to 80% by weight and the rutile part is 20 to 30% by weight. More preferably in this case a titanium dioxide catalyst with ca. 70% by weight of anatase and approx. 30% by weight of rutile. The catalyst preferably has a pore volume of 0.1 to 5 ml / g, more preferably 0.2 to 0.5 ml / g. The average pore diameter is preferably 0.005 to 0.1 mm, more preferably 0.01 to 0.06 mm. If working with highly viscous products, the average pore diameter should be chosen large. The cutting hardness is preferably greater than 20 N, more preferably > No. N. The BET surface is preferably more than 40 m2 / g, more preferably greater than 100 m2 / g. In the case of a smaller BET surface chosen, the volume of the bulk material should be chosen correspondingly larger, in order to guarantee a sufficient effect of the catalyst. The most preferred catalysts have the following properties: 100% anatase; 0.3 ml / g pore volume; 0.02 mm average pore diameter; cutting hardness 32 N; 116 m2 / g BET surface or 84% anatase weight; 16% by weight of rutile; 0.3 ml / g pore volume; 0.03 mm pore diameter averaging-cutting hardness 26 N; 46 m2 / g of BET surface. The catalysts can be prepared from powders common in the market, such as those offered, for example, Degussa, Finnti or Kemira. When a part of tungsten oxide of up to 40% by weight is used, preferably up to 30% by weight, more preferably 15 to 25% by weight of the titanium dioxide is replaced by the tungsten oxide. The preparation of the catalysts can be carried out as described in Ertl, Knózinger, eitkamp: "Handbook of heterogeneous catalysis", VCH Weinheim, 1997, p. 98 ss. The catalyst can be used in any suitable way. It is preferably used in the form of shape bodies, strands, granules, coated filler bodies or incorporated elements, especially granules. The granulate must advantageously be so large that it can be separated well from the product mixture and that it does not impair the fluidity of the product during processing. It is possible to separate it mechanically from the first pass through the granulate form of the catalyst. For example, mechanical filters or screens are provided for this at the exit of the first step. If the catalyst is also used in the second and / or in the third step, it will be advantageously presented in the same way. According to the invention, the reaction mixture obtained in the first step is transformed in Step 2 at a temperature of approx. 200 (150) to approx. 350 (400) ° C, preferably at a temperature in the range of approx. 210 (200) to approx. 330 (330) ° C and especially in the range of approx. 230 (230)? C to approx. 270 (290) ° C and a pressure that is lower than the pressure in Step 1. Preferably the pressure in the second step is at least approx. 0.5 x 106 Pa less than the pressure in Step 1, the pressure in the range of approx. 0.1 to approx. 45 x 106 Pa, preferably approx. 0.5 to approx. 15 x 106 Pa and especially approx. 2 to approx. 6 x 106 Pa (values in parentheses: without catalyst). In Step 2 the temperature and the pressure are chosen such that a first gas phase and a first liquid phase or a first solid phase or a mixture of liquid first phase and first solid phase are obtained, and the first gas phase is separated of the first liquid phase or of the first solid phase or of the mixture of first liquid phase and first solid phase. The first gas phase, which is essentially composed of ammonia and water vapor, is generally separated continuously with the aid of a distillation device, such as a distillation column. The organic components of the distillate optionally separated in this distillation, mainly untransformed aminonitrile can be returned completely or partially to Step 1 and / or Step 2. The residence time of the reaction mixture in Step 2 has no limitations, but is , however, in general of approx. 10 minutes to approx. 5 hours, preferably approx. 30 minutes to approx. 3 hours. The tubing of the product between the first step and the second passage optionally contains filler bodies such as Raschig rings or mixed elements of Sulzer, which enable a controlled distension of the reaction mixture in the gas phase. This corresponds especially to the single-phase procedure. If desired, other thermoplastic polymers and / or polyamide-forming monomers can be added to the reaction mixture of the first step, preferably in a continuous form and in the liquid phase. Preferably the reactor of the second step also contains the catalyst material according to the invention, especially in the form of granules. It was found that the reactor, in comparison with the catalyst-free reactor, enables a further improvement of the properties of the product, especially at higher pressure and / or with a large excess of water in the reaction mixture. The temperature and pressure should be chosen in such a way that the viscosity of the reaction mixture remains sufficiently low, to avoid clogging the surface of the catalyst. In accordance with the invention, sieves or filters which guarantee the purity of the reaction mixture and separate the catalyst from the reaction mixture are also used at the outlet of the second process step. In step 3 the first liquid phase or the first solid phase or the mixture of first liquid phase and first solid phase is mixed with a gaseous or liquid phase, containing water, preferably water or water vapor, with water, heated to a temperature of approx. 90 to approx. 400 ° C, preferably approx. 180 to approx. 310 ° C and especially approx. 220 to approx. 270 ° C, regulating a pressure of approx. 0.1 to approx. 15 x 10e Pa and preferably approx. 1 to approx. 10 x 106 Pa and especially approx. 4 to approx. 9 x 106 Pa. This is preferably done continuously. The amount of water added (as liquid) is preferably in the range of approx. 50 to approx. 1500 ml, more preferably approx. 100 to approx. 500 ml, referred in each case to 1 kg of the first liquid phase or of the first solid phase or of the first liquid phase mixture and of the first solid phase, provided no thermoplastic polymer is added. By this addition of water the water losses caused in Step 2 are firstly compensated and hydrolysis of the acid amide groups in the reaction mixture is favored. From here it results as another advantage of this invention, that the mixing of the output products, as used in Step 1, can only be used with a small excess of water. If, in step 3, thermoplastic polymers and polyamide-forming monomers are added separately from water, the amount of water added depends on the solubility in water and the amount of the thermoplastic polymers added. Depending on the melting point of the aggregate components, the thermoplastic polymers and the monomers are brought to the liquid phase and at the required temperature, and if desired mixed with water. To obtain a good mixture as much as possible, the mixtures are advantageously stirred. For this they are suitable, eg. , stirring vessels. The solution is then preferably brought to the reaction temperature required from the third step of the process and then mixed with the first liquid phase or the first solid phase or the mixture of solid first phase and first liquid phase. For this purpose, the mixed elements can possibly be placed in the reactor that favors the mixing of the components. Step 3 can be carried out at a temperature of 150 to 370 ° C and a pressure of 0.1 to 30 x 106 Pa, in the case of a catalyst material according to the invention the conditions governing the Step 1. The temperature is preferably 180 to 300 ° C, more preferably 220 to 280 ° C. The pressure is preferably from 1 to 10 x 106 Pa, more preferably 2 x 106 to 7 x 106 Pa.

The pressure and the temperature can be regulated one with respect to the other in such a way that the reaction mixture is in a single liquid phase or in a single solid phase. In another embodiment, the pressure and the temperature are chosen in such a way that a liquid phase or a solid phase or a mixture of solid phase and liquid phase as well as a gas phase are obtained. In this embodiment, the liquid phase or the solid phase or the mixture of liquid phase and solid phase corresponds to the product mixture, while the gas phase is separated. Within the framework of this step, the gaseous phase can be separated immediately from the liquid phase or the solid phase or from the solid phase or liquid phase mixture, or the reaction mixture that is formed inside, from this step can be present in two phases liquid-gas, solid-gas or liquid / solid-gas. At a chosen temperature the pressure can be regulated such that it is less than the equilibrium vapor pressure of the ammonia, but greater than the equilibrium vapor pressure of the remaining components in the reaction mixture at the given temperature. In this way, the separation of ammonia can be particularly favored and thus accelerate the hydrolysis of the acid amide groups.

The devices / reactors that can be used in this step can be identical to those in Step 1, as mentioned above. The time spent in this step also has no limitations, but for economic reasons it is generally chosen in the range of approx. 10 minutes to approx. 10 hours, preferably between approx. 60 to approx. 8 hours, more preferably 60 minutes at approx. 6 hours. The product mixture obtained in Step 3 can be further processed as described below. In a preferred embodiment, the product mixture of Step 3 is subjected in a fourth step to a subsequent condensation at a temperature of approx. 200 to approx. 350 ° C, preferably at a temperature of approx. 220 at 300 ° C and especially at approx. 240 to 270 ° C. Step 4 is carried out at a pressure which is below the pressure of Step 3, and preferably in a range of approx. to 1000 x 103 Pa, more preferably to approx. 10 to approx. 300 x 103 Pa. In the framework of this step the temperature and the pressure are chosen in such a way that a second gaseous phase and a second liquid or solid phase or a mixture of a second liquid phase and a second solid phase are obtained, which they contain the polyamide. According to the invention, the transformation of the reaction mixture into the fourth step can also be carried out in the presence of new aggregate thermoplastic polymers. Depending on the melting point, the thermoplastic polymers are brought to the liquid phase at temperatures in the range of 50 to 300 ° C, preferably in the range of 80 to 290 ° C. For this they are suitable, eg. , stirring vessels such as tank containers. The solution is then preferably heated to the reaction temperature required from the fourth process step and then mixed together with the liquid phase or the solid phase or the solid and liquid phase mixture of the reaction product of the third or second reaction step. . Here mixed elements can be used, which favor the mixing of the components. In another embodiment, the thermoplastic polymers in liquid or solid form are added separately from the product of the third step, in the reactor of the fourth step, and there they are mixed, e.g. , with the help of an agitator.

The subsequent condensation is preferably carried out according to step 4 in such a way that the relative viscosity (measured at a temperature of 25 ° C and a concentration of 1 g of polymer per 100 ml in 96% by weight sulfuric acid) of the Polyamide reaches a value in the range of approx. 1.6 to approx. 3.5 In a preferred embodiment, water optionally present can be removed from the liquid phase by means of an inert gas such as nitrogen. The residence time of the reaction mixture in the Step 4 depends mainly on the desired relative viscosity, temperature, pressure and amount of water added in Step 3. If Step 3 is performed in a single phase, they can be placed in the product pipe between Step 3 and Step 4 eventually filling bodies composed by ex. , by Raschig rings or mixed elements of Sulzer, which allow a controlled relaxation of the reaction mixture in the gas phase. The fourth step can also be carried out with the catalyst according to the invention. It was found that the use of the catalyst in Process Step 4 improves the molecular weight formation especially when the relative viscosity of the product of the third step procedure or - in the case of a three step procedure - of the second step is less than RV = 1.6 - and / or the molar content of the nitrile groups and acid amides in the polymer is greater than 1%, in each case referred to the number of moles of aminonitrile used. In another embodiment, step 3 can be dispensed with in accordance with the invention and steps (1), (2) and (4) can be carried out for the preparation of the polyamide. The above-described procedures, that is to say, the sequence according to the invention of Steps (1) to (3) or (1), (2) and (4) or (1) to (4) can be carried out in discontinuous form , ie in a reactor consecutively in time, or continuously, ie in consecutive reactors at the same time. Of course it is also possible to carry out a part of the steps, for example, steps (1) and (2) continuously and the remaining step (s) in discontinuous form. In a further preferred embodiment of the present invention, it is possible to return at least one of the gaseous phases obtained in the steps corresponding to at least one of the preceding steps. It is further preferred that in Step 1 or Step 3 or both in Step 1 and also in Step 3 the temperature and pressure be chosen such that a liquid phase or a solid phase or a phase mixture is obtained. liquid and solid phase and a gas phase, and the gas phase is separated.

According to the invention, in all the steps, in which there are polymers, care must be taken that a good mixture of the polymers and the monomers is carried out. Especially in Steps 2 and 4, the use of apparatuses, for example, is particularly preferred. , stirrers, which cause a good cutting effect in the reaction mixture. Furthermore, in the context of the method according to the invention, an extension of the chain or a branch or a combination thereof can be carried out. For this, substances known to those skilled in the art for branching or extending the polymer chain are added in the individual steps. Preferably these substances are added in Step 3 or 4. As substances that may be used, mention may be made of: Amines or trifunctional carboxylic acids as branching and / or crosslinking agents. Examples of suitable at least trifunctional amines or carboxylic acids are described in EP-A-0 345 648. At least trifunctional amines have at least three amino groups, which are capable of transforming the carboxylic acid groups. They do not preferably have any carboxylic acid group. The at least trifunctional carboxylic acids have at least three carboxylic acid groups capable of being transformed with amines, which may be present, for example, also in the form of their derivatives, such as esters. The carboxylic acids do not preferably have amino groups capable of reacting with carboxylic acid groups. Examples of suitable carboxylic acids are trimesinic acid, trimerized fatty acids, which can be prepared, for example, from oleic acid and can have from 50 to 60 C atoms, naphthalene-polycarboxylic acids, such as naphthalene-1 acid. , 3, 5, 7-tetracarboxylic. Preferably the carboxylic acids are defined organic compounds and not polymeric compounds. Amines with at least 3 amino groups are, for example, nitrilotrialkylamine, especially nitrilotrietanamine, dialkylenetriamine, especially diethylenetriamine, trialkylene tetramine and tetraalkylenepentamine, the alkylene radicals preferably being ethylene residues. In addition, dendrimers can be used as amines. Preferably these dendrimers have the general formula I: (R2N- (CH2) n) 2N- (CH2) xN ((CH2) n-NR2) 2 (I) wherein: R is H or - (CHz -NR1; RX, H or - (CH2) n-NR22 where R2 H or - (CH2) n-NR32, where R3 H or - (CH2) n-NH2 n has an integer value of 2 to 6 and x has an integer value of 2 a 14. Preferably n represents an integer value of 3 or 4, especially 3 and x an integer value of 2 to 6, preferably 2 to 4, especially 2. The residues R may have the indicated meaning independently of each other, preferably the rest R is a hydrogen atom or a residue (CH2) n-NH2 Suitable carboxylic acids are those with 3 to 10 carboxylic acid groups, preferably 3 or 4 carboxylic acid groups, preferred carboxylic acids are those with aromatic nuclei and / or Examples are benzyl, naphthyl, anthracene, biphenyl, triphenyl or heterocycles such as pyridine, bipyridine, pyrrole, indole, furan, thiophene, purine, quinoline, fen. antreno, porphyrin, phthalocyanine, naphthalocyanine. 3, 5,3 ', 5'-biphenyltetracarboxylic acid phthalocyanine, naphthalocyanine, 3, 5, 3', 5'-biphenyltetracarboxylic acid, 1,3,5,7-naphthaletracarboxylic acid, 2, 4, 6-acid are preferred. pyridinetricarboxylic acid, 3, 5, 3 ', 5'-bipyridyltetracarboxylic acid, 3, 5,3', 5'- benzofenone tetr acarboxy 1 i co, 1,3,6,8-acridinteracarboxylic acid, especially acid 1, 3, 5-benzene-tricarboxylic acid (trimesinic acid) and acid 1, 2, 4, 5-benzene tetracarboxylic acid. Such compounds can be obtained technically or can be prepared according to the procedures described in DE-A-43 12 182.

By using the ortho-substituted aromatic compounds, imide formation is preferably prevented by the choice of suitable transformation temperatures. These substances are at least trifunctional, preferably at least tetrafunctional. The number of functional groups can be 3 to 16, preferably 4 to 10, more preferably 4 to 8. In the process according to the invention, at least trifunctional amines or at least trifunctional carboxylic acids can be used, but no mixing of corresponding amines and carboxylic acids. But there may be small amounts of at least trifunctional amines in the trifunctional carboxylic acids and vice versa. The substances are in the amount of 1 to 50 mmoles / g of polyamide, preferably 1 to 35, more preferably 1. to 20 mmoles / g of polyamide. Preferably the substances are contained in an amount of 3 to 150, more preferably 5 to 100, especially 10 to 70 mmoles / g of polyamide in equivalents. The equivalents refer to the amount of the amino groups or functional carboxylic acid groups. The difunctional carboxylic acids or the difunctional amines serve as chain extension means. They present 2 groups of carboxylic acids, which can be transformed with amino groups, or 2 amino groups that can be transformed with carboxylic acids. The carboxylic acids or difunctional amines do not contain, in addition to the carboxylic acid groups or amino groups, any other functional group which can react with amino groups or carboxylic acid groups. Preferably they do not contain other functional groups. Examples of suitable difunctional amines are those which form salts with difunctional carboxylic acids. They may be linear aliphatics, such as C1-14 alkylene diamine, preferably alkylene diamine-C-z-e, for example, hexylene diamine. They can also be cycloaliphatic. Examples are isophoronediamine, dicycycan, laromin. Branched aliphatic diamines can also be used, one example being Vestamin TMD (trimethylhexamethylenediamine, prepared by Hüls AG). They can also be diaminas. The total amines can be substituted in each case with Cx_12 alkyl radicals, preferably CI-I? in the carbon skeleton. The difunctional carboxylic acids are, for example, those which form salts with the difunctional diamines. They can be linear aliphatic dicarboxylic acids, which are - preferably C4_20 dicarboxylic acids. Examples are, adipic acid, azelaic acid, sebacic acid, suberinic acid. They can also be aromatic. Examples are isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, as well as dimerized fatty acids. The difunctional basic components are preferably used in amounts of 1 to 55, more preferably 1 to 30, especially 1 to 15 mm / g of polyamide. According to the invention, the product mixture obtained in Step 3 or the second liquid phase or the second solid phase or the mixture of second liquid phase and second solid phase (from Step 4), which contain the mixture, is removed from the reaction vessel. polyamide, preferably a melt of polymers, according to the usual methods, for example, with the aid of a pump. The polyamide obtained according to known methods can then be prepared, as described in detail, eg. , in DE-A 43 21 683 (page 3, row 54 to page 4, row 3). In a preferred embodiment, the cyclic dimer content in the polyamide-6 obtained according to the invention can be further reduced by extracting the polyamide first with an aqueous solution of caprolactam and then extracting it with water and / or extracting it in the extraction. gaseous phase (for example, described in EP-A-0 284 968). The low molecular weight components, such as caprolactam and its linear and cyclic oligomers, which are obtained with this further treatment, can be returned to the first and / or second and / or third step. The aliphatic and aromatic carboxylic and dicarboxylic acids and catalysts, such as phosphorus compounds containing oxygen, in amounts in the range of 0.01 can be added to the starting mixture and to the reaction mixture in all the chain regulator steps. to 5% by weight, preferably from 0.2 to 3% by weight, based on the amount of aminonitriles and monomer-forming polyamides used. Suitable chain regulators are, for example, propionic acid, acetic acid, benzoic acid, terephthalic acid, as well as triaceton diamine. Additional and filler materials such as pigments, dyes and stabilizers are generally added before granulating, preferably in the second, third and fourth steps of the reaction mixture. It is especially preferred to use fillers and additional materials when the reaction mixture and / or polymers are no longer transformed in the further development of the process in the presence of fixed-bed catalysts. As additional materials, the compositions may contain from 0 to 40% by weight, preferably from 1 to 30% by weight, based on the total composition, of one or more rubbers which modify the impact resistance. They can be used, for e. , modifiers. the usual impact resistance, which are suitable for polyamides and / or polyarylene-ethers. The rubbers that increase the resistance of the. polyamides, present in general two essential characteristics: they contain an elastomeric part, which has a glass temperature of less than -10 ° C, preferably of less than -30 ° C, and contain at least one functional group, which can interact with the polyamide. Suitable functional groups are, for example, carboxylic acid groups, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid amides, carboxylic acid, amino, hydroxyl, epoxide, urethane and oxazoline imides. As rubbers that increase the strength of the mixtures, they can be mentioned, for example. , the following: EP rubbers and / or EPDM, which were grafted with the functional groups mentioned above. Suitable grafting agents are, for example, maleic anhydride, itaconic acid, acrylic acid, glycidyl acrylate and glycidyl methacrylate. These monomers can be grafted onto the polymer in the melt or in solution, optionally in the presence of a radical initiator such as eumeno hydroperoxide. The α-olefin copolymers described under the polymers, among them especially the ethylene copolymers, can be used in place of the polymers A as rubbers and can be added as such to the compositions according to the invention.

As other groups of suitable elastomers, the core-wrapped graft rubbers can be mentioned. These are graft rubbers prepared in emulsion, which are formed by at least one hard component and one soft component. The term "hard component" is generally understood to mean a polymer with a glass temperature of at least 25 ° C, under a soft component is meant a polymer with a glass temperature of at most 0 ° C. These products have a structure composed of a core and at least one shell, resulting in the structure of the monomer addition sequence. The soft components are generally derived from butadiene, isoprene, alkyl acrylates, alkyl methacrylates or siloxanes and optionally other comonomers. Suitable siloxane cores can be prepared, for example, starting from cyclic oligomer octamethyltetrasiloxane or tetravinyltetramethyltetrasiloxane. These can be transformed to the soft siloxane cores, for example, with g-mercaptopropylmethyldimethoxysilane in a cationic polymerization which opens the ring, preferably in the presence of sulfonic acids. The siloxanes can also be crosslinked, being carried out, for ex. , the polymerization reaction in the presence of silanes with hydrolysable groups such as halogen or alkoxy groups, such as tetraethoxysilane, methyltrimethoxysilane or phenyltrimethoxysilane. Suitable comonomers can be mentioned here, e.g. , styrene, acrylonitrile and crosslinking or active graft monomers with more than one polymerizable double bond such as diallyl phthalate, divinylbenzene, butanediol diacrylate or triallyl (iso) cyanurate. The hard components are generally derived from styrene, α-methylstyrene and their copolymers, wherein acrylonitrile, methacrylonitrile and methyl methacrylate are preferably mentioned as comonomers. Preferred core-wrapped graft rubbers contain a soft core and a hard shell or a hard core, a first hard shell and at least one other hard shell. The introduction of functional groups such as the carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic acid, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halogenobenzyl groups is preferably carried out by the addition of suitable functionalized monomers during the polymerization of the last shell. Suitable functionalized monomers are, for example, maleic acid, maleic anhydride, mono- or diester or maleic acid, tert-butyl (meth) acrylate, acrylic acid, glycidyl (meth) acrylate and vinyloxazoline. The part of monomers with functional groups generally comprises 0.1 to 25% by weight, preferably 0.25 to 15% by weight, based on the total weight of the core-shell graft rubber. The weight ratio between the soft and hard components is in general from 1: 9 to 9: 1, preferably 3: 7 to 8: 2. Such rubbers, which increase the strength of the polyamides, are known and described, for example, in EP-A-0 208 187. Another group of suitable impact modifiers are the thermoplastic polyester elastomers. Polyester elastomers are segmented copolyether esters, which contain long chain segments, which are generally derived from poly (alkylene) ether glycols and short chain segments, which are derived from dicarboxylic acids and from low molecular weight diols. Such products are known and described in the literature, e.g. , in US 3,651,014. In the trade you can also obtain corresponding products under the names Hytrel (R) (DuPont), Arnitel (R1 (Akzo) and PelpreneÍR (Toyobo Co. Ltd.) Of course, mixtures of various rubbers can also be used. other additional materials can be mentioned, for example, auxiliary substances for processing, stabilizers and oxidation retardants, means against decomposition by heat and decomposition by ultraviolet light, lubricants and release agents, flame retardant media, colóranteos and pigments and plasticizers. Its part generally comprises up to 40, preferably up to 15% by weight, based on the total weight of the composition. The pigments and dyes are generally contained in amounts of up to 4, preferably 0.5 to 3.5 and especially 0.5 to 3% by weight. The pigments for coloring the thermoplastics are known in general, see, eg. , R. Gachter and H. Müller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, 1983, p. 494 to 510. As the first preferred group of pigments, mention may be made of the white pigments such as zinc oxide, zinc sulphide, lead white (2 PbC03 Pb (0H) 2), lithopones, antimony white and titanium dioxide. Of the two most common modifications of the titanium dioxide crystals (rutile and anatase type), the rutile form is especially used for the white coloring of the shaped masses according to the invention. The black coloring pigments, which can be used according to the invention, are iron oxide black (Fe304), spinel black (Cu (Cr, Fe) 204), manganese black (mixture of manganese dioxide, dioxide silicon and iron oxide), cobalt black and antimony black, as well as especially carbon black, which is generally used in the form of furnace or gas carbon black (see in this connection G. Benzing, Pigmente für Anstrichmittel, Expert-Verlag (1988), page 78 ss).

Of course, inorganic color pigments such as chromium oxide green or organic color pigments such as azopigrants and phthalocyanines can be used according to the invention to adjust certain shades. Such pigments are commonly available commercially. It can also be advantageous to use the aforementioned pigments and / or dyes mixed, eg. , carbon black with copper phthalocyanines, since in general the dispersion of color in thermoplastics is facilitated. The oxidation retarders and thermal stabilizers, which can be added to the thermoplastic masses according to the invention, are, for example. , metal halides of Group I of the periodic system, eg. , halides of sodium, potassium, lithium, optionally in combination with copper (I) halides, eg. , chlorides, bromides or iodides. Halides, especially copper, may also contain electron-rich p-ligands. As an example of such copper complexes, Cu halide complexes can be mentioned with eg. , triphenylphosphine. In addition, zinc fluoride and zinc chloride can be used. In addition sterically hindered phenols, hydroquinone, substituted representatives of this group, secondary aromatic amines may be used, optionally in combination with phosphorus-containing acids and / or their salts and mixtures of these compounds, preferably in a concentration of up to 1% by weight with reference to the weight of the mixture. Examples of UV stabilizers are substituted resorcinol, salicylate, benzotriazoles and benzophenone, which can be used in general in amounts of up to 2% by weight. Lubrication and demolding substances, which are generally added in amounts of up to 1% by weight of the thermoplastic mass are stearic acid, stearyl alcohol, amides and alkyl esters of stearic acid as well as esters of pentaerythritol with long chain fatty acids. It is also possible to use calcium, zinc or aluminum salts of stearic acid as well as dialkyl ketones, eg. , distearyl ketone. The present invention also relates to a polyamide, which can be prepared according to one of the processes. Mixtures of polyamides according to the invention and / or obtained according to the invention, especially polyamide-6 and its copolymers, and thermoplastic polymers can be used for the preparation of fibers, films and shape bodies. The advantages of the process according to the invention with respect to known processes are, inter alia, that the chain length of the thermoplastic polymers is not shortened or only shortened to a very small extent, and the polymers are finely dispersed in The compositions. Furthermore, according to the invention it is possible to use aminonitriles for the preparation of polyamide-6. Another advantage is the clear self-coloring of the compositions, which can be obtained according to the process according to the invention. The invention will be elucidated below on the basis of examples. EXAMPLES Preparation of the samples and analysis The so-called relative viscosity (RV) as a measure for molecular weight formation and the degree of polymerization was determined in a 1% by weight solution of extracted material and in a 1.1% solution. by weight in a polymer not extracted in 96% sulfuric acid at ~ 25 ° C by means of a viscometer according to Ubbelohde. The non-extracted polymers were dried before analysis for 20 hours under vacuum. The determination of the content of amino and carboxyl end groups was carried out on extracted polycaprolactam and was carried out as acidimetric titration. The amino groups were titrated in phenol / methanol 70:30 (parts by weight) as solvent with perchloric acid. The carboxyl end groups were titrated in benzyl alcohol as a solvent with potassium bleach.

For the extraction, 100 parts by weight of polysaprolactam were stirred and extracted with 400 parts by weight of completely desalinated water at a temperature of 100 ° C for 32 hours at reflux and after removing the water they were gently dried., ie without further condensation, at a temperature of 100 ° C for 20 hours under vacuum. All the experiments were carried out in a multi-step procedure equipment. The first step of the process with an empty volume of 1 liter and an interior length of 1000 mm was completely filled with Raschig ring filler bodies (diameter 3 mm, length 3 mm) or with titanium dioxide granules. The granulate (Type S 150 of Finnti) was composed of 100% of Ti02, which was as the so-called anatase modification and had a strand length between 2 and 14 mm, a strand thickness of approx. 4 mm and a specific surface area of more than 100 m2 / g. As a second step, a 2 liter separating vessel was used. The third step was a circulation tube filled with Raschig rings (diameter 6 mm, length 6 mm) or with the Ti02 granulate described above (volume 1 1, length 1000 mm). The fourth step of the process was composed of a separating vessel (Volume 2 1) from which the polymer melt was removed with the aid of a pump of cogwheels in the form of strands.

The equipment of the procedure was operated with steps 1, 2 and 4 (Ex 4, 5, 6) as well as with steps 1, 2, 3 and 4 (Ex 1, 2, 3). The thermoplastic polymers- were introduced before the 4th. step in the reaction mixture. For the preparation of the comparison products and / or the comparison examples, ACN polymers were prepared under the same process conditions and / or with the same process parameters without thermoplastic polymers. Representation of the Examples in the form of, abla The parameters of the procedure and the characteristics of the product are shown below in the form of a table. As "flow rate" is meant the mass flow of the reaction mixture through the first step of the process. Thermoplastic polymers used, PS: Polyarylene ether sulfone with repeating units of Formula I2, characterized by a viscosity value of 48 ml / g, for example, Ultrason S 1010 from BASF. SAN: Poly (styrene-co-acrylonitrile), characterized by a part of acrylonitrile of 25% by weight and a viscosity value of 80 ml / g (measured in solutions of 0.5% by weight in dimethylformamide at 25 ° C.

Yes O Procedure parameters Step I Step 2 Step 3 I Examples] Flow TP1 ACN: H20 CataP T vwz3 P T CataZ4 P T vwz PA-da. w [% p] (molar) lizer: [bar] fCJ lizer! [bar] [%] [bar] 300 PS. 33% 1: 2 86 242 1 32 254 60 36 245 l / Csirtp. 300 0% 1: 2 242 32 254 60 36 245 300 PS, 33% 1: 2 242 32 254 60 36 245 2 / Oxnp. 300 0% 1: 2 242 32 254 60 36 245 460 PS, 14% 1: 2 90 270 37 252 60 36 245 3 / Comp. 460 0% 1: 2 90 270 37 252 60 36 245 300 PS, 14% 1: 4 50 250 1.7 30 251 Step do not run? . / Comp. 300 0% 1: 4 50 250 1.7 30 251 Step not corrected. 600 SAN, 9% 1: 6 60 260 1.7 30 250 Paso no correap. 2.5 600 SAN, 9% 1: 6 60 270 1.7 30 251 Step not corrected.

'TP: Addition of the thermoplastic polymer in% p, based on the mass of the reaction mixture. With S = Polyarylene ether sulfonaySAN = Poly (styrene-co-acrylonitrile) 2 +: With catalyst / -: without catalyst 2VWZ: Time of residence of the product mixture • "WZ; Addition of water in step 3, referred to the stream of enerada of the reaction mixture in step 1 of the procedure OR Comparison of the results The viscosities of the molten product are taken into account, measured by means of oscillating shear stress, and in the sulfuric acid solvent, measured by means of capillary viscoat. The content of terminal groups aai.no (AEG) and aarboxilo (CEG) of the airplanes of polymers was also analyzed. Purity of the aainocapronitrile used: 99.5%.

The regulation of the temperature of the sample was carried out at 160 ° C in the nitrogen stream and lasted 24 hours.

Claims (4)

2. A process for producing polymer blends through the reaction of at least one aminonitrile with water and the presence of thermoplastic polymers selected from polyarylene ethers, polyether imides, polyamideimides, homo- and copolymers of styrene, rubber-elastic graft copolymers, ethylene copolymers, polyamides prepared from dicarboxylic acids and amines, and mixtures thereof, and optionally other polyamide-forming monomers, which consists of the following steps: 1) the reaction Tie at least one aminonitrile with water at a temperature of 90 to 400 ° C and a pressure of 0.1 to 35 x 106 Pa to obtain a reaction mixture, 2) further to react the reaction mixture - at a temperature of 150 to 400 ° C and a pressure that is lower - than the pressure in the step 1, the temperature and pressure being selected to obtain a first gaseous phase and a first liquid phase or first solid phase, or a mixture of the first phase e solid and the first liquid phase, and the first gas phase is separated from the first liquid phase or the first solid phase or from the mixture of the first liquid phase and the first solid phase,
3. 3) mixing the first liquid phase or the first solid phase or the mixture of the first liquid phase and the first solid phase with a gaseous or liquid phase containing water at a temperature of 150 ha. 370 ° C and a pressure from 0.1 to 30 x 106 P to obtain the polymer mixture, where in one or more of the steps thermoplastic polymers and optionally other polyamide forming monomers are added, wherein the reaction in steps 1 , 2 and / or 3 is carried out in the presence of a Brónsted acid catalyst selected from a beta-zeolite catalyst, a lamellar silicat catalyst or titanium dioxide catalyst containing from 70 to 100% by weight of anatase from 0 to 30 % by weight of rutile and in which up to 40 by weight of titanium dioxide can be replaced by tungsten oxide. The process as claimed in claim 1 further comprises the following step:
4. 4) the post-condensation of the polymer mixture at a temperature of 200 to 350 ° C and a pressure that is lower than the pressure of step 3, l temperature and pressure being selected to obtain a second gas phase containing ammonia water and a second liquid phase or second solid phase or a mixture, of the second liquid phase and the second solid phase, which each contains the polymer mixture. A process for producing polymer blends by reaction of at least one aminonitrile with water and the presence of thermoplastic polymers selected from polyarylene ethers, polyether imides, polyamideimides, styrene homo- and copolymers, rubber-elastic graft copolymers, ethylene copolymers, polyamides prepared from dicarboxylic acids and diamines, and mixtures thereof, and optionally other polyamide-forming monomers, which comprises the following steps: 1) reacting at least one ammonitrile with water at a temperature of 90 to 400 ° C and a pressure from 0.1 to 35 x 1Q6 Pa to obtain a reaction mixture, 2) further to react the reaction mixture at a temperature of 150 to 400 ° C and a pressure that is lower than the pressure in the-step 1, the temperature and pressure being selected to obtain a first gas phase and a first liquid phase or first solid phase, or a mixture of the first solid phase and the first liquid phase, and the first gaseous phase is separated from the first liquid phase or the first solid phase or from the mixture the first liquid phase and the first solid phase, after condensing the first liquid phase or the first phase solid or the mixture of the first liquid phase and the first solid phase at a temperature of 200 to 350 ° C and a pressure that is lower than the pressure of step 2, the temperature and pressure being selected to obtain a second phase. 10 containing water and ammonia and a second liquid phase or second solid phase or a mixture of the second liquid phase and the second solid phase, which each contains the polymer mixture, and where in one or more of the steps are added the 15 thermoplastic polymers and "optionally other polyamide-forming monomers, wherein the reaction in steps 1, 2 and / or 3 is carried out in the presence of a catalyst- Brontosteic acid selected from a beta-zeolite catalyst, or 20 a lamellar silicate catalyst or a titanium dioxide catalyst containing from 70 to 100% by weight of anatase and from 0 to 3-0% by weight of rutile in which up to 40% by weight of titanium dioxide can be replaced by oxide of tungsten, The process as claimed in any of claims 1 to 3, wherein the aminonitriles represent in total from 30 to 100% by weight of the polyamide-forming monomers. The process as claimed in any of claims 1 to 4, wherein the content of the thermoplastic polymer of the reaction mixture is from 1 to 75% by weight, based on the complete reaction mixture. The process as claimed in any of claims 1 to 5, wherein the aminonitrile used is an aminoalkyl nitrile having an alkylene portion (-CR7-) of 4 to 12 carbon atoms or an aminoalkylarylnitrile having from 8 to 13 carbon atoms. carbon