EP4100457A1

EP4100457A1 - Cross-linked aliphatic polyketones

Info

Publication number: EP4100457A1
Application number: EP21704727.3A
Authority: EP
Inventors: Thomas Schauber; Marco SUTTER; Bjoern Hellbach; Patrick Heyer; Kira Truxius; Tina ANDRÄ; Arthur Lanziner
Original assignee: Freudenberg SE
Current assignee: Freudenberg SE
Priority date: 2020-02-05
Filing date: 2021-02-05
Publication date: 2022-12-14
Also published as: CN115066454A; JP2023514116A; WO2021156403A1; US20230081308A1

Abstract

The present invention relates to a moulded body comprising a polymer matrix that contains a cross-linked aliphatic polyketone (PK) and a method for producing such a moulded body. The invention also relates to the use in the automotive, shipping, aerospace and rail vehicle fields, in the oil and gas industry, in the food and packaging industry and in the field of medical technology, more particularly as sealing articles, stop discs, back-up rings, valves, connectors, insulators, snap-in hook, bearings, bushings, films, powders, coatings, fibres, sealing rings and O rings, pipes and lines, cables, coverings and casings, as well as housings of an electrical or chemical application, which comprise such a moulded body or consist of such a moulded body.

Description

NETWORKED ALIPHATIC POLYKETONES

description

The present invention relates to a shaped body which comprises a polymer matrix which contains a crosslinked aliphatic polyketone (PK) and a method for producing such a shaped body. The invention also relates to use in the automotive, shipping, aerospace, rail vehicles, oil and gas industry, food and packaging industry and medical technology, in particular as sealing items, thrust washers, back-up rings, valves, connectors, insulators, snap hooks, Bearings, bushings, foils, powders, coatings, fibers, sealing and O-rings, pipes and lines, cables, casings and jackets, as well as housings for an electrical or chemical application that comprise such a molded body or that consist of such a molded body.

State of the art

Thermoplastically processable plastics (thermoplastics) have found widespread use due to the productivity of their manufacture, their reversible deformability and often also because of their high-quality technical properties and are now a standard product in industrial production. They consist of essentially linear polymer chains, meaning they are not networked and usually only slightly branched or not branched at all. However, thermoplastics have an intrinsically determined limit with regard to their temperature resistance and are therefore not optimally suitable for all areas of application of polymer materials. It is therefore desirable to increase the temperature resistance of thermoplastic plastics without foregoing advantages such as processability, good mechanical properties or high chemical resistance. Cross-linked polymers (thermosets, thermosets), in which the macromolecules are connected to one another by covalent bonds, are advantageous here. At low temperatures, these are in a hard-elastic state, which is also referred to as the glass area. If thermosets are heated beyond this range, the thermal decomposition range is usually reached directly. There is therefore a great deal of interest in developing materials that combine the advantages of both thermoplastics and thermosets, ie the materials can be formed inexpensively and at the same time show a high degree of heat resistance.

Aliphatic polyketones (PK) are thermoplastics that have good mechanical properties, in particular high impact strength and good media resistance. They have an alternating structure in which an ethylene or propylene group is followed by a keto group (carbonyl group), the proportions of the propylene groups being small and variable as a rule. PK are particularly characterized by good strength properties, high impact strength values at low temperatures, high mechanical fatigue strength, a low tendency to creep deformation as well as good sliding and wear behavior.

Aliphatic polyketones (PK) are linear polymers that are produced from carbon monoxide and α-olefins, the arrangement of the monomeric units in the polymeric chain in a strictly alternating manner. Nowadays, polyketone terpolymers are used almost exclusively instead of the classic polyketone copolymers, which are only produced from carbon monoxide and ethylene. These polyketone terpolymers consist of carbon monoxide, ethylene and preferably small amounts of propylene.

The reason for using terpolymers instead of copolymers is the significantly reduced brittleness of the terpolymers. Due to their strictly alternating polymer chain with an extremely low defect rate (one defect per million monomeric units) and the high number of polar keto groups, polyketone copolymers, consisting of carbon monoxide and ethylene, are highly crystalline, very hard but also very brittle, which makes their possible applications as polymer material significantly restricts. By adding small amounts of propylene (about 5%) during the synthesis, it was possible to disturb the crystallinity in such a way that the melting point falls from 255 ° C (copolymer of carbon monoxide and ethylene) to 220 ° C (terpolymer) and you an extremely tough polymer instead of a brittle one. Aliphatic polyketones are characterized, among other things, by high impact strength, low creep behavior, high chemical resistance and good tribological properties. However, the PC also have the aforementioned intrinsically given limit with regard to temperature resistance, which is typical for thermoplastics. Using the PK for the maximum long-term use temperature of around 80 ° C to 100 ° C (heat resistance HDT / A according to ISO 75) is therefore disadvantageous. The possible uses of this class of polymers are therefore significantly limited.

It would therefore be advantageous if the long-term service temperature of the aliphatic polyketones could be increased. To the temperature resistance and To further increase the mechanical stability of the PC, it has been proposed to crosslink the polymer chains. This principle has already been successfully applied to polyaryletherketones (PAEK).

Aliphatic polyketones differ from polyaryletherketones (PAEK), such as polyetheretherketones (PEEK), in that they do not contain any aromatic rings or ether groups. Polyaryletherketones (PAEK), such as polyetheretherketones (PEEK), are semi-crystalline high-performance polymers that have a high temperature and media resistance. They consist of alternating keto, ether and aryl groups. One advantage of PAEK is its thermoplastic processability. However, thermoplastics have an intrinsically given limit in terms of temperature resistance. In order to increase the temperature resistance and the mechanical stability of the PAEK, it has been proposed to crosslink the polymer chains. In the prior art, methods are used for crosslinking in which the PAEKs are crosslinked with diamines. Imine bonds (Schiff's bases) are formed, which can give the crosslinked polymers greater stability. The disadvantage here is that such crosslinked polymers are not flowable. They cannot therefore easily be processed thermoplastically from a melt of the polymer.

The process for chemical crosslinking of polyetheretherketones (PEEK) with diamines has been known since the 1980s. In this process, polyetheretherketone is first modified in diphenylsulfone as a solvent by attaching para-phenylenediamine. The solvent must then be removed by drying and further cleaning. It is problematic that with the method described, and also with the covalent attachment, cross-links are already formed. On the one hand, the temperature resistance increases, but on the other hand the glass transition temperature also increases and the thermoplastic processability is reduced lost. The polymer mass obtained is therefore not crosslinked thermoplastically from the melt, but rather by hot pressing.

It is also known to first modify the PAEK by analogous reaction of PEEK and phenylenediamine in diphenylsulfone as solvent and, after separating off the solvent and cleaning it, to crosslink it by hot pressing. Thermoplastic processing is also not described. The investigation shows that the products have a higher stability than uncrosslinked PEEK, which, however, is still in need of improvement.

WO 2010/011725 A2 describes a large number of amine crosslinkers in order to crosslink PAEK. However, the document contains only a single synthesis example which describes the crosslinking of PAEK with diphenylamine according to the literature cited above, in which a reaction initially takes place in diphenyl sulfone as solvent.

A method for crosslinking PAEK with non-amine crosslinkers is proposed in US Pat. No. 6,887,408 B2.

In order to crosslink PAEK, it has also been proposed in the prior art to functionalize the polymers themselves with crosslinkable amino groups. Such methods are described, for example, in US 2017/0107323 A1. The disadvantage here is that the functionalization of the PAEK with amino groups is relatively complex. In addition, the crosslinking of functionalized PAEK cannot be controlled as easily and variably as with a low molecular weight crosslinker.

WO2020 / 056052 describes crosslinkable polymer compositions comprising at least one aromatic polymer and at least one crosslinking compound which is capable of the at least one aromatic Crosslink polymer. Derivatives of fluorene, diphenylmethanes and dihydroanthracenes are used as crosslinking compounds.

The processes described in the prior art for crosslinking PAEK with diamines as low molecular weight crosslinkers are carried out in the presence of a high proportion of solvent, the moldings being produced by hot pressing (compression molding). The products are more temperature stable than comparable non-crosslinked PAEKs. However, it is disadvantageous that PAEK crosslinked in this way has a relatively low rigidity, since the crystallinity of the PAEK is lost when the polymers are dissolved in the solvent. During further processing, the crystallinity can only be recovered to a small extent because of the intrinsic steric hindrance of the chains through the crosslinking points. In addition, it is disadvantageous that the processes as a whole are very complex because they also require a large number of work steps because of the removal of the solvent. Another disadvantage is that the moldings are produced by hot pressing, which limits the application possibilities compared to thermoplastic processing. Hot pressing and comparable processes are carried out with non-flowable materials that cannot be converted into thermoplastic melts. As a result, the deformability is limited and no thin-walled or complex shaped bodies can be produced. For these reasons, such processes can only be automated to a very limited extent. Therefore, no efficient and cost-effective industrial production can take place on the basis of the known solvent-based processes.

WO 2010/011725 A2 describes very generally the production of moldings from crosslinked PAEK by extrusion. However, this is only a theoretical approach, as products are only manufactured on a laboratory scale and by hot pressing. There is no evidence that those with low molecular weight Crosslinkers crosslinked PAEK can be extruded, let alone that products with advantageous properties can be obtained in the process. A person skilled in the art also does not expect adequate success for PAEK and crosslinkers containing amino groups to be plasticized in the extruder and then subjected to a shaping step. On the one hand, it is problematic that at the required high melting temperatures, at which the components have to be mixed and processed, the crosslinking begins. On the other hand, it was not to be expected that PAEKs would be miscible and processable with such amine crosslinkers in the absence of a solvent. In practice, when low molecular weight components are incorporated into polymers, segregation processes are often observed. However, the homogeneous distribution of the crosslinker in the polymer is absolutely necessary for obtaining a stable product.

WO2020 / 030599 A2 describes a process for the production of a PAEK-containing, crosslinked molding, the crosslinker being a di (aminophenyl) compound in which the two aminophenyl rings are linked to one another via an aliphatic group which has a carbocyclic radical. Specifically, the crosslinking component 1- (4-aminophenyl) - 1,3,3-trimethylindan-5-amine DAPI (CAS No. 54628-89-6), the isomer mixture with 1- (4-aminophenyl) -1, 3, 3-trimethylindan-6-amine or the isomer mixture with the CAS no. 68170-20-7 is used. On the one hand, the high costs of producing the crosslinker are disadvantageous. On the other hand, the physico-chemical properties of the PAEK cross-linked with DAPI are in need of improvement.

Like the polyaryletherketones, the aliphatic polyketones contain keto groups, which can react with amines to form Schiff bases. But since aliphatic polyketones at elevated temperatures lead to a tautomerization of their keto groups into these corresponding Forms of enol and then tend to an uncontrollable further reaction of these enol groups, these reactions usually enter into dominant competition with crosslinking, which makes the transferability of the above-mentioned process to aliphatic polyketones less likely.

However, it would be very desirable to obtain crosslinked aliphatic polyketones, as these would be characterized, among other things, by improved mechanical properties as well as improved heat resistance, reduced creep behavior and increased chemical resistance.

Since volatile diamines are also associated with considerable hazards for the user and high environmental pollution at high temperatures, it would also be desirable to design the above-described method and the reagents used therein in such a way that there is no risk to users or the environment.

The invention is based on the object of providing methods and moldings which overcome the disadvantages described above.

The aim is to provide materials based on aliphatic polyketone (PK) that have improved temperature resistance, lower flammability and higher rigidity (module) at high temperatures. In addition, they should have good resistance to chemicals and a low tendency to creep.

In particular, the invention is based on the object of providing moldings which have materials with improved stability, but which are nevertheless easy to process. The materials should be able to be produced efficiently and inexpensively in a simple manner and should in particular be thermoplastic be processable. In doing so, it should be possible to avoid inefficient processes such as industrial presses.

The processes should also be as environmentally friendly as possible and feasible without endangering the user.

Surprisingly, the object on which the invention is based is achieved by methods, molded bodies and sealing articles, a crosslinking polyketone being crosslinked with a special diamine source with the formation of imine groups. In this case, a plasticized mixture of polyketone and diamine source can first be subjected to a shaping process to produce a molded body. The shaped body can then be subjected to crosslinking.

Summary of the invention

A first object of the invention is a shaped body comprising a matrix from the crosslinking of an aliphatic polyketone with at least one diamine source as crosslinker with the formation of imine groups, the diamine source being selected from

Di (aminophenyl) compounds in which the two aminophenyl rings are linked to one another via an aliphatic group which has a carbocyclic radical,

Diamine compounds selected from compounds of the formulas (I),

(II) and (III) where R ¹ , R ² , R ³ and R ^{4 are} independently selected from hydrogen,

Halogen, nitro, cyano, hydroxy, amino, Ci-Cö-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C6-Ci4-aryl, where the alkyl group, alkenyl group and alkynyl group are unsubstituted or ^{substituted by R a} and where the Aryl group is unsubstituted or substituted ^{by R b,}

R ⁵ , R ⁶ , R ^7, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are} independently selected from hydrogen, halogen, nitro, cyano, hydroxy, amino, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C6-Ci4-aryl, where the alkyl group, alkenyl group and alkynyl group are unsubstituted or ^{substituted by R a} and where the aryl group is unsubstituted or substituted ^{by R b,}

R ¹³ , R ¹⁴ , R ^15, R ¹⁶ , R ¹⁷ and R ^{18 are} independently selected from hydrogen, halogen, nitro, cyano, hydroxy, amino, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl , C6-Ci4-aryl, where the alkyl group, alkenyl group and alkynyl group are unsubstituted or ^{substituted by R a} and where the aryl group is unsubstituted or substituted ^{by R b,} X is selected from a bond, oxygen, sulfur, carbonyl, sulfonyl, sulfoxide, Ci-C6-alkylene, C2-C6-alkenylene and phenylene,

R ^{a is} selected from halogen, nitro, cyano, hydroxy, carboxyl, amino, C6-Ci2-aryl, the aryl group being unsubstituted or substituted ^{by R c,}

R ^{b is} selected from halogen, nitro, cyano, amino, Ci-C4-alkyl and C1-C4-haloalkyl,

R ^{c is} selected from halogen, nitro, cyano Ci-C4-alkyl and Ci-C4-haloalkyl,

- oligo / polymers which have at least two amide groups,

- Saturated, alicyclic compounds, the at least two primary

Have amine groups, oligo / polymers that contain these incorporated and

- Mixtures of these.

The invention further provides a method for producing a molded body, comprising the steps i) providing a mixture containing at least one aliphatic polyketone and at least one crosslinker, ii) producing a molded body from the mixture obtained in step i), and iii) thermal Treating the shaped body at a temperature at which the aliphatic polyketone is crosslinked, and wherein the crosslinker is selected from Di (aminophenyl) compounds in which the two aminophenyl rings are linked to one another via an aliphatic group which has a carbocyclic radical,

Diamine compounds, selected from compounds of the formulas (I), (II) and (III) in which

R ¹ , R ² , R ³ and R ^{4 are} independently selected from hydrogen, halogen, nitro, cyano, hydroxy, amino, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C6-Ci4-aryl where the alkyl group, alkenyl group and alkynyl group are unsubstituted or ^{substituted by R a} and where the aryl group is unsubstituted or substituted ^{by R b,}

R ⁵ , R ⁶ , R ^7, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are} independently selected from hydrogen, halogen, nitro, cyano, hydroxy, amino, Ci-C6-alkyl, C2-C6-alkenyl , C2-C6-alkynyl, C6-Ci4-aryl, where the alkyl group, alkenyl group and alkynyl group are unsubstituted or ^{substituted by R a} and where the aryl group is unsubstituted or substituted ^{by R b,} R ¹³ , R ¹⁴ , R ^15, R ¹⁶ , R ¹⁷ and R ^{18 are} independently selected from hydrogen, halogen, nitro, cyano, hydroxy, amino, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl , C6-Ci4-aryl, where the alkyl group, alkenyl group and alkynyl group are unsubstituted or ^{substituted by R a} and where the aryl group is unsubstituted or substituted ^{by R b,}

X is selected from a bond, oxygen, sulfur, carbonyl, sulfonyl, sulfoxide, Ci-C6-alkylene, C2-C6-alkenylene and phenylene,

R ^c is selected from halogen, nitro, cyano Ci-C4-alkyl and C1-C4-haloalkyl,

Oligo / polymers which have at least two amide groups, saturated, alicyclic compounds which have at least two primary amine groups, oligo / polymers which contain these incorporated and

Mixtures thereof.

The invention also relates to the moldings obtained by this process.

Another subject matter is polymer mixtures containing at least one polyketone (PK) and at least one crosslinker selected from

Di (aminophenyl) compounds in which the two aminophenyl rings are linked to one another via an aliphatic group which has a carbocyclic radical, Diamine compounds selected from compounds of the formula (I), (II) and (III), in which

R ⁵ , R ⁶ , R ^7, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are} independently selected from hydrogen, halogen, nitro, cyano, hydroxy, amino, Ci-C6-alkyl, C2-C6-alkenyl , C2-C6-alkynyl, C6-Ci4-aryl, where the alkyl group, alkenyl group and alkynyl group are unsubstituted or ^{substituted by R a} and where the aryl group is unsubstituted or ^{substituted by R b} , R ¹³ , R ¹⁴ , R ^15, R ¹⁶ , R ¹⁷ and R ^{18 are} independently selected from

Hydrogen, halogen, nitro, cyano, hydroxy, amino, Ci-Cö-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C6-Ci4-aryl, where the alkyl group, alkenyl group and Alkynyl group unsubstituted or ^{substituted by R a} and where the aryl group is unsubstituted or substituted ^{by R b,}

R ^{c is} selected from halogen, nitro, cyano Ci-C4-alkyl and Ci-C4-haloalkyl,

Oligo / polymers which have at least two amide groups, saturated, alicyclic compounds which have at least two primary amine groups, and oligo / polymers which contain these incorporated and mixtures thereof.

Another object of the invention is the use of a shaped body as defined above and below, or obtainable by a method as defined above and below, in the fields of automobiles, shipping, aerospace, rail vehicles, oil and gas industry, food - and packaging industry and medical technology, in particular as sealing articles, thrust washers, back-up rings, valves, connectors, insulators, snap hooks, bearings, sockets, foils, powders, coatings, fibers, sealing and O-rings, pipes and lines, cables , Casings and casings and housings for an electrical or chemical application that consists of a molded articles according to the invention or obtained by the process according to the invention exist or contain such a molded article.

Description of the invention

In the following, the terms “crosslinker” and “diamine source” are used synonymously.

The molded body according to the invention and the method according to the invention have the following advantages:

Substances that are potentially harmful to the environment and health, such as volatile aromatic amines, are avoided in the method according to the invention.

The crosslinked polyketones used according to the invention and the moldings according to the invention are distinguished by an increased temperature resistance and a higher maximum operating temperature than uncrosslinked PC.

The method according to the invention is characterized by low costs. The diamine sources used according to the invention are commercially available raw materials with generally low production costs.

The polyamides can serve as a source of low molecular weight polyamides and diamines. Depending on the reaction conditions, it is possible to regulate which crosslinking component is formed from the polyamides. By using polyamides as a source of diamine, PKs can also be crosslinked with low-boiling aliphatic diamines which otherwise cannot be implemented for procedural / safety / environmental reasons. The process according to the invention can be carried out in a technically simple manner, since only two components (preferably two granulates) have to be conveyed and mixed.

The moldings according to the invention have good tribological properties, in particular very good abrasion behavior. They are suitable for materials for use under abrasive wear conditions, e.g. as seals and plain bearing materials in conveyor systems for aggressive and abrasive media.

The molding according to the invention shows less swelling. Due to the long established components used, a reach registration is not necessary for the polymers.

The method according to the invention is sustainable. The non-crosslinked residues can be easily and easily recycled and do not have to be disposed of.

Polyketone

In principle, any aliphatic polyketones can be used as the polymer component. According to the invention, aliphatic polyketones (PK) are linear polymers which are produced from carbon monoxide and α-olefins, the arrangement of the monomeric units in the polymeric chain, preferably strictly, alternating. The aliphatic polyketone differs from polyaryletherketones (PAEK), such as polyetheretherketones (PEEK), in that it does not contain any aromatic rings or ether groups. PC preferred according to the invention are polyketone terpolymers. These polyketone terpolymers consist of carbon monoxide, ethylene and preferably small amounts of propylene.

CH, According to the invention, the aliphatic polyketones have linear polymer chains consisting of alternating alkylene units and keto groups. The alkylene units preferably comprise ethylene units as the main component, particularly preferably ethylene units as the main component combined with 1-methylethylene units. The aliphatic polyketones can differ in their average molecular weight and in the ratio of the starting materials used for the preparation, carbon monoxide, ethylene and a further alkene, for example propylene or 1- or 2-butylene. The aliphatic polyketones have keto groups which can be linked to form imine bonds. According to the invention, it is also possible to use mixtures of different aliphatic polyketones which differ, for example, in terms of their molecular weight or their composition. However, it is preferred to use a single PK because this allows a higher crystallinity and the associated temperature stability to be achieved.

In a preferred embodiment, the aliphatic polyketone has an average average molecular weight M _n (number average) in the range from 60,000 g / mol to 100,000 g / mol or an average average molecular weight Mw (mass average) in the range from 132,000 g / mol to 320,000 g / mol (determined by GPC measurements). The polydispersity of the aliphatic polyketones is preferably between 2.2 and 3.2. The aliphatic polyketones preferably also have a glass transition point of 10 to 14 ° C., a melting point of 218 to 226 ° C. and / or a recrystallization temperature of 170 to 182 ° C. (determined by DSC, DIN EN ISO 11357-1 to 3, 20 ° C / min heating rate). It has been found that PC, which is crosslinked according to the invention, has particularly advantageous properties, in particular improved mechanical and chemical properties. Preferably, the aliphatic polyketone (PK) at 240 ° C a melt flow index (MFR) in the range of 2 cm ^3/10 min to 200 cm ^3/10 min, in particular of 6 cm ^3/10 min to 60 cm ^3/10 min . The measurement is carried out in accordance with DIN ISO 1133, the material being melted at 240 ° C. and loaded with a 2.16 kg punch, after which the flowability is determined. An example of a particularly suitable aliphatic polyketone is, for example, M330A from Flyosung. The melt flow index generally correlates with the molecular weight of the polymer chains. It has been found that such a melt flow index is advantageous because, according to the invention, both good thermoplastic processability and miscibility can be achieved and a homogeneous product with high stability, and in particular high rigidity, can be obtained.

Suitable PK are commercially available, e.g. M230A (MFR = 150 g / 10 min at 240 ° C and 2.16 kg), M330A (MFR = 60 g / 10 min at 240 ° C and 2.16 kg), M340A (MFR = 60 g / 10 min at 240 ° C and 2.16 kg), M630A (MFR = 6 g / 10 min at 240 ° C and 2.16 kg) and M640A (MFR = 6 g / 10 min at 240 ° C and 2.16 kg) from Hyosung Corporation Co ., Ltd. as well as AKROTEK® PK-VM (MFR = 60 g / 10 min at 240 ° C and 2.16 kg), AKROTEK® PK-HM (MFR = 6 g / 10 min at 240 ° C and 2.16 kg) and AKROTEK® PK-XM (MFR = 2 g / 10 min at 240 ° C and 2.16 kg) from AKRO-PLASTIC GmbH.

It is particularly preferred to have such a PK with a melt flow index as mentioned above and the crosslinker in an amount of 0.05% by weight to 15% by weight, in particular 0.1% by weight to 5% by weight. %, based on the total amount of PK and crosslinker to be used. In a preferred embodiment, the proportion of the crosslinker is 0.1 to 1.5% by weight, in particular 0.4 to 1.0% by weight, based on the total amount of PC and crosslinker. With such a ratio and properties of the starting materials, the products are particularly easy to process accessible. In particular, the rigidity is particularly high, which is characterized by a high tensile modulus. Furthermore, such a PC can be processed at a temperature which still allows thermoplastic mixing with the crosslinker without the crosslinking reaction proceeding too quickly during the preparation of the mixing (= step i)). This gives a plasticized mass which can be used very well in a molding process for producing a molded body (= step ii)). The moldings obtained in this way can then be subjected to a thermoplastic treatment (= step iii), in which the final material properties are achieved by crosslinking the PC.

According to the invention, the shaped body is preferably a shaped body based on PK. "On the basis of PC" means that the PC is the essential structure-giving polymer component of the molding. In one embodiment it is preferred that the PC is the only polymer component of the molded body. In a further embodiment, the PK is present as a mixture with other polymers, in particular thermoplastic polymers. Preferred further polymers include thermoplastic polyurethanes (TPU) and other thermoplastic elastomers, polyesters, liquid crystalline polyesters (LCP), polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and polycarbonate (PC). Preferred mass ratios between PK and the further polymers, in particular thermoplastic further polymers, are 1: 1 to 100: 1, preferably 5: 1 to 100: 1, particularly preferably 10: 1 to 100: 1. Furthermore, the shaped body can contain fillers such as fibers and / or customary additives such as processing aids and / or functional components. The cross-linked PC forms a matrix in which any additives that may be present are evenly distributed. Crosslinker

The at least one crosslinker preferably contains at least 80% by weight, in particular at least 90% by weight, in particular at least 99% by weight, based on the total weight of the crosslinker, of a diamine source selected from

Diamine compounds selected from compounds of the formula (I), (II) and (III),

Oligo- / polymers which have at least two amide groups, saturated, alicyclic compounds which have at least two primary amine groups, oligo- / polymers which contain these incorporated and

Mixtures thereof.

In a preferred embodiment, the at least one crosslinker contains at least 80% by weight, in particular at least 90% by weight, in particular at least 99% by weight, based on the total weight of the crosslinker, of a diamine source selected from oligo / - Polymers which have at least two amide groups, saturated, alicyclic compounds which have at least two primary amine groups, oligomers / polymers which contain these incorporated and mixtures thereof.

The amount of crosslinker is adjusted with a view to the desired degree of crosslinking. The proportion of the crosslinking agent is preferably 0.05% by weight to 15% by weight, in particular 0.1% by weight to 5% by weight, based on the total amount of aliphatic polyketone and crosslinking agent. In a In a preferred embodiment, the proportion of the crosslinker is 0.1 to 1.5% by weight, in particular 0.4 to 1.0% by weight. It has been found that the stability of the product with such a crosslinker content can be particularly advantageous.

In a preferred embodiment, the crosslinker has a boiling point of 1013 mbar, which is at least 300 ° C., in particular at least 350 ° C., in a special embodiment at least 400 ° C. This is advantageous because such crosslinkers only have a relatively low vapor pressure at the required high processing temperatures. The boiling point of the crosslinker is preferably 1013 mbar in a range from 300.degree. C. to 500.degree. C., in particular in a range from 350.degree. C. to 500.degree. The melting point of the crosslinker is advantageously below the melting point of the aliphatic polyketone (PK). This results in good processability and low risk to the user.

In a preferred embodiment, the diamine source used as a crosslinker is an oligo / polymer which has at least two amide groups.

In the following, the term polyamide is used synonymously with an oligo / polymer which has at least two amide groups.

Insofar as the polyamides are referred to below as crosslinkers, this term also includes the lower molecular weight products formed during the reaction in the process according to the invention (e.g. from hydrolytic cleavage of amide groups with the formation of amine groups capable of reacting with the keto groups of the PK) to the extent that these are capable of networking the PK. To this extent, both the polyamides used to provide the mixture of PC and crosslinker and any oligomers and diamine monomers thereof containing amine groups can serve as crosslinkers. The term polyamides is used below to summarize homo- and copolyamides. In the context of the invention, to designate the polyamides, some customary abbreviations are used, which consist of the letters PA and the numbers and letters that follow. Some of these abbreviations are defined in DIN EN ISO 1043-1. Polyamides which can be derived from aminocarboxylic acids of the type H2N- (CH2) z-COOH or the corresponding lactams are identified as PA Z, where Z denotes the number of carbon atoms in the monomer. So stands z.

B. PA 6 for the polymer of e-caprolactam or e-aminocaproic acid. Polyamides derived from diamines and dicarboxylic acids of the types H2N- (CH2) x- NH2 and HOOC- (CH2) _y -COOH are identified as PA xy, where x is the number of carbon atoms in the diamine and y is the number of carbon atoms referred to in the dicarboxylic acid. To designate copolyamides, the components are listed in the order of their proportions, separated by slashes. So is z. B. PA 66/610 the copolyamide of hexamethylenediamine, adipic acid and sebacic acid. The following abbreviations are used for the monomers used according to the invention with an aromatic or cycloaliphatic group: T = terephthalic acid, I = isophthalic acid, MXDA = m-xylylenediamine, IPDA = isophoronediamine, PACM = 4,4'-methylenebis (cyclohexylamine), MACM = 2, 2'-dimethyl-4,4'-methylenebis (cyclohexylamine).

The polyamides can be described by the monomers used for their production. A polyamide-forming polymer is a monor suitable for polyamide formation.

In a preferred embodiment, the crosslinker contains a polymer which has at least two amide groups, the polymer polyamide-forming monomers in copolymerized form, which are selected from

A) unsubstituted or substituted aromatic dicarboxylic acids and derivatives of unsubstituted or substituted aromatic dicarboxylic acids,

B) unsubstituted or substituted aromatic diamines,

C) aliphatic or cycloaliphatic dicarboxylic acids,

D) aliphatic or cycloaliphatic diamines,

E) monocarboxylic acids,

F) monoamines,

G) at least trivalent amines,

Fl) lactams,

I) w amino acids, and

K) from A) to I) different compounds cocondensable therewith, and mixtures thereof.

In a preferred embodiment of the invention, polyamides, preferably with a melting point of at most 260 ° C., are used as crosslinking agents. In particular, aliphatic polyamides are used. In addition, the stipulation applies that at least one of the components A) or B) and at least one of the components C) or D) must be present. In a special embodiment, the proviso applies that at least one component A) and at least one component D) must be present.

The aromatic dicarboxylic acids A) are preferably selected from unsubstituted or substituted phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acids or diphenyldicarboxylic acids and the derivatives and mixtures of the aforementioned aromatic dicarboxylic acids. Substituted aromatic dicarboxylic acids A) have preferably at least one Ci-C4-alkyl radical. Substituted aromatic dicarboxylic acids A) particularly preferably have one or two C1-C4-alkyl radicals. These are preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, particularly preferably methyl, ethyl and n-butyl, very particularly preferably methyl and ethyl and especially methyl . Substituted aromatic dicarboxylic acids A) can also carry further functional groups which do not interfere with the amidation, such as, for example, 5-sulfoisophthalic acid, its salts and derivatives. Of these, the sodium salt of dimethyl 5-sulfoisophthalate is preferred. The aromatic dicarboxylic acid A) is preferably selected from unsubstituted terephthalic acid, unsubstituted isophthalic acid, unsubstituted naphthalenedicarboxylic acids, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid and 5-sulfoisophthalic acid. The aromatic dicarboxylic acid A) used is particularly preferably terephthalic acid, isophthalic acid or a mixture of terephthalic acid and isophthalic acid.

The aromatic diamines B) are preferably selected from bis (4-aminophenyl) methane, 3-methylbenzidine, 2,2-bis (4-aminophenyl) propane, 1,1-bis (4-aminophenyl) -cyclohexane, 1,2-diaminobenzene, 1,4-diaminobenzene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,3-diaminotoluene (s), m-xylylenediamine, N, N'-dimethyl-4,4 '-biphenyl-diamine, bis- (4-methyl-aminophenyl) -methane, 2,2-bis- (4-methylaminophenyl) -propane or mixtures thereof. The aromatic diamine used is particularly preferably m-xylylenediamine.

The aliphatic or cycloaliphatic dicarboxylic acids C) are preferably selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane-1,11-dicarboxylic acid, dodecane-1,12-dicarboxylic acid, maleic acid, fumaric acid or itaconic acid, cis- and trans-cyclohexane-1,2-dicarboxylic acid, cis- and trans-cyclohexane-1,3-dicarboxylic acid, cis- and trans-cyclohexane-1,4-dicarboxylic acid, cis- and trans-cyclopentane-1 , 2-dicarboxylic acid, cis- and trans-cyclopentane-1,3-dicarboxylic acid and mixtures thereof.

The aliphatic or cycloaliphatic diamines D) are preferably selected from ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, decamethylenediamine, 2-methylenediamine, 2,2-methylenediamine, dodecamethylenediamine , 4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 2,4-dimethyloctamethylenediamine, 5-methylnonanediamine, bis- (4-aminocyclohexyl) methane, 3,3'-dimethyl-4,4'diaminodicyclohexylmethane and Mixtures thereof.

The diamine D) is particularly preferably selected from hexamethylenediamine, 2-methylpentamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, 1,3 -Bis- (aminomethyl) -cyclohexane and 1, 4-bisaminomethylcyclohexane, 5-amino-2,2,4- trimethyl-1 -cyclopentanemethylamine, 5-amino-1, 3,3- trimethylcyclohexanemethylamine (isophoronediamine), 3,3 '-Dimethyl-4,4'-diaminodicyclohexyl methane, [3- (aminomethyl) -2-bicyclo [2.2.1] heptanyl] methanamine, aminated dimer fatty acids and mixtures thereof. In a preferred embodiment of the invention, the aqueous solution contains at least one diamine D), which is selected from hexamethylene diamine, bis (4-aminocyclohexyl) methane (PACM), 3,3'-dimethyl-4,4'diaminodicyclohexylmethane (MACM) , Isophoronediamine (IPDA), and mixtures thereof. The monocarboxylic acids E) serve to end-cap the polyamide oligomers used according to the invention. In principle, all monocarboxylic acids which are capable of reacting with at least some of the available amino groups under the reaction conditions of the polyamide condensation are suitable. Suitable monocarboxylic acids E) are aliphatic monocarboxylic acids, alicyclic monocarboxylic acids and aromatic monocarboxylic acids. These include acetic acid, propionic acid, n-, iso- or tert. - Butyric acid, valeric acid, trimethylacetic acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, cyclohexanecarboxylic acid, oleic acid, phenylbenzoic acid, 1-naphthalenic acid, phenyl-naphthoic acid, oleic acid, phenylbenzoic acid, oleic acid, naphthoic acid, naphthoic acid, pelargonic acid, caprylic acid, pelargonic acid, phenylbenzoic acid , Linoleic acid, linolenic acid, erucic acid, fatty acids from soy, linseed, castor and sunflower, acrylic acid, methacrylic acid, tertiary saturated monocarboxylic acids (for example Versatic® acids from Royal Dutch Shell plc) and mixtures thereof.

If unsaturated carboxylic acids or their derivatives are used as monocarboxylic acids E), it can be useful to add commercially available polymerization inhibitors to the aqueous solution. The monocarboxylic acid E) is particularly preferably selected from acetic acid, propionic acid, benzoic acid and mixtures thereof. In a very particularly preferred embodiment, the aqueous solution contains exclusively acetic acid as monocarboxylic acid E). In a further very particularly preferred embodiment, the aqueous solution contains exclusively propionic acid as monocarboxylic acid E). In a further very particularly preferred embodiment, the aqueous solution contains exclusively benzoic acid as monocarboxylic acid E). The monoamines F) serve to end-cap the polyamide oligomers used according to the invention. In principle, all monoamines which are capable of reacting with at least some of the available carboxylic acid groups under the reaction conditions of the polyamide condensation are suitable. Suitable monoamines F) are aliphatic monoamines, alicyclic monoamines and aromatic monoamines. These include methylamine, ethylamine, propylamine, butylamine, flexylamine, fleptylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dicyclohexylamine, aniline, toluidine, diphenylamine, naphthylamine, and mixtures thereof.

Suitable at least trivalent amines G) are selected from N '- (6-aminohexyl) hexane-1,6-diamine, N' - (12-aminododecyl) - dodecane-1, 12-diamine, N'- (6-aminohexyl) dodecane-1,12-diamine, N '- [3- (aminomethyl) -3,5,5-trimethyl-cyclohexyl] hexane-1,6-diamine, N' - [3- (aminomethyl) -3.5, 5-trimethyl-cyclohexyl] dodecane-1, 12-diamine, N '- [(5-amino-1, 3,3-trimethyl-cyclohexyl) methyl] hexane-1, 6-diamine, N' - [(5- amino-1, 3,3-trimethyl-cyclohexyl) methyl] dodecane-1, 12-diamine, 3 - [[[3- (aminomethyl) -3,5,5-trimethyl-cyclohexyl] amino] methyl] -3, 5,5-trimethyl-cyclohexanamine, 3 - [[(5-amino-1, 3,3-trimethyl-cyclohexyl) methylamino] methyl] -3,5,5-trimethyl-cyclohexanamine, 3- (aminomethyl) -N- [3- (aminomethyl) -3,5,5-trimethyl-cyclohexyl] -3,5,5-trimethyl-cyclohexanamine. Preferably no at least trivalent amines G) are used.

Suitable lactams F1) are e-caprolactam, 2-piperidone (d-valerolatam), 2-pyrrolidone (g-butyrolactam), capryllactam, enanthlactam, lauryllactam and mixtures thereof.

Suitable w-amino acids I) are 6-aminocaproic acid, 7-aminoheptanoic acid,

11-aminoundecanoic acid, 12-aminododecanoic acid and mixtures thereof. Suitable compounds K) different from A) to I) and thus cocondensable are at least trivalent carboxylic acids, diaminocarboxylic acids, etc. Suitable compounds K) are furthermore 4 - [(Z) -N- (6-aminohexyl) -C-hydroxycarbonimidoyl] benzoic acid, 3 - [(Z) -N- (6-aminohexyl) -C-hydroxycarbonimidoyl] benzoic acid, (6Z) -6- (6-aminohexylimino) -6-hydroxycarboxylic acid, 4 - [(Z) - N - [(5-Amino-1, 3,3-trimethyl-cyclohexyl) methyl] -C-hydroxy-carbonimidoyl] benzoic acid, 3 - [(Z) -N - [(5-amino-1,3,3- trimethyl-cyclohexyl) methyl] -C-hydroxy-carbonimidoyl] benzoic acid, 4 - [(Z) -N- [3- (aminomethyl) -3,5,5-trimethyl-cyclohexyl] -C-hydroxycarbonimidoyl] benzoic acid, 3 - [(Z) -N- [3- (aminomethyl) -3,5,5-trimethyl-cyclohexyl] -C-hydroxy-carbonimidoyl] -benzoic acid and mixtures thereof.

In a further preferred embodiment of the invention, a crosslinker selected from polyamides, their copolymers and mixtures thereof is used, the crosslinker having a melting range from 200 ° C to 250 ° C, preferably a melting range from 220 ° C to 240 ° C, in particular a Melting range from 220 ° C to 230 ° C.

In a further preferred embodiment, the at least one crosslinker is selected from a saturated, alicyclic compound which has at least two primary amine groups and oligomers / polymers which contain these incorporated. Suitable compounds are those whose boiling point is greater than 300 ° C. In a preferred embodiment, these compounds are in the form of a liquid in step i). They can thus serve as an internal solvent in melt blending. The saturated, alicyclic compound is preferably an aminated fatty acid dimer (dimer fatty acid).

The term "fatty acid dimer" as used herein refers to the dimerized product of the reaction of two or more than two simple or polyunsaturated fatty acids. Such fatty acid dimers are well known in the art and typically exist as mixtures.

Aminated dimer fatty acids (also known as aminated dimerized fatty acids or dimer acids) are mixtures that are produced by the oligomerization of unsaturated fatty acids. Unsaturated C12 to C22 fatty acids can be used as starting materials. Depending on the number and position of the double bonds of the C12 to C22 fatty acids used to produce the dimer fatty acids, the amine groups of the dimer fatty acids are linked to one another by hydrocarbon radicals which predominantly have 24 to 44 carbon atoms. These hydrocarbon radicals can be unbranched or branched and can have double bonds, C6-cycloaliphatic hydrocarbon radicals or O6-aromatic hydrocarbon radicals; the cycloaliphatic radicals and / or the aromatic radicals can also be present in condensed form. The radicals which connect the amine groups of the dimer fatty acids preferably have no aromatic hydrocarbon radicals, very particularly preferably no unsaturated bonds. Dimers of Cie fatty acids, i.e. fatty acid dimers with 36 carbon atoms, are particularly preferred. These can be obtained, for example, by dimerizing oleic acid, linoleic acid and linolenic acid and mixtures thereof. Following the dimerization, a hydrogenation and then an amination may take place.

In a particular embodiment, the saturated, alicyclic compound is

In a particular embodiment, the saturated, alicyclic compound is A special embodiment are polymers which contain at least one aminated dimer fatty acid incorporated. An even more specific embodiment are polymers that make up the compound built-in included.

In a further preferred embodiment, the at least one crosslinker is a mixture containing an oligomer / polymer which has at least one amide group and a saturated, alicyclic compound which has at least two primary amine groups.

In a further preferred embodiment, the at least one crosslinker is a mixture containing an oligo / polymer which has at least one amide group and an oligo / polymer which contains in copolymerized form at least one saturated, alicyclic compound which has at least two primary amine groups. In a further preferred embodiment, the at least one crosslinker is a diamine compound selected from compounds of the formulas (I), (II) and (III) where R ¹ , R ² , R ³ and R ^{4 are} independently selected from hydrogen,

R ^{c is} selected from halogen, nitro, cyano, Ci-C4-alkyl and Ci-C4-haloalkyl. Examples of Ci-C4-alkyl groups are, in particular, methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl and tert-butyl.

Examples of Ci-C6-alkyl groups are in particular the aforementioned C1-C4-alkyl groups as well as n-pentyl and n-hexyl.

Ci-C4-haloalkyl preferably represents one of the aforementioned C1-C4-alkyl groups, which preferably has 1, 2, 3, 4 or 5, preferably 1, 2 or 3 halogen substituents. This includes, for example, trifluoromethyl.

Halogen represents fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.

Unsubstituted C6-Ci4-aryl is preferably phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular phenyl or naphthyl. Substituted C6-Ci4-aryl preferably has 1, 2, 3, 4 or more than 4 radicals, preferably selected from halogen, nitro, cyano, Ci-C4-alkyl and Ci-C4-haloalkyl. Examples of C6-Ci4-aryl substituted with Ci-C4-alkyl are tolyl, xylyl, mesityl. Ci-C6-alkylene is preferably -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2- or -C (CH ₃ ) ₂ -.

In a preferred embodiment, the at least one crosslinker is a compound of the formula (I) or (II), where

R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and R ^{11 represent} hydrogen,

R ¹ and R ^{4 are} independently selected from hydrogen, halogen, nitro, cyano, hydroxy, amino, Ci-Cö-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C6-Ci4-aryl, where the alkyl group, Alkenyl group and alkynyl group are unsubstituted or ^{substituted by R a} and wherein the aryl group is unsubstituted or substituted ^{by R b,}

R ⁹ and R ^{12 are} independently selected from hydrogen, halogen, nitro, cyano, hydroxy, amino, Ci-Cö-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C6-Ci4-aryl, where the alkyl group, Alkenyl group and alkynyl group unsubstituted or ^{substituted by R a} and where the aryl group is unsubstituted or substituted ^{by R b,}

R ^{b is} selected from halogen, nitro, cyano, amino, Ci-C4-alkyl and C1-C4-haloalkyl, and

R ^c is selected from halogen, nitro, cyano Ci-C4-alkyl and Ci-C4-haloalkyl. In a particularly preferred embodiment, the at least one crosslinker is a compound of the formula (Ia) or (II. A) R ¹ , R ⁴ , R ⁹ and R ¹² and X have the following meanings In a further preferred embodiment, the crosslinker is selected from compounds of the formulas (III.a) and (III.b):

(lll.a) (IN. b)

In a special embodiment, the crosslinker is selected from compounds (III.a1) and (III.b1):

(lll.al) (III. b1)

In a further preferred embodiment, the at least one crosslinker is a di (aminophenyl) compound in which the two aminophenyl rings are linked to one another via an aliphatic group which has a carbocyclic radical.

Di (aminophenyl) compounds used as crosslinkers (or as a source of diamine) have two aminophenyl rings connected to one another. The compounds are therefore primary diamines. In one embodiment of the invention, each phenyl ring has only a single amino group. However, it is also conceivable that the phenyl rings independently of one another have two or three amino groups. The compounds are low molecular weight and not polymers. In addition to the amino groups, the phenyl rings can have further substituents, such as alkyl or

Halogen groups. The two aminophenyl rings are linked to one another via an aliphatic group. Aliphatic groups consist only of carbon and hydrogen and are not aromatic. The di (aminophenyl) compounds used as crosslinkers (or as a source of diamine) have apart from the two phenyl rings, preferably no further double or triple bonds. The aliphatic group has a carbocyclic radical. Carbocyclic radicals are hydrocarbon rings which, for example, can have 4 to 7 carbon atoms, preferably 5 or 6 carbon atoms. The carbocyclic radical can comprise double bonds of the phenyl rings. The carbocyclic group preferably has only a single aliphatic hydrocarbon ring. The aliphatic group preferably has a total of 5 to 15 carbon atoms, in particular 6 to 8 carbon atoms. Because of the aliphatic group between the carboyclic radicals, the two phenyl rings are not conjugated.

According to the invention, it has surprisingly been found that PK which is crosslinked with such di (aminophenyl) compounds has particularly advantageous properties. In particular, the crosslinked PC has improved thermal stability and increased mechanical stability.

In a preferred embodiment, the di (aminophenyl) compound used as a crosslinker (or as a source of diamine) is a fused compound in which only one of the two phenyl rings is fused to the carbocyclic radical. Anellation (condensation) refers to the addition of another ring to a ring of a cyclic molecule. The two fused rings share two carbon atoms and thus a C-C double bond of the phenyl ring. The use of such fused crosslinkers has the advantage that a particularly rigid and regular connection can be formed between the PK chains, as a result of which particularly high temperature stability and rigidity of the products can be achieved.

The amino groups of the di (aminophenyl) compound used as a crosslinker (or as a source of diamine) can in principle be at any positions in the Phenyl group be present, so in ortho-, meta- or para-position with respect to the aliphatic connection of the two phenyl rings. In the embodiment that each phenyl group has only a single amino group, it is preferred that the two amino groups are as far apart from one another as possible. This can be achieved if the two amino groups are attached to the para position with respect to the aliphatic compound and / or to the 4- and 4'-positions of the phenyl rings. Thus, in a preferred embodiment, the Diaminodiphenylverbindung is a 4,4 ^{'-Diaminodiphenylverbindung.} In general, the advantage of amino groups that are as far apart as possible from one another can be that the formation of undesired intramolecular reactions in which a crosslinker forms two bonds with the same PK polymer chain is reduced. Such intramolecular reactions with the crosslinker can disrupt the crystalline structure of the PK without being effective for crosslinking and thereby reduce the stability of the product.

In a preferred embodiment of the invention, the di (aminophenyl) compound used as a crosslinker (or as a source of diamine) is an asymmetric compound.

In a preferred embodiment of the invention, the di (aminophenyl) compound used as a crosslinker (or as a source of diamine) is a compound of the general formula (IV) in which R ¹⁹ and R ^{20 are} independently selected from H, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, in particular with 1 to 4 carbon atoms, in particular methyl or ethyl, substituted or unsubstituted aryl with 5 to 12 carbon atoms, F and CI, and where Z is the aliphatic group containing a carbocyclic radical. Each phenyl ring can have one, two or three radicals R ¹⁹ or R ²⁰ , which are selected independently of one another. A phenyl ring preferably has only one radical R ¹⁹ and / or R ²⁰ . The radicals R ¹⁹ and R ^{20 are} each particularly preferably H. Crosslinkers without additional radicals R ¹⁹ and R ²⁰ are relatively readily available and can be processed into more stable, crosslinked PC.

The radical Z can be linked to each phenyl radical via two or one bond. The radical Z is preferably connected to a phenyl radical via two bonds and to the second phenyl radical via one bond.

In a further preferred embodiment of the invention, the crosslinker is a compound of the general formula (IV.a) in which

X is 3 or 4 depending on the number of bonds of the ^{phenyl ring substituted with R 19} to the group Z, y is 3 or 4 depending on the number of bonds of the ^{phenyl ring substituted with R 20} to the group Z, the radicals R ^{19 are} in each case independently selected from hydrogen, unsubstituted or substituted or alkyl with 1 to 20 carbon atoms, unsubstituted or substituted or aryl with 5 to 14 carbon atoms, F and CI, the radicals R ^{20 are} in each case independently selected from hydrogen, unsubstituted or substituted or alkyl with 1 to 20 carbon atoms, unsubstituted or substituted or aryl with 5 to 14 carbon atoms, F and CI,

Z is an aliphatic group which has a carbocyclic radical, where Z is linked to each of the two phenyl rings via one or via two bonds.

Z is preferably ^{bonded to the phenyl ring substituted by R 19} via two bonds. In the compounds (IV.a), x then stands for 3. Z is preferably bonded to the phenyl ring substituted ^{by R 20 via a bond.} In the compounds (IV.a) y then stands for 4. Specifically, x stands for 3 and y stands for 4. In particular, Z and the two phenyl rings form an indane structure to which a phenyl ring is bonded.

In the compounds of the formulas (IV) and (IV.a), alkyl with 1 to 20 carbon atoms preferably includes the definition given above for Ci-C6-alkyl and additionally n-heptyl, n-octyl, 2-ethylhexyl, n- Nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-flexadecyl, n-fleptadecyl, n-octadecyl, n-nonadecyl, arachinyl and their constitutional isomers. Alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl, is particularly preferred.

Substituted alkyl with 1 to 20 carbon atoms has at least 1 (for example 1, 2, 3, 4 or more than 4) substituents, preferably selected from flalogen, nitro, cyano and Ci-C4-alkoxy. Substituted alkyl stands specifically for C1-C4- Haloalkyl, which preferably has 1, 2, 3, 4 or 5, preferably 1, 2 or 3 halogen substituents. These include, for example, trifluoromethyl.

In the compounds of the formulas (IV) and (IV.a), unsubstituted aryl having 5 to 14 carbon atoms preferably represents phenyl, naphthyl, anthracenyl and phenanthrenyl, in particular phenyl or naphthyl. Unsubstituted aryl with 5 to 12 carbon atoms stands in particular for phenyl or naphthyl. Substituted aryl with 5 to 14 carbon atoms or substituted aryl with 5 to 12 carbon atoms preferably has 1, 2, 3, 4 or more than 4 radicals, preferably selected from halogen, nitro, cyano, Ci-C4-alkyl and C1 -C4 haloalkyl. Examples of substituted aryl with 5 to 14 carbon atoms or substituted aryl with 5 to 12 carbon atoms are tolyl, xylyl, mesityl.

In the compounds of the formula (IV.a), the radicals R ^{19 are} preferably selected from hydrogen, substituted or unsubstituted alkyl having 1 to 4 carbon atoms, F and Cl. The radicals R ¹⁹ are particularly preferably selected from hydrogen and unsubstituted alkyl having 1 to 4 carbon atoms.

In the compounds of the formula (IV.a), the radicals R ^{20 are} preferably selected from hydrogen, substituted or unsubstituted alkyl having 1 to 4 carbon atoms, F and Cl. The radicals R ²⁰ are particularly preferably selected from hydrogen and unsubstituted alkyl having 1 to 4 carbon atoms.

Each phenyl ring preferably has no, one or two radicals R ¹⁹ or R ²⁰ which are different from hydrogen. In a special embodiment, the radicals R ¹⁹ and R ²⁰ all represent hydrogen. Compounds of formula (IV.a) in which the radicals R ¹⁹ and R ²⁰ all represent hydrogen are relatively readily available and can be processed into more stable, crosslinked PC. In a preferred embodiment, the crosslinker is a compound of the general formula (V) where R ¹⁹ and R ^{20 are} independently selected from H, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, in particular with 1 to 4 carbon atoms, in particular methyl or ethyl, substituted or unsubstituted aryl with 5 to 12 carbon atoms , F and CI, and where R ^{21 is} a carbocyclic radical which has 2 to 3 carbon ring atoms and which can be substituted by at least one alkyl group with 1 to 4 carbon atoms, in particular methyl or ethyl. The radicals R ¹⁹ and R ²⁰ are particularly preferably each H. The carbocyclic radical R ²¹ is therefore a pentyl or flexyl radical. Such crosslinkers have the advantage that a particularly good combination of temperature stability and mechanical stability of the crosslinked PC can be obtained.

In a preferred embodiment, the crosslinker is a compound of the general formula (Va): where R ^{21 is} selected as indicated above. Such crosslinkers have the advantage that a particularly good combination of temperature stability and mechanical stability of the crosslinked PC can be obtained. In a preferred embodiment, the crosslinker has the formula (V.a1): In the tests carried out, the connection led to a particularly advantageous combination of temperature stability and mechanical stability of the crosslinked PC. The chemical name is 1- (4-aminophenyl) -1, 3,3-trimethyl-indan-5-amine (CAS No. 54628-89-6). In a further preferred embodiment, the crosslinker has the formula (V.b1): In the tests carried out, the connection also leads to a particularly advantageous combination of temperature stability and mechanical stability of the crosslinked PC. The chemical name is 1- (4-aminophenyl) -1, 3,3-trimethyl-indan-6-amine. In a further preferred embodiment, the crosslinker has a mixture of compounds of the formulas (V.a1) and (V.b1). In the tests carried out, this crosslinker likewise leads to a particularly advantageous combination of temperature stability and mechanical stability of the crosslinked PC.

In a further preferred embodiment, the crosslinker has the formula (VII):

In the tests carried out, this crosslinker likewise leads to a particularly advantageous combination of temperature stability and mechanical stability of the crosslinked PC. The chemical name is 1- (4-aminophenyl) -1, 3,3-trimethyl-indan-amine (CAS No. 68170-20-7). The amino group on the aromatic ring of the indane can also occur in all positions. Also included are mixtures of 1- (4-aminophenyl) -1,3,3-trimethyl-indan-amines in which the amino group on the aromatic ring of the indane is in different positions. It is preferred according to the invention to use a single specific crosslinker in order to obtain material properties that are as uniform as possible. However, it is also possible to use mixtures of two or more crosslinkers. The method according to the invention relates to a crosslinking reaction in which the polymer chains of the polyketones are covalently and intramolecularly linked to one another.

Step i)

In step (i) a mixture is provided which contains the polyketone and the crosslinker. The mixture provided in step (i) can be produced by customary compounding processes. In step i), the at least one polyketone, the at least one crosslinker, optionally a filler and reinforcing material and optionally a further different additive is preferably melt-blended or dry-blended (compounded).

When mixing in the melt or melt mixing, the polymers are heated above their melting temperature and intensively mixed by rolling, kneading or extrusion. The temperature in step (i) is preferably set so that the mixture is easy to process and has a viscosity suitable for compounding. In addition, the temperature in step (i) is preferably set so that no significant reaction takes place between the polyketone and the crosslinker. In addition, the residence time at temperatures at which a reaction between the PC and the crosslinker already takes place should be kept as short as possible. In contrast to PAEK, in which the reactivity of the reacting carbonyl groups is reduced by mesomeric effects of the neighboring phenylene groups, the amine crosslinking of PK with the crosslinker described according to the invention preferably begins in the melt. According to the invention, it is not necessary, as in the case of the processes described in the prior art, for the crosslinkers to be covalently attached to the PC via aminic bonds. This is beneficial because According to the invention, such an additional reaction step can be dispensed with, which would have to be precisely controlled in order to prevent an undesired further reaction of the intermediates and a premature crosslinking resulting therefrom.

In one embodiment, in step i) the at least one polyketone, the at least one crosslinker, optionally a filler and reinforcing material and optionally a further additive different therefrom is fed into an extruder, mixed with plasticization and optionally granulated.

The temperature in step i) during melt mixing is preferably in the range from 220 to 260 ° C.

In a further embodiment, in step i) the at least one polyketone, the at least one crosslinking agent, optionally a filler and reinforcing material and optionally a further different additive is preferably subjected to dry mixing. The components mentioned can be mixed using any known dry mixing technique. A dry blend of polyketone, the at least one crosslinker, optionally the filler and reinforcing material and optionally a further additive different therefrom is obtained.

The temperature in step i) during dry mixing is below the softening range of PK, preferably in the range from 0.degree. C. to 100.degree.

When the mixture is frozen, thorough mixing takes place by suitable means, such as stirring or kneading devices, in order to achieve a uniform distribution of the crosslinking agent in the polymer. This is of great importance in order to obtain uniform material properties with regard to stability. The crosslinkable mixture is preferred after the freezing point without further intermediate steps which change the composition are processed further in step (ii).

When mixing (compounding) an intermediate product can be obtained, for example a granulate. These intermediate products are stable for a long time at temperatures in the range of less than 80 ° C, preferably less than 50 ° C, especially at ambient temperature and below, and can, for example, be temporarily stored and / or transported to another location and processed further.

In a particularly preferred embodiment of the invention, the mixture does not contain any solvent. In particular, no external solvent is added to the mixture. According to the invention, it was surprisingly found that mixtures of the PC and the crosslinker can be processed without the use of a solvent, with thorough mixing taking place.

The mixture is preferably heated to a temperature at which it is in liquid or flowable (plasticized) form. In order to obtain a homogeneous mixture, it is preferred to choose the temperature and residence time so that there is no significant crosslinking.

In a preferred embodiment, to produce a mixture in step i), the crosslinker is added continuously to the PC. The components can be in liquid or solid form. In this way a particularly uniform mixture can be obtained. The crosslinking agent is preferably added with thorough mixing, for example with stirring, kneading, rolling and / or extrusion. In a preferred embodiment, the crosslinker is supplied in the form of a concentrate.

This has the advantage that the crosslinker can be better dosed, whereby the uniformity of the mixture can be improved. Overall, with continuous addition of the crosslinker, a particularly homogeneous mixture can be obtained, so that particularly regular crosslinking is achieved. This can prevent areas of different degrees of crosslinking from arising, which can lead to inhomogeneities and possible damage to the product in the event of thermal or mechanical stress. In this way, particularly good properties with regard to temperature stability and mechanical stability can be achieved.

Step (ii)

In step (ii) a molding is produced from the mixture. Step (ii) of producing the shaped body comprises all measures by which the mixture is brought into a three-dimensional shape that is retained in the cured, crosslinked state. The molding is preferably produced by means of molding processes such as are customary for thermoplastics. It is preferred here for the molding to be produced before the crosslinking and / or during the crosslinking. It is generally not critical if the mixture used in step ii) already contains small proportions of crosslinked products. It is particularly preferable for the shaping to take place before step (iii) because the mixture can advantageously be thermoplastically processed and shaped before crosslinking, in particular by hot pressing, extrusion, injection molding and / or 3D printing.

If the components are mixed by dry mixing in step i), the dry mixture is melted in step ii) and subjected to a shaping step as described above.

In one embodiment, steps i) and ii) take place separately in succession. In a preferred embodiment, the molding is produced in step (ii) by thermoplastic reshaping. This means that the mixture can be formed from the melt in a non-crosslinked and / or at least not significantly crosslinked state, since otherwise thermoplastic processing would no longer be possible. If there are too many crosslinking points, the PK intermediate product is no longer flowable and can no longer be readily thermoplastically formed. Before shaping, the mixture should only be exposed to the high processing temperatures for a short period of time. The thermoplastic processing is therefore preferably carried out in such a way that the dwell time of the mixture in the device is as short as possible. It is preferred that the processing is carried out in such a way that the essential part of the crosslinking reaction, and for example more than 80%, more than 90% or more than 95% of the crosslinks, only takes place after the shaping, ie in step (iii) .

In a preferred embodiment, the mixture is processed in step (ii) by extrusion, hot pressing, injection molding and / or 3D printing and is shaped in the process. These methods are particularly suitable for the simple and efficient processing of thermoplastic polymer compositions. "Reshaping" means that a shape that was first given is changed again later. Typical forming processes are bending, embossing, stretching and deep drawing, etc.

The extrusion can be carried out by known methods. During extrusion, solid to viscous hardenable materials are continuously pressed out of a shaping opening (also known as a nozzle, die or mouthpiece) under pressure. This creates bodies with the cross-section of the opening, called extrudate, in theoretically any length. The extrusion is preferably carried out at a temperature of at least 220 ° C, preferably between 220 ° C and 265 ° C, and in particular between 230 ° C and 250 ° C.

Hot pressing is a process in which the molding compound is introduced into the previously heated cavity. The cavity is then closed using a pressure piston. The pressure gives the molding compound the shape given by the tool. The hot pressing is preferably carried out at a temperature of at least 220.degree. C., preferably between 220.degree. C. and 265.degree. C., and in particular between 230.degree. C. and 250.degree.

Injection molding (often also referred to as injection molding or injection molding process) is a molding process that is used in plastics processing. The plastic is plasticized with an injection molding machine and injected into a mold, the injection molding tool, under pressure. In the tool, the material returns to its solid state when it cools down and is removed as a molded body after the tool is opened. The cavity of the tool determines the shape and surface structure of the product.

In 3D printing, for example, the method known as fused deposition modeling (FDM) can be used to shape the molding compositions according to the invention. FDM is basically based on the three elements print bed (the desired object is printed on this), filament spool (supplies the print material) and print head (also called extruder). The filament consisting of the thermoplastic molding compound is unrolled during the process, fed to the extruder, melted there and deposited layer by layer on the printing plate.

Processing is particularly preferably carried out by extrusion and subsequent injection molding. The mixture of the PK and the crosslinker is melted in these processes if it is not already in liquid form. In step (ii), the mixture is preferably introduced into an extruder, an injection molding machine or a hot press, melted at high temperatures, for example in the range from 220 ° C. to 250 ° C., and brought into a desired shape.

Step (iii)

Step (iii) comprises the thermal treatment of the shaped body at a temperature at which PK is crosslinked, as a result of which the crosslinked shaped body is obtained. As a result, the PK can be crosslinked intermolecularly with the crosslinker. The polyamide is hydrolyzed and split into diamine components. During crosslinking, two imine bonds are formed between two keto groups of the PK chains and the two amino groups of the diamine released from the crosslinker. The resulting bridge in the form of an imine is also known as Schiff's base, since the imine nitrogen does not carry a hydrogen atom, but is linked to an organic molecule. The crosslinking takes place as completely as possible, so that as far as possible all amino groups of the crosslinker used react with the carbonyl groups of the PC. The advantages of complete crosslinking are increased heat resistance and increased rigidity (module). Nonetheless, only partial networking is also intended to be encompassed by the term “networked”. An only partial crosslinking can exist if not enough crosslinkers have been used for a complete integration of all PK chains in the network. In this case, the material usually has a higher elongation at break than the fully crosslinked material. The imine bonds give the shaped body a high degree of stability. According to the invention, the shaped body is preferably a shaped body based on PK. "Based on PK" means that the PK is the essential structure-giving polymer component of the Molded body is. In one embodiment it is preferred that the PC is the only polymer component of the molded body.

The temperature in step (iii) can be set relatively high, since the crosslinkers which can be used according to the invention have relatively high melting and boiling points. This is advantageous because such crosslinking reactions are generally favored at high temperature. However, the temperature is preferably below the melting range of PK and below the softening point of the not yet fully crosslinked shaped body.

Surprisingly, it was found that in the system according to the invention the crosslinking reactions take place even below the melting range of the polymer and the molding. This was unexpected, since it is generally assumed that crosslinking reactions preferably take place at temperatures above the melting range of the polymer and of the molding.

In the prior art it is also assumed that such crosslinking reactions take place relatively quickly within minutes or a few hours. According to the invention it has been found that the crosslinked PC can have particularly advantageous properties if the heating of the molding in step (iii), depending on the crosslinking temperature, is preferably carried out over a period of at least 1 hour, for example from 1 hour to 2 days. It has been found that the thermal stability, the modulus of elasticity and the tensile strength can be significantly increased by such a thermal treatment.

In particular, it was found that the thermal treatment can improve the rigidity of the samples at elevated temperatures. It was observed that a thermal treatment for a certain duration can significantly improve the rigidity, with a subsequent Saturation can occur, so that the rigidity is not or only insignificantly improved with further thermal aftertreatment. However, further thermal aftertreatment generally shows an improvement in the heat resistance. It has been found that the heat resistance can increase even with prolonged thermal aftertreatment.

In a preferred embodiment, the shaped body obtained in step (ii) is subjected to a thermal treatment over a shorter period of time. The thermal treatment of the shaped body in step (iii) is preferably carried out for a maximum of 6 hours, for example from 5 minutes to 6 hours, more preferably from 0.5 minutes to 5 hours and in particular from 1 hour to 4 hours. Flieran is advantageous that parallel self-crosslinking reactions of the aliphatic polyketone can be reduced.

Alternatively, however, it can also be expedient to subject the thermal treatment of the shaped body in step (iii) to a thermal treatment over a relatively long time, preferably of at least 6 hours, in particular for more than 2 days. In a further embodiment of the invention, the thermal treatment is carried out over a period of 2 to 10, in particular for 2 to 6 days. The thermal treatment is preferably carried out with the exclusion of oxygen.

In a preferred embodiment, the thermal treatment in step (iii) takes place at a temperature of at least 160.degree. C., preferably at least 180.degree. The temperature in step (iii) is preferably between 160.degree. C. and 240.degree. C., particularly preferably between 190.degree. C. and 230.degree. C. and in particular between 190.degree. C. and 210.degree. At such temperatures, efficient three-dimensional crosslinking can take place sufficiently quickly without the thermoplastically produced articles are adversely affected, for example by undesired deformation of the molded body.

The moldings are cooled after crosslinking and can be used or further processed.

As described above, both the mixture in step (i) and the shaped body can contain fillers and reinforcing materials and / or optionally a different additive. The cross-linked PC forms a matrix in which any fillers and reinforcing materials and / or additives that may be present are evenly distributed.

Suitable fillers and reinforcing materials are selected from glass fibers, e.g. in the form of glass fabrics, mats, nonwovens, glass silk rovings or cut glass silk, wollastonite, calcium carbonate, glass balls, quartz powder, silicon and boron nitride, amorphous silica, asbestos, magnesium carbonate, calcium silicate, calcium metasilicate, Kaolin, mica, feldspar, talc and mixtures thereof.

Suitable additives are selected from antioxidants, UV and heat stabilizers, lubricants and mold release agents, colorants, such as dyes and pigments, nucleating agents, plasticizers and mixtures.

For example, the fillers and reinforcing materials can be obtained in an amount of up to 80% by weight, for example from 0.1% by weight to 80% by weight, especially from 1% by weight to 60% by weight based on the total weight of the components used to position the molding.

For example, the additives can each be used in an amount of up to 20% by weight, for example from 0.1% by weight to 20% by weight, more particularly 0.1% by weight up to 18% by weight, based in each case on the total weight of the components used to produce the molding, can be used.

The shaped body can in particular be obtained by the processes according to the invention which are described in the context of this invention. The molded body preferably has the advantageous properties that are described in the context of this invention for the crosslinked PC. In the context of this invention, the term molded body refers to products made from crosslinked PC which have a defined three-dimensional shape. It is not necessary here for the shaped body to be a defined object, but rather it can also be a coating, for example. The molded body can consist of the crosslinked PC or contain it, for example as a composite material or laminate.

In a preferred embodiment, the shaped body according to the invention is post-tempered. In a first variant, the shaped body according to the invention is post-tempered for a period of 5 minutes to 6 hours.

In a second variant, the shaped body according to the invention is post-tempered over a period of more than 6 hours up to several days.

Different advantageous properties can be achieved in each case through the different variants.

The shaped body is preferably post-tempered for a period of 5 minutes to 6 hours and, compared to shaped bodies made of uncrosslinked PC, has advantageous, improved mechanical properties which are characterized by increased tensile modulus, increased yield stress and increased elongation. The shaped body according to the invention, post-tempered over a period of 5 minutes to 6 hours, preferably has a tensile modulus of at least 1800 MPa, in particular of at least 1900 MPa, and particularly preferably of at least 2000 MPa. Preferred the molding according to the invention, post-tempered over a period of 5 minutes to 6 hours, has a yield strength of at least 65 MPa, in particular of at least 68 MPa, and particularly preferably of at least 70 MPa. The molding according to the invention which has been post-baked over a period of 5 minutes to 6 hours preferably has an improved elongation of at least 20%, and particularly preferably of at least 23%.

The shaped body is preferably post-tempered for a period of more than 6 hours to several days and, compared with shaped bodies made of uncrosslinked PC, exhibits advantageous, increased stiffness, which is characterized by a high tensile modulus and increased tensile strength. However, if the crosslinking is too strong, the elongation is significantly reduced. The shaped body post-tempered over a period of more than 6 hours to several days preferably has a tensile modulus of at least 2000 MPa, in particular of at least 2250 MPa and particularly preferably of at least 2500 MPa. In particular, the tensile modulus is between 2000 MPa and 3000 MPa or between 2250 MPa and 3000 MPa. The tensile modulus of uncrosslinked PK, on the other hand, is between 1400 and 1800 MPa. The tensile modulus is determined according to DIN EN IS0527-2.

It may be desirable not to completely crosslink the PC in the shaped body, since the elongation at break of the material can decrease with increasing crosslinking. The degree of crosslinking is therefore preferably set with a view to the desired application, for example via the proportion of crosslinker and the type and duration of the thermal treatment.

The degree of crosslinking is preferably not measured directly, but rather it is determined by suitable test methods, such as, for example, a flea temperature tensile test, whether the shaped body has the desired properties having. At very high temperatures, it is advisable to determine the dynamic modulus.

The shaped bodies can be used in particular in technical fields in which high mechanical stability, and in particular high rigidity, are required. They are particularly suitable for applications in the automotive, shipping, aerospace, rail vehicles, oil and gas industry, food and packaging industry and medical technology and, in particular, as sealing items, preferably sealing and O-rings, bushings, foils, powders, coatings, Fibers, bearings, back-up rings, valves, thrust washers, coupling elements, snap hooks, pipes or lines, cables, casings and sheaths, housings or as a component thereof. They are particularly suitable for uses where high chemical resistance and resistance to abrasion are required. This applies in particular to applications in oil and gas production, aerospace technology and the chemical industry, including the manufacture of safety-relevant parts, and the field of energy generation and the automotive industry. Likewise conceivable applications are connectors and insulators in the electronics sector, since the networking leads to good insulation properties.

The methods, moldings and sealing articles according to the invention achieve the object on which the invention is based. Compared to the non-crosslinked PC, they have an improved temperature resistance and higher mechanical stability combined with good processability. In particular, the shaped bodies have high rigidity, in particular above the glass transition temperature. The high rigidity goes hand in hand with reduced creep behavior at high temperatures. The improved temperature resistance is evident both at the maximum temperature and at the long-term use temperature. The products show a very good rating Chemical resistance and reduced flammability, as the material does not melt due to the crosslinking and no burning material drips off.

In addition, the moldings according to the invention can be produced in a simple and efficient manner by thermoplastic molding processes. For example, the Fierstellung can be done by simply extruding. The processes are also environmentally friendly and can be carried out without endangering the user, since the crosslinkers used have relatively high boiling points and are not very volatile.

The invention is to be explained with the aid of the following examples, without, however, being restricted to the specifically described embodiments.

EXAMPLES

Brief description of the figures:

Figure 1 shows the results of the theological investigations on two moldings according to the invention (PK with 1.00% DAPI, thermally aftertreated for 1 h, described in embodiment 2 (dark gray curves) and PK with 1.00% DAPI, thermally aftertreated for 2 h, described in embodiment 3 (light gray curves) compared to the standard base material (PK without thermal treatment (black curves)). The storage module G '(symbol: square) and the loss module G “(symbol: triangle) are shown on the Y-axis The measuring time is shown on the X-axis.

FIG. 2 shows the development of the complex dynamic module with increasing temperature of a molding according to the invention (PK with 1.00% DAPI, thermally treated, measuring point indicated by asterisks) in Comparison to the standard base material (PC without thermal treatment, measuring points indicated by squares).

With regard to the standards described, the versions valid on the day of registration apply, unless otherwise stated.

Abbreviations:

DAPI: 1- (4-aminophenyl) -1, 3,3-trimethyl-indan-6-amine, and isomers thereof PK: aliphatic polyether ketone (MVR: 60 cm ^3/10 min (@ 240 ° C / 2.16 kg) , M.p .: 220 ° C)

Embodiment 1

The DAPI-isomer mixture having the CAS Number 68170-20-7 (crosslinking agent having the formula VII) by means of twin-screw compounder in a commercial PK with a melting point of about 220 ° C and an MVR of 60 cm ^3/10 min (at 240 ° C and 2.16 kg weight load) are mixed in and the strand is chopped into granules.

The granulate is processed into test specimens by injection molding and then also subjected to a thermal aftertreatment over a period of 1 hour in a vacuum oven.

After completion of the thermal aftertreatment, a tensile test according to ISO 527-2 was carried out and the values compared with uncrosslinked PK base material (Table 1). Table 1:

Due to the chemical post-crosslinking, the tensile modulus of elasticity of the PK has increased by approx. 13% compared to the non-crosslinked base material. Furthermore, the yield stress is increased by approx. 11% and the elongation by approx. 24% compared to the uncrosslinked base material.

Embodiment 2 The DAPI-isomer mixture having the CAS Number 68170-20-7 (crosslinker of formula VII) is carried out at using twin screw compounder in a commercial PK with a melting point of about 220 ° C and an MVR of 60 cm ^3/10 min ( 240 ° C and 2.16 kg weight load) mixed in and the strand chopped into granules.

The granulate is processed into test specimens by injection molding and then also subjected to a thermal aftertreatment over a period of 2 hours in a vacuum oven. After completion of the thermal aftertreatment, a tensile test according to ISO 527-2 was carried out and the values compared with uncrosslinked PK base material (Table 2). Table 2:

Due to the chemical post-crosslinking, the tensile modulus of elasticity of the PK has increased by approx. 14% compared to the non-crosslinked base material. Furthermore, the yield stress is increased by approx. 13% and the elongation by 31% compared to the uncrosslinked base material.

In addition to the tensile tests, rheological tests were carried out on an Anton Paar rheometer type MCR-302, which show the chemical postcrosslinking of the aliphatic polyketone with the crosslinker DAPI. Two moldings according to the invention (PK with 1.00% DAPI, thermally aftertreated for 1 h, described in embodiment 2 and PK with 1.00% DAPI, thermally aftertreated for 2 h, described in embodiment 3) in comparison to the standard base material ( PK without thermal treatment). The test conditions are listed in Table 3.

Table 3:

Embodiment 4

The granulate is processed into test specimens by injection molding and then also subjected to a thermal aftertreatment over a period of 6 days in a heating furnace under a protective gas atmosphere.

After completion of the thermal aftertreatment, a tensile test according to ISO 527-2 was carried out and the values compared with uncrosslinked PK base material (Table 4). Table 4:

As a result of the post-crosslinking, the tensile modulus of elasticity of the PK has more than doubled compared to the non-crosslinked base material. The crosslinked material no longer shows ductile behavior and the maximum strength is approximately 10 MPa higher than that of the uncrosslinked material. The The elasticity of the material is severely restricted, as a result of which the elongation at break is reduced to 2.5%.

While the uncrosslinked PK base material melts at around 220 ° C., no more melting is observed for the postcrosslinked material.

The uncrosslinked base material and the postcrosslinked PC were tested by means of DMA in a T-sweep, the result shown in FIG. 2 being obtained. Dynamic mechanical analysis (DMA) is a thermal method to determine the physical properties of plastics. The temperature gradient (temperature sweep) shows the development of the dynamic module and thus also the rigidity over the measured temperature range.

The temperature gradients were measured with test specimen strips (width approx. 4 mm, thickness approx. 3 mm, length approx. 45 mm) under the following conditions: heating rate 2 K / min, contact force 0.5 N, frequency 1.0 Hz, mean elongation 0, 5%, elongation ampl. +/- 0.1%. The results are shown graphically in FIG.

FIG. 2 shows the development of the complex dynamic module with increasing temperature of the molding according to the invention (PK with 1.0% DAPI, thermally treated, measuring points represented by asterisks) compared to the standard base material PK (PK without thermal treatment, measuring points represented by squares).

The results show that the PC crosslinked according to the invention has advantageous thermal properties. As already proven by the tensile test according to ISO 527-2, the material shows an increased modulus (see Table 4) and increased heat resistance. While the sharp drop in the If the module is caused by a melting of the material in the uncrosslinked PK from approx. 210 ° C, the loss of module in the crosslinked material is not caused by melting, but by the formation of cracks in the material.

Claims

1. Shaped body comprising a matrix from the crosslinking of an aliphatic polyketone with at least one diamine source as a crosslinker with the formation of imine groups, the diamine source being selected from

Diamine compounds selected from compounds of the formula (I), (II) and (III), in which

R ¹ , R ² , R ³ and R ⁴ independently of one another are selected from hydrogen, flalogen, nitro, cyano, flydroxy, amino, Ci-Cö-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C6-Ci4- Aryl, where the alkyl group, alkenyl group and alkynyl group are unsubstituted or with R ^a substituted and where the aryl group is unsubstituted or substituted ^{by R b,}

R ¹³ , R ¹⁴ , R ^15, R ¹⁶ , R ¹⁷ and R ^{18 are} independently selected from hydrogen, halogen, nitro, cyano, hydroxy, amino, Ci- C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C6-Ci4-aryl, where the alkyl group, alkenyl group and alkynyl group are unsubstituted or ^{substituted by R a} and where the aryl group is unsubstituted or substituted ^{by R b,}

X is selected from a bond, oxygen, sulfur,

Carbonyl, sulfonyl, sulfoxide, Ci-C6-alkylene, C2-C6-alkenylene and phenylene,

R ^{b is} selected from halogen, nitro, cyano, amino, Ci-C4-alkyl and Ci-C4-haloalkyl,

R ^{c is} selected from halogen, nitro, cyano Ci-C4-alkyl and C1-C4-haloalkyl,

Oligo- / polymers that have at least two amide groups, saturated, alicyclic compounds which have at least two primary amine groups, and oligo / polymers which contain these incorporated and

Mixtures thereof.

2. Shaped body according to claim 1, which comprises at least one filler and reinforcing material and / or an additive different therefrom.

3. A method for making a molding, comprising the steps of i) providing a mixture containing at least one aliphatic polyketone and at least one crosslinker, ii) making a molding from the mixture obtained in step i), and iii) thermal treatment of the molding in a Temperature at which the aliphatic polyketone is crosslinked, and where the crosslinker is selected from

Diamine compounds selected from the formula (I), (II) and (III)

(I) (II) in which

R ¹ to R ^{18 have} the meaning as defined in claim 1, oligo- / polymers which have at least two amide groups, - saturated, alicyclic compounds which have at least two primary

Have amine groups, oligo- / polymers that contain these incorporated, and

Mixtures thereof.

4. The method according to claim 3, wherein the crosslinker is a di (aminophenyl) compound in which the two aminophenyl rings are connected to one another via an aliphatic group which has a carbocyclic radical and wherein one of the two phenyl rings is fused to the carbocyclic radical.

5. The method according to claim 3 or 4, wherein the crosslinker is and a 4,4 ^{'-Diaminodiphenylverbindung} / or an asymmetrical

Connection is.

6. The method according to any one of claims 3 to 5, wherein the crosslinker is a compound of the general formula (IV): , in which

R ¹⁹ and R ^{20 are} independently selected from hydrogen, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, in particular with 1 to 4 carbon atoms, in particular methyl or ethyl, substituted or unsubstituted aryl with 5 to 12 carbon atoms, F and CI, and where Z is the aliphatic group containing a carbocyclic radical.

7. The method according to any one of claims 3 to 6, wherein the crosslinker is a compound of the general formula (V):

R ¹⁹ and R ^{20 are} independently selected from H, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, in particular with 1 to 4 carbon atoms, in particular methyl or ethyl, substituted or unsubstituted aryl with 5 to 12 carbon atoms, F and CI, and where R ^{21 is} a carbocyclic radical which has 2 to 3 carbon ring atoms and which can be substituted by at least one alkyl group with 1 to 4 carbon atoms, in particular methyl or ethyl.

8. The method according to any one of claims 3 to 7, wherein the crosslinking agent is the compound of the formula (V.a1): 9. The method according to claim 3, wherein the crosslinker is an oligo / polymer which has at least two amide groups, the oligo / polymer containing monomers in polymerized form which are selected from A) in each case unsubstituted or substituted aromatic dicarboxylic acids and derivatives of unsubstituted or substituted aromatic dicarboxylic acids, B) unsubstituted or substituted aromatic

Diamines, C) aliphatic or cycloaliphatic dicarboxylic acids, D) aliphatic or cycloaliphatic diamines, E) monocarboxylic acids, F) monoamines, G) at least trivalent amines, Fl) lactams, I) w - amino acids, and K) different from A) to I) , thus cocondensable compounds, and mixtures thereof.

10. The method according to any one of claims 3 or 9, wherein the crosslinker is an oligo- / polymer which has at least two amide groups, the oligo- / polymer containing polyamide-forming monomers in polymerized form, which are selected from unsubstituted or substituted aromatic dicarboxylic acids and Derivatives of unsubstituted or substituted aromatic dicarboxylic acids and aliphatic or cycloaliphatic diamines.

11. The method according to claim 10 wherein the aromatic dicarboxylic acids are selected from unsubstituted or substituted phthalic acid, Terephthalic acid, isophthalic acid, naphthalenedicarboxylic acids or diphenyldicarboxylic acids and the derivatives and mixtures of the aforementioned aromatic dicarboxylic acids.

12. The method according to claim 10 or 11, wherein the aliphatic or cycloaliphatic diamines are selected from ethylenediamine, propylenediamine, tetramethylenediamine, heptamethylenediamine, hexamethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 2-methyl-1, 8-octamethylenediamine, decodamethylenediamine, undecamethylenediamine 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 2,4-dimethyloctamethylenediamine, 5-methylnonanediamine, bis (4-aminocyclohexyl) methane, 2,2-bis (4 -aminocyclohexyl) propane, 1,3-bis (aminomethyl) -cyclohexane and 1,4-bisaminomethylcyclohexane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1, 3,3- trimethylcyclohexanemethylamine (isophoronediamine), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, [3- (aminomethyl) -2-bicyclo [2.2.1] heptanyl] methanamine, aminated dimer fatty acids, and mixtures thereof.

13. The method according to any one of claims 3 and 9 to 12, wherein the crosslinker is selected from oligomers / polymers as defined in claims 1, 3 and 9 to 12, their copolymers and mixtures thereof, wherein the crosslinker has a melting range of 200 ° C to 250 ° C, preferably a melting range of 220 ° C to 240 ° C, especially a melting range of 220 ° C to 230 ° C.

14. The method according to claim 3, wherein the crosslinker is a saturated, alicyclic compound which has at least two primary amino groups selected from aminized dimer fatty acids, polymers containing aminated dimer fatty acids in copolymerized form and mixtures thereof, in particular the compound or oligo- / polymers which contain this compound in copolymerized form.

15. The method according to claim 3, wherein the crosslinker is at least one

Compound of formula (I) or (II), where R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and R ^{11 are} hydrogen and R ¹ , R ⁴ , R ⁹ , R ¹² and X have the meaning as defined in claim 1.

16. The method according to claims 3 or 15, wherein the crosslinking agent is at least one compound of the formula (Ia) or (II. A) in which

R ¹ , R ⁴ , R ⁹ and R ^{12 have the} following meanings Tert-butyl tert-butyl

17. The method according to any one of claims 3 to 16, wherein in step i) the at least one aliphatic polyketone, the at least one crosslinker, optionally a filler and reinforcing material and optionally a further different additive is subjected to melt mixing or dry mixing.

18. The method according to any one of claims 3 to 17, wherein in step i) the at least one aliphatic polyketone, the at least one crosslinker, optionally a filler and reinforcing material and optionally a further different additive is fed into an extruder, mixed with plasticization and optionally is granulated.

19. A method according to any one of claims 3 to 18, wherein the aliphatic polyketone at 240 ° C has a melt viscosity in the range of 2 cm ^3/10 min to 200 cm ^3/10 min, measured according to DIN ISO 1130th

20. The method according to any one of claims 3 to 19, wherein the mixture contains no added solvent.

21. The method according to any one of claims 3 to 20, wherein the temperature in step ii) is at least 220 ° C.

22. The method according to any one of claims 3 to 21, wherein the mixture is processed in step ii) by extrusion, hot pressing, injection molding and / or 3D printing.

23. The method according to any one of claims 3 to 22, wherein the molded body obtained in step ii) is subjected to a thermal treatment in step iii) for 5 minutes to 6 hours.

24. The method according to claim 23, wherein the thermal treatment in step iii) takes place at a temperature of at least 160 ° C.

25. Shaped bodies obtainable by a process as defined in claims 3 to 24.

26. Polymer mixture containing at least one polyketone (PK) and at least one crosslinker selected from

Diamine compounds selected from compounds of the formula (I), (II) and (III),

(I) (II) in which

R ¹ , R ² , R ³ and R ^{4 are} independently selected from hydrogen, halogen, nitro, cyano, hydroxy, amino, Ci-Cö-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C6-Ci4- Aryl, where the alkyl group,

Alkenyl group and alkynyl group unsubstituted or ^{substituted by R a} and where the aryl group is unsubstituted or substituted ^{by R b,}

R ⁵ , R ⁶ , R ^7, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are} independently selected from hydrogen, halogen, nitro, cyano, hydroxy,

Amino, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C6-Ci4-aryl, the alkyl group, alkenyl group and alkynyl group being unsubstituted or ^{substituted by R a} and the aryl group being unsubstituted or substituted ^{by R b} , R ¹³ , R ¹⁴ , R ^15, R ¹⁶ , R ¹⁷ and R ^{18 are} independently selected from hydrogen, halogen, nitro, cyano, hydroxy, amino, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl , C6-Ci4-aryl, where the alkyl group, alkenyl group and alkynyl group are unsubstituted or ^{substituted by R a} and where the aryl group is unsubstituted or substituted ^{by R b,}

X is selected from a bond, oxygen, sulfur,

Carbonyl, sulfonyl, sulfoxide, Ci-C6-alkylene, C2-C6-alkenylene and phenylene, R ^{a is} selected from halogen, nitro, cyano, hydroxy, carboxyl, amino, C6-Ci2-aryl, the aryl group being unsubstituted or substituted ^{by R c,}

R ^{c is} selected from halogen, nitro, cyano Ci-C4-alkyl and C1-C4-haloalkyl,

Oligo- / polymers which have at least two amide groups, saturated, alicyclic compounds which have at least two primary amine groups, and oligo- / polymers which contain these incorporated and

Mixtures thereof.

27. Use of a molded body as defined in claims 1, 2 and 25 or obtainable by a process as defined in claims 3 to 24 in the fields of automobiles, shipping, aerospace, rail vehicles, and the oil and gas industry , Food and packaging industry and medical technology.

28. Sealing articles, thrust washers, back-up rings, valves, connectors, insulators, snap hooks, bearings, bushings, foils, powders, coatings, fibers, sealing rings and O-rings, pipes and cables,

Cable, sheaths and sheaths, housings for an electrical or chemical application, consisting of or containing a molded body according to claim 1, 2 or 25.