Flame-retardant molded articles for electrical equipment

Abstract

To provide a device for storage, generation, transmission, distribution and / or use of electrical energy, comprising a flame retardant molded article, which comprises a polymer matrix containing a crosslinked aliphatic polyketone (PK) in combination with at least one flame retardant, and a method for improving the flame retardant properties of molded articles for electrical devices.SOLUTION: The present invention provides a device for storage, generation, transmission, distribution and / or use of electrical energy, comprising a flame retardant molded article, which comprises a polymer matrix of crosslinking an aliphatic polyketone with at least one diamine source as a crosslinking agent to form imine groups, wherein the diamine source is a predetermined one, as well as at least one flame retardant (A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to devices for storing, generating, transmitting, distributing, and / or using electrical energy, comprising flame-retardant molded articles that include a polymer matrix containing a cross-linked aliphatic polyketone (PK) in combination with at least one flame retardant, as well as methods for improving the flame retardancy of molded articles for electrical devices. The present invention further relates to electrically powered transportation devices, battery energy storage systems, power tools, and power generation devices, and components thereof, that include flame-retardant molded articles that include a polymer matrix containing a cross-linked aliphatic polyketone (PK) in combination with at least one flame retardant.

[0002] <Background of the invention> The world is currently moving towards a sustainable economy, with increasing the share of renewable energy and improving energy efficiency being key elements. Under the term "energy transition," a shift from a fossil fuel-based concept to one based on renewable energy is taking place. A key area of ​​this ecological transformation concerns new drive concepts that allow for a reduction in the impact of transportation on climate change, air pollution, and other environmental issues. The trend towards electromobility is associated with new vehicle designs that use lighter components and a higher proportion of plastic parts. New battery solutions, not only in transportation but also in many other areas, such as power tools, require innovative and at the same time safe concepts.

[0003] Currently, there are many electric vehicles (EVs) for road, rail, maritime and air transport with completely different drive concepts. EVs can be powered, for example, by overhead lines, conductor rails or batteries, which can be recharged, inter alia, by internal combustion engine-driven generators, solar panels or fuel cells. Currently, electric vehicles are mainly chosen from fuel cell electric vehicles (FCEVs), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs) and battery electric vehicles (BEVs).

[0004] Battery electric vehicles (BEVs) (also known as pure electric vehicles, only electric vehicles, fully electric vehicles, or all-electric vehicles) have no secondary propulsion source (e.g., an internal combustion engine) and use only chemical energy stored in a rechargeable battery pack. This concept has several advantages: Fully electric vehicles (EVs) have zero tailpipe emissions and are environmentally friendly, especially when they use renewable energy sources instead of fossil fuels; fully EV drivetrains are less complex and have lower maintenance costs than internal combustion vehicles; and their overall energy efficiency (including charging efficiency, motor efficiency, and DC / AC conversion rate) exceeds 70%, compared to the efficiency of many ICE vehicles, which are below 20%.

[0005] BEV electric motors typically operate at several hundred volts and are powered by modularized batteries consisting of numerous cells assembled into a battery pack. BEV applications require batteries to provide both power for acceleration and energy for range. Battery manufacturers are currently striving to further extend the range of electric vehicles. This is typically achieved by increasing the energy density of the cells. Today's electric vehicles rely almost exclusively on lithium-ion batteries (LIBs). LIB chemistry poses significant safety concerns, primarily due to its flammable electrolyte, which can lead to exothermic decomposition reactions of the anode and cathode materials if the battery fails. The aftermath of a LIB failure is often a so-called thermal runaway, characterized by an exponential increase in the temperature inside the cell, where the rate of heat generation exceeds the rate of heat removal. In the worst case scenario, this can lead to an increase in internal cell pressure, triggering the release of overpressure devices or the rupture of the cell housing. This can result in the release of hot, flammable gases and the risk of fire. Because the cells are densely packed, thermal runaway can easily spread to adjacent cells, ultimately igniting the entire battery and the vehicle.

[0006] The risk of so-called thermal runaway events forces manufacturers of portable and stationary battery solutions, vehicles, power tools, etc. to use only flame-retardant plastics in the installation space around the battery. However, during thermal testing of components, it is often found that flame-retardant thermoplastics cannot withstand the harsh conditions of some fire tests because, although they do not burn due to their flame-retardant properties, they do soften and melt, which can cause the component to lose its functionality. This challenge could be solved if flame-retardant thermoplastic materials that exhibit thermosetting behavior after processing were available.

[0007] Thermoplastically processable plastics (thermoplastics) have become widely used and are now standard products in industrial production due to their manufacturability, reversible moldability, and often high-quality technical properties. Thermoplastics consist of essentially linear polymer chains; i.e., they are not crosslinked and usually have little or no branching. However, thermoplastics have inherent limitations in their heat resistance, making them not ideally suited for all applications in electrical devices, such as powered transportation and power tool components. In particular, there is a risk that flame-retardant plastics will melt and completely lose their functionality during a thermal runaway event. Therefore, it is desirable to increase the heat resistance of thermoplastics without sacrificing their advantages, such as processability, excellent mechanical properties, and high chemical resistance. In terms of heat resistance, crosslinked polymers (thermosets), in which the macromolecules are linked by covalent bonds, are often advantageous. At low temperatures, these crosslinked polymers exist in a hard, elastic state, also known as the glass transition region. When thermosets are heated above this range, they generally enter directly into the thermal decomposition region. Therefore, there is great interest in developing new materials that combine the advantages of thermoplastics and thermosets, i.e., materials that can be molded cost-effectively and exhibit high heat resistance after molding. This combination would be particularly advantageous for plastics used in electromobility.

[0008] Aliphatic polyketones (PK) are thermoplastics with excellent mechanical properties, especially high impact strength and excellent media resistance. They have an alternating structure of ethylene or propylene groups followed by keto (carbonyl) groups, with the proportion of propylene groups usually small and variable. Aliphatic polyketones are particularly characterized by very good resilience, high impact strength values ​​even at low temperatures, high mechanical fatigue strength, low creep deformation tendency, and good sliding and wear behavior.

[0009] Aliphatic polyketones are linear polymers made from carbon monoxide and α-olefins, with strictly alternating monomer unit configurations in the polymer chain. Today, polyketone terpolymers are used almost exclusively, rather than the classic polyketone copolymers made solely from carbon monoxide and ethylene. These polyketone terpolymers consist of carbon monoxide, ethylene, and preferably a small amount of propylene.

[0010] [ka]

[0011] The reason for using terpolymers rather than copolymers is that terpolymers have significantly reduced brittleness. Polyketone copolymers consisting of carbon monoxide and ethylene are highly crystalline, very hard, and very brittle due to their strictly alternating polymer chains, extremely low defect rate (one defect per million monomer units), and abundant polar keto groups, which severely limits their potential applications as polymeric materials. Adding a small amount of propylene (approximately 5%) during synthesis disrupts the crystallinity, thereby lowering the melting point from 255°C (carbon monoxide and ethylene copolymer) to 220°C (terpolymer), resulting in a very tough polymer rather than a brittle one. Aliphatic polyketones are particularly characterized by high impact strength, low creep, high chemical resistance, and good tribological properties. However, PK also exhibits inherent limitations in terms of heat resistance, which, as mentioned above, is typical of thermoplastics. Therefore, the use of PK at maximum continuous use temperatures of approximately 80°C to 100°C (heat distortion temperature HDT / A according to ISO 75) is disadvantageous. The applicability of this polymer class is therefore very limited.

[0012] WO 97 / 14743 relates to a non-crosslinked polyketone blended with a mixture of reinforcing materials and flame retardants.

[0013] To further enhance the heat resistance and mechanical stability of PK, cross-linking of the polymer chains has been proposed.

[0014] The method of chemically crosslinking polyetheretherketone (PEEK) with diamines has been known since the 1980s.

[0015] The crosslinking reaction of PK with amines can be explained as follows: the keto groups of aliphatic polyketones react with amines to form Schiff bases. However, because aliphatic polyketones tend to undergo chaotic follow-up reactions after the keto groups tautomerize to the corresponding enol forms at high temperatures, these reactions often compete with crosslinking, making ordered crosslinking of the material much more difficult.

[0016] Furthermore, handling volatile diamines at high temperatures poses significant risks to the user and has a significant environmental impact, and it would be desirable to design the above process and the reagents used therein in such a way that they do not pose any risks to the user or the environment.

[0017] Recent publications describe attempts to remedy this shortcoming.

[0018] WO 2020 / 030599 describes a method for producing a PAEK-containing crosslinked molded article, in which the crosslinker is a di(aminophenyl) compound in which two aminophenyl rings are linked to each other by an aliphatic group containing a carbocyclic group. Specifically, the crosslinker component is 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (DAPI, CAS No. 54628-89-6), an isomer mixture of DAPI and 1-(4-aminophenyl)-1,3,3-trimethylindan-6-amine, or an isomer mixture of DAPI and CAS No. 68170-20-7. One drawback is the high production cost of the crosslinker. Meanwhile, the physicochemical properties of PAEK crosslinked with DAPI also need improvement.

[0019] WO2021156403 describes a molded article comprising a polymer matrix containing crosslinked aliphatic polyketones (PK), wherein the crosslinker is selected from various diamino compounds, oligomers / polymers containing amide groups, and saturated alicyclic amino compounds.

[0020] However, no prior art documents have proposed flame retardant technology for PK polymers.

[0021] It would therefore be highly desirable to provide crosslinked aliphatic polyketones for use in flame retardant molded electrical parts, particularly transportation equipment parts and power tool parts, that are characterized by improved mechanical properties, improved heat resistance, reduced creep and improved chemical resistance while exhibiting low flammability or flame retardancy.

[0022] In one aspect, it is an object of the present invention to provide a flame-retardant molded electrical component comprising a PK with optimized flame retardancy, whereby the aforementioned properties are improved or at least not impaired.

[0023] Surprisingly, this problem is solved by a flame-retardant molded electrical component comprising a polymer matrix containing a) an aliphatic polyketone crosslinked with at least one specific diamine source as a crosslinker to form imine groups, and b) at least one flame retardant.

[0024] In another aspect, it is an object of the present invention to provide a method for improving the flame retardancy of a molded article for use in an apparatus for the storage, generation, transmission, distribution and / or use of electrical energy.

[0025] This problem is solved by a method in which a polyketone is subjected to crosslinking with a specific diamine source to form imine groups in the presence of a flame retardant. In this method, a plasticized mixture of at least one polyketone, at least one flame retardant, and at least one diamine source can be first subjected to a molding process to produce a molded article. The molded article can then be subjected to crosslinking. Preferably, depending on the crosslinking chemistry selected, the molded article is crosslinked during the molding step or subsequently in a post-cure step.

[0026] <Summary of the Invention> The present invention provides the following: a) a polymer matrix in which an aliphatic polyketone is crosslinked with at least one diamine source as a crosslinking agent to form imine groups, the diamine source being selected from the group consisting of: - di(aminophenyl) compounds in which two aminophenyl rings are linked to each other by an aliphatic group having a carbocyclic group; Formulas (I), (II) and (III) [ka] [In the formula, R1 , R 2 , R 3 and R 4 are each independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C6-C 14 aryl, and the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C6-C 14 aryl, and the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C6-C 14 aryl, and the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by X is selected from a bond, oxygen, sulfur, carbonyl, sulfonyl, sulfoxide, C1-C6 alkylene, C2-C6 alkenylene, and phenylene; R ais halogen, nitro, cyano, hydroxy, carboxyl, amino, C6-C 12 aryl, wherein the aryl group is unsubstituted or selected from R c is replaced by R b is selected from halogen, nitro, cyano, amino, C1-C4 alkyl and C1-C4 haloalkyl; R c is selected from halogen, nitro, cyano, C1-C4 alkyl and C1-C4 haloalkyl; - oligomers / polymers having at least two amide groups, - saturated alicyclic compounds having at least two primary amino groups, and oligomers / polymers containing such compounds in an incorporated form, - A mixture of these shall be selected from the group consisting of: b) Flame retardant (A) The present invention relates to an apparatus for storing, generating, transmitting, distributing and / or using electrical energy, comprising a flame-retardant molded article comprising:

[0027] The present invention also relates to a motorized transport device, a battery energy storage system, a power tool or a power generating device comprising at least one flame retardant molded article as defined above and below.

[0028] The present invention also provides a method for improving the flame retardancy of a molded article for electrical equipment, the method comprising: i) providing a mixture comprising at least one aliphatic polyketone, at least one crosslinking agent, and at least one flame retardant, as defined herein; ii) producing a shaped article from the mixture obtained in step i), and / or iii) heat treating the shaped article at a temperature at which the aliphatic polyketone crosslinks. Including, The crosslinking agent may be: - di(aminophenyl) compounds in which two aminophenyl rings are linked to each other by an aliphatic group having a carbocyclic group; Formulas (I), (II) and (III) [ka] [In the formula, R 1 , R 2 , R 3 and R 4 are each independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C6-C 14 aryl, and the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C6-C 14 aryl, and the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C6-C 14 aryl, and the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R aand the aryl group is unsubstituted or substituted with R b is replaced by X is selected from a bond, oxygen, sulfur, carbonyl, sulfonyl, sulfoxide, C1-C6 alkylene, C2-C6 alkenylene, and phenylene; R a is halogen, nitro, cyano, hydroxy, carboxyl, amino, C6-C 12 aryl, wherein the aryl group is unsubstituted or selected from R c is replaced by R b is selected from halogen, nitro, cyano, amino, C1-C4 alkyl and C1-C4 haloalkyl; R c is selected from halogen, nitro, cyano, C1-C4 alkyl and C1-C4 haloalkyl; - oligomers / polymers having at least two amide groups, - saturated alicyclic compounds having at least two primary amino groups, and oligomers / polymers containing such compounds in an incorporated form, - A mixture of these The present invention relates to a method selected from the group consisting of:

[0029] <Detailed explanation> In principle, the invention relates to a device for the storage, generation, transmission, distribution and / or use of electrical energy, comprising at least one flame-retardant molded article.

[0030] Preferably, the electrical device is selected from an electric vehicle (EV), a battery energy storage system (BESS), a power tool, and a power generation device.

[0031] Electric vehicles (EVs) are explained in more detail below.

[0032] A battery energy storage system is a type of energy storage system that uses batteries to store and distribute energy, for example in the form of electricity generated by wind or solar power plants, or electricity generated via grid connections during periods of low demand. A particular embodiment of a BESS is a stationary battery energy storage system. A further particular embodiment is a battery energy storage system for lithium-ion batteries.

[0033] A power tool is a tool operated by an additional power source and mechanism that is different from the simple manual task for which a hand tool is used. According to the present invention, a power tool includes a corded or cordless electrical device with at least one electric motor that draws power from a rechargeable power source, such as a rechargeable battery pack, particularly a lithium-ion battery pack. Power tools are used in industry, construction, gardens, for household tasks such as cooking and cleaning, and around the home for purposes such as driving, drilling, cutting, shaping, filing, grinding, routing, polishing, painting, and heating. Suitable stationary or portable power tools include cordless drills, impact drivers, hammer drills, rotary hammers, power screwdrivers, jigsaws, reciprocating saws, circular saws, miter saws, band saws, chainsaws, biscuit joiners, angle grinders, bench grinders, disc sanders, wood routers, nail guns, and the like.

[0034] Further electrical equipment is, for example, switchgear, transformers, in particular distribution transformers or power transformers, electrical rotating machines, generators, motors, drives, semiconducting components, power electronic equipment, converter stations, etc.

[0035] A preferred embodiment of the present invention is an electric transport part. The flame-retardant molded article for an electric device according to the present invention, the device (particularly an electric transport) according to the present invention, and the method for improving the flame retardancy of a molded article for an electric device according to the present invention (particularly a method for improving the flame retardancy of an electric transport part) have the following advantages: The crosslinked polyketones used according to the invention and the molded articles according to the invention are flame retardant. The flame-retardant crosslinked polyketones used according to the invention and the molded articles according to the invention exhibit improved heat resistance, reduced flammability and improved stiffness (modulus) at high temperatures. The flame-retardant crosslinked polyketones used according to the invention and the molded articles according to the invention exhibit improved stability and still exhibit satisfactory processability. The flame-retardant crosslinked polyketones used according to the invention and the molded articles according to the invention exhibit improved flame retardancy and improved dimensional stability under direct flame impact, in other words, in the event of a fire, these materials remain dimensionally stable and do not burn. The process according to the invention and the resulting molded articles, in particular motorized transport parts, are characterized by a significantly improved flame retardancy compared to parts without flame retardant A). The combination of crosslinked aliphatic polyketones, a specific diamine source used as a crosslinker, and at least one flame retardant A) allows the production of molded articles for electrical equipment, particularly for electric transportation components, that provide protection under extreme conditions, particularly those encountered during thermal runaway events in cells. These components are resistant to high-temperature gases and flames. They do not melt and maintain their structural shape even after prolonged exposure to fire. Advantageously, these components are also suitable for preventing or slowing the spread of fire. In the event of a battery cell experiencing thermal runaway, the components according to the present invention prevent the flame from spreading to other areas, for example, from one cell to another or from one cell compartment to another. Electric vehicle components are also suitable for protecting sensitive components, such as control electronics and cable harnesses, from direct exposure to the flames, hot gases, and pollutants that may form during a fire. Advantageously, these components maintain a high electrical resistance even after exposure to flames. Furthermore, the combination of crosslinked aliphatic polyketones with a specific diamine source used as crosslinking agent and at least one flame retardant A) makes it possible to produce molded articles for electrical devices with low gas diffusion properties. The use of molded parts for electric vehicles according to the present invention allows the replacement of metal-based components in electric vehicles. This is associated with numerous advantages, such as significant weight savings and the possibility of integrating multiple functions into a single component, since the material is suitable for molding difficult components. For example, it is possible to arrange cooling channels directly in the battery module's holding frame or to integrate battery components such as casings, spacers, brackets, and covers with the cooling system. In this way, it is possible to increase the temperature distribution within the module and / or enable a substantially uniform temperature distribution. This allows for good cooling performance despite the thermoplastic resin's lower thermal conductivity compared to metals. As a result, integrated functions that increase capacity and power are realized with fewer components, less space, and at lower costs. The molded articles for electrical equipment according to the invention have good tribological properties, in particular very good polishing behavior. They are suitable for use in materials that are subjected to abrasive wear conditions, for example as seals or plain bearings in conveying devices for aggressive abrasive media. The molded articles for electrical equipment according to the invention exhibit low swelling. The molded articles for electrical equipment according to the invention have good chemical resistance and exhibit a low tendency to creep.

[0036] Hereinafter, the terms "crosslinker" and "diamine source" are used interchangeably.

[0037] In the following, the terms curable polymer composition and curable polymer composition are also used synonymously.

[0038] For purposes of this application, the term "blend" refers to a composition essentially comprising two or more polymeric components.

[0039] For purposes of this application, the term "compounding" refers to the formation of a mixture of a polymer component and at least one additive. The polymer component may be a single polymer, a polymer blend, or a component containing at least one additive. The term "electric vehicle" (EV) for purposes of this application encompasses any type of vehicle that is partially or fully powered by electricity. Preferred embodiments include road-based electric vehicles, track-based electric vehicles, marine electric vehicles, electric aircraft, and electric spacecraft. In a particular embodiment, the electric vehicle is a road-based electric vehicle. An EV can be powered, for example, by a power collection system (e.g., overhead lines or ground power supply), a battery (e.g., charged by a generator, solar panels, fuel-to-electricity conversion using a fuel cell, etc.), or the like. A particular embodiment is an EV that is powered (partially or exclusively) by a battery.

[0040] Preferably, the electric vehicle is selected from a fuel cell electric vehicle (FCEV), a hybrid electric vehicle (HEV), a plug-in hybrid electric vehicle (PHEV) and a battery electric vehicle (BEV).

[0041] A fuel cell electric vehicle (FCEV) generates electricity using a fuel cell, which utilizes a chemical reaction between a fuel, usually hydrogen, and oxygen to produce electrical energy, producing water. Currently, most FCEVs use a battery to recover braking energy, provide additional power during acceleration events, and smooth the power supplied by the fuel cell, but typically do not have the ability to plug in to charge the battery.

[0042] A hybrid electric vehicle (HEV) is powered by an internal combustion engine (ICE) and at least one electric motor that uses energy stored in a battery that is charged by the ICE and / or regenerative braking, but typically cannot be connected to an external power source.

[0043] A plug-in hybrid electric vehicle (PHEV) is a hybrid electric vehicle that can charge its battery pack by connecting to an external power source, by an ICE, or by regenerative braking. The vehicle typically runs on electric power until the battery is nearly depleted, after which it automatically switches over to using the ICE.

[0044] A battery electric vehicle (BEV), also known as a pure electric vehicle, only electric vehicle, fully electric vehicle, or all-electric vehicle, is a type of electric vehicle (EV) that does not have a secondary propulsion source (e.g., a hydrogen fuel cell, an internal combustion engine, etc.) and uses only chemical energy stored in a rechargeable battery pack. A battery electric vehicle is one specific embodiment of an electric vehicle according to the present invention.

[0045] The present invention makes it possible to provide flame-retardant molded parts for electric vehicles (hereinafter also referred to as "transportation equipment parts") for all areas of EV parts, particularly those related to batteries, thermal systems, DC-DC converters, electric motors, power inverters, charging ports, on-board chargers, bus bars, control devices, transmissions, cooling pipes, housings, mounts, etc.

[0046] Other common applications are centering sleeves, protective sleeves and clamping sleeves for electromobility.

[0047] The flame-retardant molded parts of electric vehicles are preferably selected from battery components, cooling systems, and power electronics components. In a preferred embodiment, the transportation parts are selected from battery components of electric vehicles. EV batteries generally consist of cells, modules, and packs. A battery cell is a basic unit that extracts electrical energy by charging and discharging. By combining a cross-linked aliphatic polyketone, a specific diamine source used as a cross-linking agent, and at least one flame retardant A), it is possible to produce a cell case with a large capacity per unit volume, high reliability and stability that can withstand impacts transmitted during driving and high and low temperatures.

[0048] A cluster of cells constitutes a module, and a cluster of modules constitutes a pack. The transportation part of the present invention can be used in assembling battery cells into a frame to form a module, protecting the cells from external impact, heat, or vibration. A battery pack is the final battery system installed in an EV. The battery pack includes modules and additional components, such as control and / or protection systems including a battery management system (BMS) and a cooling system. A battery pack typically includes a box body and multiple battery modules fixed to the box body by mounting devices. The flame-retardant molded part for electric transportation according to the present invention can be selected from any type of plastic battery pack component.

[0049] The flame-retardant molded parts for electric transport are selected in particular from battery cell cases, heat shields between cells, crash absorbers, boxes and covers for battery packs, in particular boxes and covers for lithium-ion batteries, busbar fixing and protection systems, busbar jackets, media transport lines, components of battery cooling systems, connectors, harnesses, seals, sensors, capacitors, fuses.

[0050] The use of molded parts for electric vehicles according to the present invention allows for the replacement of metal-based components in electric vehicles. This allows, for example, significant weight savings and the integration of multiple functions into a single part, since the material is suitable for molding otherwise difficult components. For example, it is possible to directly position cooling channels in the battery module's holding frame, or to integrate battery components such as casings, spacers, brackets, and covers with the cooling system. In this way, it is possible to increase the temperature distribution within the module and / or enable a substantially uniform temperature distribution. This allows for good cooling performance despite the thermoplastic resin's lower thermal conductivity compared to metals. As a result, integrated functions that increase capacity and power can be realized with fewer components, less space, and at lower cost.

[0051] In a further specific embodiment, the flame-retardant molded part for an electric vehicle according to the present invention is a flame-retardant bracket or barrier. Panels and brackets made of the flame-retardant plastic material according to the present invention can be advantageously used in EV battery housings. As described above, the material is resistant to flames and hot gases, providing protection, particularly during a cell thermal runaway event. The material prevents flames from spreading to other areas, including between cells and / or cell compartments. The part for an electric vehicle according to the present invention can be an entire pane or an end cover. The part can be designed as required by the customer's design, including complex shapes such as channels and brackets.

[0052] An EV battery pack typically consists of multiple battery cells, which must be assembled to form strong mechanical and electrical connections. These connections are typically achieved using busbars. In a further specific embodiment, the flame-retardant molded part for electric vehicles of the present invention is used in busbar applications. The transportation part of the present invention is, in particular, a busbar holder or busbar protective cover. One specific embodiment is a flame-retardant snap-on busbar cover. The transportation part is, in particular, a fire- and heat-resistant plastic cover for the top of an electric busbar used in an EV battery system. This cover provides protection from flames and hot gases generated during a cell runaway event. This cover is particularly suitable for protecting the busbar from direct exposure to flames and contaminants that may be generated during a cell thermal runaway event. This also provides arc protection. Advantageously, due to its specific components and manufacturing method, the transportation part of the present invention maintains its structural shape and does not melt. This prevents sagging or warping of the assembly and allows the busbars to separate as designed. The cover can be in the form of a snap-on / over design, an overmolding of the metal busbar, or a more complex assembly over the busbar connection. The material also maintains high electrical resistance after flame exposure, improving safety against discharges from the busbar to other parts of the transportation equipment.

[0053] In a further specific embodiment, the flame-retardant molded part for electric vehicles according to the present invention is a component of a battery cooling system. The transportation component is, in particular, a cooling tube for an EV battery system. The combination of a crosslinked aliphatic polyketone, a specific diamine source used as a crosslinker, and at least one flame retardant A) allows for the production of cooling tubes for use in battery cooling systems that do not melt or burst when exposed to high heat or flame. This is a significant advantage over conventional plastics, which melt and / or burn when directly exposed to flame, shortening the tube's lifespan or bursting the fluid. The added protection provided by the flame-retardant plastic improves heat resistance and extends the time to failure. The tubes according to the present invention ensure that the cooling fluid remains within the cooling system during a thermal runaway event, maintaining temperature control of the battery system.

[0054] In a further particular embodiment, the flame-retardant molded part for electric transport according to the invention is a plastic part for power electronics, such as a housing, bracket, cover, etc. Power electronics includes inverters, DC-DC converters, on-board chargers, etc.

[0055] <Polyketone> In principle, any aliphatic polyketone can be used as the polymer component. According to the present invention, aliphatic polyketones (PK) are polymers with a linear structure produced from carbon monoxide and α-olefins, and the arrangement of the monomer units in the polymer chain is preferably strictly alternating. Aliphatic polyketones differ from polyaryletherketones (PAEKs) such as polyetheretherketones (PEEKs) in that they do not contain aromatic rings or ether groups. The preferred PAEs according to the present invention are polyketone terpolymers. These polyketone terpolymers consist of carbon monoxide, ethylene, and preferably a small amount of propylene.

[0056] [ka]

[0057] According to the present invention, the aliphatic polyketone has a linear polymer chain consisting of alternating alkylene units and keto groups. The alkylene units preferably comprise ethylene units as the main component, and particularly preferably comprise ethylene units as the main component in combination with 1-methylethylene units. The aliphatic polyketones may differ in their average molecular weight and the ratio of the reactants carbon monoxide, ethylene, and other alkenes used in their production, such as propylene or 1- or 2-butylene. The aliphatic polyketones contain keto groups that can be linked to form imine bonds. According to the present invention, a mixture of various aliphatic polyketones, for example, differing in molecular weight or composition, may also be used. However, using a single PK is preferred because this achieves higher crystallinity and the associated temperature stability.

[0058] In one preferred embodiment, the aliphatic polyketone has an average molecular weight M in the range of 60,000 g / mol to 100,000 g / mol. n (number average) or average molecular weight M in the range of 132,000 g / mol to 320,000 g / mol w (weight average) (determined by GPC measurement). The polydispersity of the aliphatic polyketone is preferably 2.2 to 3.2. The aliphatic polyketone further preferably has 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, heating rate 20°C / min). It has been found that the crosslinked PK according to the invention exhibits particularly advantageous properties, in particular improved mechanical and chemical properties.

[0059] Preferably, the aliphatic polyketone (PK) is 2 cm 3 / 10min~200cm 3 / 10min, especially 6cm 3 / 10min~60cm 3The melt flow index (MFR) at 240°C is in the range of 1 / 10 min. This measurement is carried out in accordance with DIN ISO 1133, in which the material is melted at 240°C and the flowability is measured after a 2.16 kg load is applied to the die. An example of a particularly suitable aliphatic polyketone is M330A manufactured by Hyosung. The melt flow index generally correlates with the molecular weight of the polymer chain. According to the present invention, such a melt flow index has been found to be advantageous, since it allows both good thermoplastic processability and miscibility to be achieved, resulting in a homogeneous product with high stability, particularly high rigidity.

[0060] Suitable PKs are commercially available, for example, M230A (MFR = 150 g / 10 min at 240°C, 2.16 kg), M330A (MFR = 60 g / 10 min at 240°C, 2.16 kg), M340A (MFR = 60 g / 10 min at 240°C, 2.16 kg), M630A (MFR = 6 g / 10 min at 240°C, 2.16 kg), and M640A (MFR = 6 g / 10 min at 240°C, 2.16 kg) manufactured by Hyosung Corporation Co., Ltd., and AKRO-PLASTIC The three 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) manufactured by AKROTEK GmbH.

[0061] It is particularly preferred to use such PKs having the melt flow index described above with a crosslinker in an amount of 0.05% to 15% by weight, especially 0.1% to 5% by weight, based on the total amount of PK and crosslinker. In a preferred embodiment, the proportion of crosslinker used is 0.1 to 1.5% by weight, especially 0.3 to 1.0% by weight, based on the total amount of PK and crosslinker. These ratios and properties of the starting materials allow for particularly good processability of the product. In particular, it is characterized by a particularly high stiffness and a high modulus of elasticity. Furthermore, such PKs can be processed at temperatures at which thermoplastic mixing with the crosslinker is still possible, without the crosslinking reaction proceeding too quickly during the mixing process (= step i). This results in a plasticized compound that can be very easily used in a molding process to produce molded articles (= step ii). The molded article thus obtained can then be subjected to a post-cure (= step iii), in which the PK is crosslinked to obtain the final material properties. In other words, when using slow-reacting aromatic crosslinkers, the resulting molded part can be subjected to a post-cure (= step iii) in which the PK is crosslinked to obtain the final material properties. In the case of fast-reacting aliphatic crosslinkers, the resulting molded part may already be crosslinked after molding.

[0062] According to the present invention, the molded article is preferably based on PK. "Based on PK" here means that PK is the essential structure-imparting polymer component of the molded article. In one embodiment, PK is the only polymer component of the molded article. In a further embodiment, PK is present in a blend with an additional polymer, in particular a thermoplastic polymer. Preferred additional polymers include thermoplastic polyurethane (TPU), as well as other thermoplastic elastomers, polyester, liquid crystal polyester (LCP), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), and polycarbonate (PC). In this case, the preferred weight ratio of PK to the additional polymer, in particular the thermoplastic additional polymer, is 1:1 to 100:1, preferably 5:1 to 100:1, particularly preferably 10:1 to 100:1. Furthermore, the molded article may contain fillers, such as fibers, and / or conventional additives, such as processing aids and / or functional components. The crosslinked PK forms a matrix in which the additives present are uniformly dispersed.

[0063] <Crosslinking agent> Preferably, the at least one cross-linking agent is: di(aminophenyl) compounds in which two aminophenyl rings are linked together by an aliphatic group containing a carbocyclic group; a diamine compound selected from compounds of formulae (I), (II) and (III), - oligomers / polymers having at least two amide groups, saturated alicyclic compounds having at least two primary amino groups, oligomers / polymers containing these in an incorporated form, and - A mixture of these The crosslinker preferably contains at least 80 wt. %, particularly at least 90 wt. %, more particularly at least 99 wt. %, based on the total weight of the crosslinker, of a diamine source selected from the group consisting of:

[0064] In a preferred embodiment, the at least one crosslinker contains at least 80 wt. %, in particular at least 90 wt. %, more in particular at least 99 wt. %, based on the total weight of the crosslinker, of a diamine source selected from oligomers / polymers having at least two amide groups, saturated alicyclic compounds having at least two primary amino groups, oligomers / polymers containing these in an incorporated form, and mixtures thereof.

[0065] The amount of crosslinking agent is adjusted depending on the desired degree of crosslinking. Preferably, the amount of crosslinking agent is 0.05 to 15% by weight, particularly 0.1 to 5% by weight, based on the total amount of aliphatic polyketone and crosslinking agent. In a preferred embodiment, the amount of crosslinking agent is 0.1 to 1.5% by weight, particularly 0.3 to 1.0% by weight. It has been found that the stability of products using such a proportion of crosslinking agent can be particularly advantageous.

[0066] In a preferred embodiment, the crosslinking agent has a boiling point at 1013 mbar of at least 300°C, in particular at least 350°C, and in one particular embodiment at least 400°C. This is advantageous because such crosslinking agents have a relatively low vapor pressure at the required high processing temperatures. Preferably, the boiling point of the crosslinking agent at 1013 mbar is in the range of 300°C to 500°C, in particular in the range of 350°C to 500°C. Advantageously, the melting point of the crosslinking agent is below the melting point of the aliphatic polyketone (PK). This results in good processability and reduced risk to the user.

[0067] In one preferred embodiment, the diamine source used as the crosslinker is an oligomer / polymer having at least two amide groups.

[0068] An oligomer is a molecule made up of multiple structurally identical or similar units (monomers). When a relatively large number of monomers (more than 50) are present, the term polymer is used.

[0069] In the following, the term polyamide is used synonymously with an oligomer / polymer having at least two amide groups.

[0070] In the following, when polyamides are referred to as crosslinkers, this term also includes low 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 amino groups capable of reacting with keto groups of PK), if these products are capable of crosslinking PK. In this respect, both the polyamides used to provide the mixture of PK and crosslinker and the oligomers containing amino groups and their diamine monomers can act as crosslinkers.

[0071] In the following, the term polyamide will be used to refer to homopolyamides and copolyamides. In the context of the present invention, polyamides may be represented by standard abbreviations consisting of the letters PA followed by numbers and letters. Some of these abbreviations are defined in DIN EN ISO 1043-1: H2N-(CH2) z Polyamides derived from aminocarboxylic acids of the -COOH type or the corresponding lactams are represented by PAZ, where Z represents the number of carbon atoms in the monomer. For example, PA6 represents a polymer derived from ε-caprolactam or ε-aminocaproic acid. H2N-(CH2)x-NH2 and HOOC-(CH2) y Polyamides derived from diamines and dicarboxylic acids of the -COOH type are designated PAxy, where x is the number of carbon atoms in the diamine and y is the number of carbon atoms in the dicarboxylic acid. To designate a copolyamide, the components are listed in order of their quantitative proportions, separated by a slash. For example, PA66 / 610 is a copolyamide of hexamethylenediamine, adipic acid, and sebacic acid. The following letter abbreviations are used for the monomers containing aromatic or alicyclic groups used in the present invention: T = terephthalic acid, I = isophthalic acid, MXDA = m-xylylenediamine, IPDA = isophoronediamine, PACM = 4,4'-methylenebis(cyclohexylamine), MACM = 2,2'-dimethyl-4,4'-methylenebis(cyclohexylamine).

[0072] Polyamides can be described by the monomers used in their production: Polyamide-forming polymers are monomers suitable for polyamide formation.

[0073] In one preferred embodiment, the crosslinker is a polymer having at least two amide groups, the polymer being 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 alicyclic dicarboxylic acids, D) aliphatic or cycloaliphatic diamines, E) monocarboxylic acids, F) monoamines, G) at least trivalent amines; H) lactams, I) ω-amino acids, and K) Compounds different from A) to I) and capable of co-condensing therewith, as well as mixtures thereof In copolymerized form, the polyamide-forming monomers are selected from the group consisting of:

[0074] In a preferred embodiment of the present invention, polyamides, preferably having a melting point of 260° C. or less, are used as crosslinking agents. In particular, aliphatic polyamides are used. For this purpose, at least one component A) or B) and at least one component C) or D) must be present. However, in one particular embodiment, at least one component A) and at least one component D) must be present.

[0075] The aromatic dicarboxylic acid A) is preferably selected from unsubstituted or substituted phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or diphenyldicarboxylic acid, as well as derivatives and mixtures of the aforementioned aromatic dicarboxylic acids. The substituted aromatic dicarboxylic acid A) preferably has at least one C1-C4 alkyl group. Particularly preferred are substituted aromatic dicarboxylic acids A) with one or two C1-C4 alkyl groups. These are preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, particularly preferably methyl, ethyl, and n-butyl, very particularly preferably methyl and ethyl, and particularly preferably methyl. The substituted aromatic dicarboxylic acid A) may also have additional functional groups that do not interfere with amidation, such as 5-sulfoisophthalic acid, its salts, and derivatives. Among these, the sodium salt of 5-sulfoisophthalic acid dimethyl ester is preferred. Preferably, the aromatic dicarboxylic acid A) is selected from unsubstituted terephthalic acid, unsubstituted isophthalic acid, unsubstituted naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid and 5-sulfoisophthalic acid. Particularly preferred aromatic dicarboxylic acids A) are terephthalic acid, isophthalic acid or a mixture of terephthalic acid and isophthalic acid.

[0076] The aromatic diamine B) is 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, m-xylylenediamine, N,N'-dimethyl-4,4'-biphenyldiamine, bis-(4-methylaminophenyl)methane, 2,2-bis-(4-methylaminophenyl)propane, or mixtures thereof. A particularly preferred aromatic diamine is m-xylylenediamine.

[0077] The aliphatic or cycloaliphatic dicarboxylic acid C) is preferably selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic 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.

[0078] The aliphatic or cycloaliphatic diamine D) is preferably selected from ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2-methylpentamethylenediamine, 2,2,4-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.

[0079] Particularly preferably, the diamine D) is 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′-diaminodicyclohexylmethane, [3-(aminomethyl)-2-bicyclo[2.2.1]heptanyl]methanamine, aminated dimer fatty acids, and mixtures thereof. In one preferred embodiment of the invention, the aqueous solution contains at least one diamine D) selected from hexamethylenediamine, bis-(4-aminocyclohexyl)methane (PACM), 3,3'-dimethyl-4,4'diaminodicyclohexylmethane (MACM), isophoronediamine (IPDA) and mixtures thereof.

[0080] Monocarboxylic acids E) are used for the final capping of the polyamide oligomers used according to the invention. In principle, all monocarboxylic acids are suitable that can react with at least a portion of the available amino groups under the reaction conditions of the polyamide condensation. Suitable monocarboxylic acids E) are aliphatic, cycloaliphatic 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, benzoic acid, methylbenzoic acid, 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, phenylacetic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, erucic acid, fatty acids derived from soybean, linseed, castor bean and sunflower, acrylic acid, methacrylic acid, tertiary saturated monocarboxylic acids (e.g., Versatic® acid from Royal Dutch Shell plc), and mixtures thereof.

[0081] When using an unsaturated carboxylic acid or its derivative as the monocarboxylic acid E), it may be useful to add a commercially available polymerization inhibitor to the aqueous solution. Particularly preferably, the monocarboxylic acid E) is selected from acetic acid, propionic acid, benzoic acid, and mixtures thereof. In a very particularly preferred embodiment, the aqueous solution contains only acetic acid as the monocarboxylic acid E). In an even more particularly preferred embodiment, the aqueous solution contains only propionic acid as the monocarboxylic acid E). In an even more particularly preferred embodiment, the aqueous solution contains only benzoic acid as the monocarboxylic acid E).

[0082] Monoamine F) is used for the final capping of the polyamide oligomer used according to the invention. In principle, any monoamine capable of reacting with at least a portion of the available carboxyl groups under the reaction conditions of the polyamide condensation is suitable. Suitable monoamines F) are aliphatic, cycloaliphatic, and aromatic monoamines. These include methylamine, ethylamine, propylamine, butylamine, hexylamine, heptylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dicyclohexylamine, aniline, toluidine, diphenylamine, naphthylamine, and mixtures thereof.

[0083] Suitable at least trivalent amines G) are 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-trimethylcyclohexyl]hexane-1,6-diamine, N'-[3-(aminomethyl)-3,5,5-trimethylcyclohexyl]dodecane-1,12-diamine, N'-[(5-amino-1,3,3-trimethylcyclohexyl)methyl]hexane-1,6-diamine, N '-[(5-amino-1,3,3-trimethylcyclohexyl)methyl]dodecane-1,12-diamine, 3-[[[3-(aminomethyl)-3,5,5-trimethylcyclohexyl]amino]methyl]-3,5,5-trimethylcyclohexanamine, 3-[[(5-amino-1,3,3-trimethylcyclohexyl)methylamino]methyl]-3,5,5-trimethylcyclohexanamine, 3-(aminomethyl)-N-[3-(aminomethyl)-3,5,5-trimethylcyclohexyl]-3,5,5-trimethylcyclohexanamine. Preferably, at least trivalent amines G) are not used.

[0084] Suitable lactams H) are ε-caprolactam, 2-piperidone (δ-valerolactam), 2-pyrrolidone (γ-butyrolactam), capryllactam, enantholactam, lauryllactam and mixtures thereof.

[0085] Suitable ω-amino acids I) are 6-aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and mixtures thereof.

[0086] Suitable compounds K) which are different from A) to I) and which can be co-condensed with them are at least trivalent carboxylic acids, diaminocarboxylic acids, etc. Suitable compounds K) further include 4-[(Z)-N-(6-aminohexyl)-C-hydroxycarbonimidoyl]benzoic acid, 3-[(Z)-N-(6-aminohexyl)-C-hydroxycarbonimidoyl]benzoic acid, (6Z)-6-(6-aminohexylimino)-6-hydroxyhexanecarboxylic acid, 4-[(Z)-N-[(5-amino-1,3,3-trimethylcyclohexyl)methyl]-C-hydroxycarbonimidoyl]benzoic acid, 3 -[(Z)-N-[(5-amino-1,3,3-trimethylcyclohexyl)methyl]-C-hydroxycarbonimidoyl]benzoic acid, 4-[(Z)-N-[3-(aminomethyl)-3,5,5-trimethylcyclohexyl]-C-hydroxycarbonimidoyl]benzoic acid, 3-[(Z)-N-[3-(aminomethyl)-3,5,5-trimethylcyclohexyl]-C-hydroxycarbonimidoyl]benzoic acid, and mixtures thereof.

[0087] In another preferred embodiment of the present invention, a crosslinking agent selected from polyamides, their copolymers and mixtures thereof is used, which has a melting range of 200°C to 250°C, preferably a melting range of 220°C to 240°C, in particular a melting range of 220°C to 230°C.

[0088] In another preferred embodiment, the at least one crosslinking agent is selected from saturated alicyclic compounds having at least two primary amino groups and oligomers / polymers incorporating these. Suitable compounds are those with a boiling point above 300°C. In a preferred embodiment, these compounds are present as liquids in step i). Therefore, they can function as an internal solvent during melt mixing. Preferably, the saturated alicyclic compound is an aminated fatty acid dimer (dimer fatty acid).

[0089] As used herein, the term "fatty acid dimer" refers to the dimerization product of the reaction of two or more monounsaturated or polyunsaturated fatty acids. Such fatty acid dimers are well known in the art and typically exist as mixtures.

[0090] The mixtures produced by the oligomerization of unsaturated fatty acids are called aminated dimer fatty acids (also known as aminated dimer fatty acids or dimer acids). 12 ~C 22 Fatty acids can be used as starting materials. C used in the production of dimer fatty acids 12 ~C 22 Depending on the number and position of the double bonds in the fatty acid, the amino groups of the dimer fatty acid are linked together mainly by hydrocarbon groups having 24 to 44 carbon atoms. These hydrocarbon groups may be unbranched or branched, and may contain double bonds, C6 alicyclic hydrocarbon groups, or C6 aromatic hydrocarbon groups, and the alicyclic and / or aromatic groups may also be present in condensed form. Preferably, the groups linking the amino groups of the dimer fatty acid do not contain aromatic hydrocarbon groups, and very preferably do not contain unsaturated bonds. C 18 Particularly preferred are fatty acid dimers, i.e., fatty acid dimers having 36 carbon atoms. These can be obtained, for example, by dimerization of oleic acid, linoleic acid, linolenic acid, and mixtures thereof. Dimerization is optionally followed by hydrogenation and then amination.

[0091] In one particular embodiment, the saturated alicyclic compound is [ka] is.

[0092] In another particular embodiment, the saturated alicyclic compound is [ka] is.

[0093] In one particular embodiment, the polymer comprises at least one aminated dimer fatty acid incorporated therein. In an even more particular embodiment, the polymer comprises the compound [ka] or [ka] It contains in an incorporated form.

[0094] In another preferred embodiment, the at least one crosslinking agent is a mixture comprising an oligomer / polymer having at least one amide group and a saturated alicyclic compound having at least two primary amino groups.

[0095] In another preferred embodiment, the at least one crosslinking agent is a mixture comprising an oligomer / polymer having at least one amide group and an oligomer / polymer having therein, in polymerized form, at least one saturated alicyclic compound having at least two primary amino groups.

[0096] In another preferred embodiment, at least one crosslinker is selected from the group consisting of: [ka] [In the formula, R 1 , R 2, R 3 and R 4 are independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C6-C 14 aryl, and the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C6-C 14 aryl, and the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C6-C 14 aryl, and the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by X is selected from a bond, oxygen, sulfur, carbonyl, sulfonyl, sulfoxide, C1-C6 alkylene, C2-C6 alkenylene, and phenylene; R a is halogen, nitro, cyano, hydroxy, carboxyl, amino, C6-C 12aryl, wherein the aryl group is unsubstituted or selected from R c is replaced by R b is selected from halogen, nitro, cyano, amino, C1-C4 alkyl and C1-C4 haloalkyl; R c is selected from halogen, nitro, cyano, C1-C4 alkyl and C1-C4 haloalkyl.

[0097] Examples of C1-C4 alkyl groups are especially methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl and tert-butyl.

[0098] Examples of C1-C6 alkyl groups are in particular the previously mentioned C1-C4 alkyl groups, as well as the n-pentyl and n-hexyl groups.

[0099] C1-C4 haloalkyl preferably denotes one of the above mentioned C1-C4 alkyl groups, preferably having 1, 2, 3, 4 or 5, preferably 1, 2 or 3 halogen substituents, including for example trifluoromethyl.

[0100] Halogen represents fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.

[0101] Unsubstituted C6~C 14 Aryl preferably represents phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthacenyl, more preferably phenyl or naphthyl. 14 Aryl preferably has 1, 2, 3 or 4 or more groups selected from halogen, nitro, cyano, C1-C4 alkyl and C1-C4 haloalkyl. 14 Examples of aryl are tolyl, xylyl and mesityl.

[0102] C1-C6 alkylene is preferably -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2- or -C(CH3)2-.

[0103] In a preferred embodiment, at least one crosslinker is represented by formula (I) or (II): [In the formula, R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 is hydrogen, R 1 and R 4 are independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C6-C 14 aryl, and the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by R 9 and R 12 are independently selected from hydrogen, halogen, nitro, cyano, hydroxy, amino, C-C alkyl, C-C alkenyl, C-C alkynyl, C-C aryl, and the alkyl, alkenyl, and alkynyl groups are unsubstituted or a and the aryl group is unsubstituted or substituted with R b is replaced by X is selected from a bond, oxygen, sulfur, carbonyl, sulfonyl, sulfoxide, C1-C6 alkylene, C2-C6 alkenylene, and phenylene; R a is halogen, nitro, cyano, hydroxy, carboxyl, amino, C6-C 12 aryl, wherein the aryl group is unsubstituted or selected from R c is replaced by Rb is selected from halogen, nitro, cyano, amino, C1-C4 alkyl and C1-C4 haloalkyl, and R c is selected from halogen, nitro, cyano, C1-C4 alkyl and C1-C4 haloalkyl.

[0104] In one particularly preferred embodiment, at least one crosslinker is a compound of formula (Ia) or (II.a) [ka] [In the formula, R 1 , R 4 , R 9 and R 12 and X is: [Table 1] [Table 2] It is a compound of the formula:

[0105] In another preferred embodiment, the crosslinker has formula (III.a) and (III.b): [ka] The compound is selected from the group consisting of:

[0106] In one particular embodiment, the crosslinker is a compound selected from the group consisting of (III.a1) and (III.b1): [ka] The compound is selected from the group consisting of:

[0107] In a further preferred embodiment, at least one cross-linking agent is a di(aminophenyl) compound in which two aminophenyl rings are linked to each other by an aliphatic group bearing a carbocyclic group.

[0108] The di(aminophenyl) compound used as a crosslinker (or diamine source) has two aminophenyl rings linked together. Therefore, this compound is a primary diamine. Therefore, in one embodiment of the present invention, each phenyl ring has only a single amino group. However, it is also possible for each phenyl ring to independently have two or three amino groups. This compound is a small molecule, not a polymer. In addition to the amino group, the phenyl ring may have further substituents, such as alkyl or halogen groups. The two aminophenyl rings are connected by an aliphatic group. The aliphatic group consists only of carbon and hydrogen and is not aromatic. The di(aminophenyl) compound used as a crosslinker (or diamine source) preferably has no double or triple bonds other than those between the two phenyl rings. The aliphatic group has a carbocyclic group. The carbocyclic group is a hydrocarbon ring that can have, for example, 4 to 7 carbon atoms, preferably 5 or 6 carbon atoms. The carbocyclic group can include a double bond in the phenyl ring. Preferably, the carbocyclic group has only a single aliphatic hydrocarbon ring. Preferably, the aliphatic group has a total of 5 to 15 carbon atoms, especially 6 to 8. Because the aliphatic group is between the carbocyclic groups, the two phenyl rings are not conjugated.

[0109] According to the present invention, it has surprisingly been found that PKs crosslinked with such di(aminophenyl) compounds exhibit particularly advantageous properties: in particular, the crosslinked PKs exhibit improved thermal stability and improved mechanical stability.

[0110] In a preferred embodiment, the di(aminophenyl) compound used as the crosslinker (or diamine source) is a condensed compound in which only one of two phenyl rings is condensed to a carbocyclic group. Annelation (condensation) refers to the addition of another ring to a ring of a cyclic molecule. The two condensed rings share two carbon atoms, thus the C—C double bond of the phenyl ring. The use of such a condensed crosslinker has the advantage of forming particularly rigid and regular bonds between PK chains, which allows the product to achieve particularly high temperature stability and rigidity.

[0111] The amino groups of the di(aminophenyl) compound used as a crosslinker (or diamine source) can, in principle, be located at any position on the phenyl group, i.e., ortho, meta, or para relative to the aliphatic bond between the two phenyl rings. In embodiments in which each phenyl group has only a single amino group, it is preferable for the two amino groups to be as far apart as possible. This can be achieved when the two amino groups are attached para to the aliphatic bond and / or at the 4- and 4'-positions on the phenyl ring. Thus, in a preferred embodiment, the diaminodiphenyl compound is a 4,4'-diaminodiphenyl compound. Overall, the advantage of spacing the amino groups as far apart as possible is that it reduces the formation of undesired intramolecular reactions in which the crosslinker forms two bonds with the same PK polymer chain. Such intramolecular reactions with the crosslinker could disrupt the PK crystalline structure without providing a crosslinking effect, thereby reducing the stability of the product.

[0112] In one preferred embodiment of the present invention, the di(aminophenyl) compound used as the crosslinker (or diamine source) is an asymmetric compound.

[0113] In one preferred embodiment of the present invention, the di(aminophenyl) compound used as the crosslinker (or diamine source) is represented by the general formula (IV): [ka] [In the formula, R 19 and R 20 are independently selected from H, substituted or unsubstituted alkyl having 1 to 20 C atoms, in particular 1 to 4 C atoms, in particular methyl or ethyl, substituted or unsubstituted aryl having 5 to 12 C atoms, F and Cl, and Z is an aliphatic group having a carbocyclic group. In this respect, each phenyl ring may be provided with 1, 2 or 3 R independently selected from each other. 19 or R 20Preferably, the phenyl ring has an R 19 and / or R 20 Particularly preferably, the group R 19 and R 20 are each H. Additional groups R 19 and R 20 Crosslinkers that do not have this feature are relatively readily available and can be processed into more stable crosslinked PKs.

[0114] The group Z may be linked to each phenyl group by two bonds or by one bond, preferably the group Z is linked to one phenyl group by two bonds and to the second phenyl group by one bond.

[0115] In another preferred embodiment of the present invention, the crosslinker has the general formula (IV.a) [ka] [In the formula, x is the R 19 is 3 or 4 depending on the number of bonds in the phenyl ring substituted with y is the R 20 is 3 or 4 depending on the number of bonds in the phenyl ring substituted with In each case, R 19 are independently selected from hydrogen, unsubstituted or substituted alkyl or having 1 to 20 carbon atoms, unsubstituted or substituted aryl or having 5 to 14 carbon atoms, F, and Cl; R 20 is independently selected at each occurrence from hydrogen, unsubstituted or substituted alkyl or having 1 to 20 carbon atoms, unsubstituted or substituted aryl or having 5 to 14 carbon atoms, F, and Cl; Z is an aliphatic group having a carbocyclic moiety, where Z is linked to each of the two phenyl rings by one or two bonds.

[0116] Preferably, Z is connected to R by two bonds.19 In that case, in compound (IV.a), x is 3. Preferably, Z is connected by one bond to R 20 In that case, in compound (IV.a), y is 4. In particular, x is 3 and y is 4. In particular, Z forms an indane skeleton with the two phenyl rings to which it is attached.

[0117] In the compounds of the formulae (IV) and (IV.(a)), alkyl having 1 to 20 C atoms preferably includes the definition given above for C1-C6 alkyl, and further includes n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, arachidyl and their structural isomers. Particularly preferred is alkyl having 1 to 4 C atoms, in particular methyl or ethyl.

[0118] Substituted alkyl having 1 to 20 C atoms preferably has at least one (e.g. 1, 2, 3 or more) substituent(s) selected from halogen, nitro, cyano and C1-C4 alkoxy. Substituted alkyl particularly represents C1-C4 haloalkyl, preferably having 1, 2, 3, 4 or 5, preferably 1, 2 or 3 halogen substituents. This includes, for example, trifluoromethyl.

[0119] In the compounds of formulae (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 having 5 to 12 carbon atoms preferably represents phenyl or naphthyl. Substituted aryl having 5 to 14 carbon atoms or substituted aryl having 5 to 12 carbon atoms preferably has one, two, three, or more than four groups selected from halogen, nitro, cyano, C1-C4 alkyl, and C1-C4 haloalkyl. Examples of substituted aryl having 5 to 14 carbon atoms or substituted aryl having 5 to 12 carbon atoms are tolyl, xylyl, and mesityl.

[0120] In the compounds of formula (IV.a), the group R 19 is preferably selected from hydrogen, substituted or unsubstituted alkyl having 1 to 4 C atoms, F and Cl. Particularly preferred is the group R 19 is selected from hydrogen and unsubstituted alkyl having 1 to 4 C atoms.

[0121] In the compounds of formula (IV.a), the group R 20 is preferably selected from hydrogen, substituted or unsubstituted alkyl having 1 to 4 carbon atoms, F and Cl. Particularly preferred is the group R 20 is selected from hydrogen and unsubstituted alkyl having 1 to 4 carbon atoms.

[0122] Preferably, each phenyl ring contains a group R other than hydrogen. 19 or R 20 In one particular embodiment, R 19 and R 20 are all hydrogen. 19 and R 20 Compounds of formula (IV.a) in which are all hydrogen are relatively readily available and can be processed to more stable cross-linked PKs.

[0123] In one preferred embodiment, the crosslinker has the general formula (V): [ka] [In the formula, R 19 and R 20 are independently selected from H, substituted or unsubstituted alkyl having 1 to 20 C atoms, in particular having 1 to 4 C atoms, in particular methyl or ethyl, substituted or unsubstituted aryl having 5 to 12 C atoms, F and Cl, R 21 is a carbocyclic group having 2 to 3 C ring atoms, which may be substituted by at least one alkyl group having 1 to 4 C atoms, in particular methyl or ethyl. Particularly preferred is the group R 19 and R 20 are each H. Thus, the carbocyclic group R 21 is a pentyl or hexyl group. Such crosslinkers have the advantage that they provide a particularly good combination of temperature and mechanical stability of the crosslinked PK.

[0124] In one preferred embodiment, the crosslinker has the general formula (Va): [ka] [In the formula, R 21 is selected as above. Such crosslinkers have the advantage that they provide a particularly good combination of temperature and mechanical stability of the crosslinked PK.

[0125] In one preferred embodiment, the crosslinker has the formula (V.a1): [ka] It has.

[0126] This compound provided a particularly advantageous combination of thermal and mechanical stability for cross-linked PK in the experiments carried out. Its chemical name is 1-(4-aminophenyl)-1,3,3-trimethylindan-5-amine (CAS number 54628-89-6).

[0127] In another preferred embodiment, the crosslinker has the formula (V.b1): [ka] It has.

[0128] In the experiments carried out, this compound also provides a particularly advantageous combination of thermal and mechanical stability of cross-linked PK. Its chemical name is 1-(4-aminophenyl)-1,3,3-trimethylindan-6-amine.

[0129] In another preferred embodiment, the crosslinker comprises a mixture of compounds of formula (V.a1) and (V.b1). In the experiments carried out, this crosslinker also provides a particularly advantageous combination of thermal and mechanical stability of the crosslinked PK.

[0130] In a further preferred embodiment, the crosslinker has formula (VII): [ka] It has.

[0131] In the tests carried out, this crosslinker also provides a particularly advantageous combination of temperature and mechanical stability for crosslinked PC. Its chemical name is 1-(4-aminophenyl)-1,3,3-trimethylindanamine (CAS number 68170-20-7). Here, the amino group on the aromatic ring of the indan may be present in any position. Also included are mixtures of 1-(4-aminophenyl)-1,3,3-trimethylindanamines in which the amino group on the aromatic ring of the indan is present in different positions.

[0132] According to the invention, it is preferred to use a single specific crosslinking agent in order to obtain material properties that are as uniform as possible, but it is also possible to use a mixture of two or more crosslinking agents.

[0133] <Flame retardant (A)> According to the present invention, the molded article and the curable polymer composition contain at least one flame retardant (A). The term flame-retardant PK means that the PK comprises at least one flame retardant (A). The term flame-retardant molded article means that the molded article comprises at least one flame retardant (A). The term flame-retardant curable polymer composition means that the polymer composition comprises at least one flame retardant (A).

[0134] The flame retardant (A) is selected from organic compounds, inorganic compounds and mixtures thereof.

[0135] The inorganic flame retardant A) is preferably selected from compounds of phosphorus, magnesium, calcium, boron, aluminum, antimony, tin, zinc and mixtures thereof.Another suitable but not preferred inorganic flame retardant A) is red phosphorus.To avoid the generation of phosphine gas by reaction with moisture, the material can be stabilized by chemical modification of red phosphorus.

[0136] Specific inorganic flame retardants A) are selected from magnesium hydroxide, aluminum hydroxide (also written as aluminum trihydrate, ATH), calcium borate, calcium-based hydrated minerals, boron, antimony trioxide, tin oxide, zinc borate, zinc stannate, zinc hydroxystannate, molybdenum trioxide, red phosphorus, ammonium polyphosphate, and mixtures thereof. Preferably, flame retardants A) are selected from magnesium hydroxide, calcium borate, calcium-based hydrated minerals, boron, antimony trioxide, tin oxide, zinc borate, zinc stannate, zinc hydroxystannate, molybdenum trioxide, and mixtures thereof.

[0137] The preferred inorganic flame retardants are metal hydroxides. During a fire, metal hydroxides release only water and do not form toxic or corrosive exhaust gas products. Furthermore, these hydroxides can reduce the concentration of smoke gases during a fire.

[0138] In one preferred embodiment, the flame retardant A) comprises or consists of magnesium hydroxide (Mg(OH)2). In particular, the magnesium hydroxide has a particle size ranging from a submicron particle size, preferably in the range of less than 1 micrometer up to 6 micrometers. Particularly preferred is a particle size in the range of 1 to 2 micrometers. In particular, the magnesium hydroxide has a large particle surface area, preferably 2 to 35 m 2 / g, particularly preferably 2 to 10 m 2 / g。 In one particular embodiment, the magnesium hydroxide particles are coated with surfactants such as various fatty acids or salts or esters of fatty acids. Particularly preferred surfactants include calcium stearate and stearic acid.

[0139] The organic flame retardants A) are preferably selected from organic phosphorus compounds, organic nitrogen-containing compounds, organic halogen compounds and mixtures thereof.

[0140] Halogenated organic flame retardants are highly effective because they exhibit excellent flame retardancy even in small amounts, and therefore function well in the molded articles described herein. Examples of suitable halogenated organic flame retardants include polybrominated diphenethyl ethers (PBDEs), such as DecaBDE, polybrominated biphenyls (PBBs), brominated polystyrene, tetrabromobisphenol A (TBBPA), brominated cyclic hydrocarbons, such as hexabromocyclododecane (HBCD), or brominated phenol derivatives, such as tribromophenol. Many halogenated chemicals are persistent, bioaccumulative, toxic, and / or critical for waste disposal, so their use, although advantageous in individual cases, is generally not preferred in the present invention.

[0141] Preferably, the molded article or curable polymer composition according to the invention contains an organic phosphorus-containing flame retardant. Most known phosphorus-containing flame retardants can be used in PK according to the invention.

[0142] Preferred organophosphorus compounds are selected from phosphates, polyphosphates, phosphites, phosphinates, phosphonites, phosphoric and phosphonic acid esters, dihydrooxaphosphophenanthrene derivatives (DOPO) and phosphazenes.

[0143] Phosphates within the meaning of the present invention are salts and esters of orthophosphoric acid (H3PO4).

[0144] Suitable phosphates are selected from melamine phosphate, alkyl phosphates, aryl phosphates, oligomeric phosphates, aliphatic diphosphates, pentaerythritol phosphate, halogen-containing phosphates, ammonium polyphosphates, and mixtures thereof.

[0145] The melamine phosphate is, for example, melamine orthophosphate, melamine orthophosphate dimelamine, melamine pyrophosphate or melamine polyphosphate.

[0146] Alkyl phosphates are, for example, dimethyl phosphate, diethyl phosphate, dipropyltrimethyl phosphate, triethyl phosphate, tripropyl phosphate, tris(2-ethylhexyl) phosphate or pentaerythritol phosphate.

[0147] Aryl phosphates are, for example, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, resorcinol and bisphenol A bis(diphenyl) phosphate).

[0148] A preferred alkylaryl phosphate is 2-ethylhexyl diphenyl phosphate.

[0149] The oligomeric phosphate is, for example, oligomeric ethyl ethylene phosphate.

[0150] Halogen-containing phosphates are, for example, tris(2-chloroethyl)phosphate, tris(1-chloro-2-propyl)phosphate (TCPP), tris(1,3-dichloro-2-propyl)phosphate, and tris(tribromoneopentyl)phosphate.

[0151] Phosphonates within the meaning of the present invention are salts and esters of phosphonic acid (HP(O)(OH)2) and organic phosphonic acids derived therefrom (RPO(OH)2, where R is selected from alkyl or aryl).

[0152] Suitable phosphonates are, for example, dimethylmethylphosphonate (DMMP), diethylethylphosphonate, diethylpropylphosphonate, and cyclic phosphonates such as Amgard CU from Solvay and spirobis(methylphosphonate) from THOR GmbH, halogen-containing phosphonates such as bis(2-chloroethyl)-2-chloroethylphosphonate, and mixtures thereof.

[0153] Phosphinates are salts and esters of phosphinic acid (H2P(O)(OH)).

[0154] In one preferred embodiment, the flame retardant A) has the general formula (P1) and / or (P2) [ka] [In the formula, R 30 and R 31 are independently selected from linear or branched C1-C8 alkyl and aryl; R 32 is a linear or branched C1-C 10 -Alkylene, C6-C 10 -arylene, C1-C4-alkyl-C6-C 10 -Arylene and C6-C 10 -aryl-C1-C4-alkylene; M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Li, Na, K or a protonated nitrogen base; m is 2 or 3, n is 1 or 3, and x is 1 or 2] and / or a polymer thereof.

[0155] In particular, the flame retardant A) is selected from calcium, aluminum and zinc salts of dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, n-propylmethylphosphinic acid, n-propylethylphosphinic acid, di-n-propylphosphinic acid, diisopropylphosphinic acid and diphenylphosphinic acid. Suitable commercial products are aluminum diethylphosphinate (DEPAL) and zinc diethylphosphinate. Aluminum diethylphosphinate, zinc diethylphosphinate and mixtures thereof are particularly preferred flame retardants A).

[0156] Phosphites for the purposes of this invention are esters and salts of phosphorous acid (P(OH)3).

[0157] Suitable phosphites include triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, The phosphate group is selected from the group consisting of pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris-(tert-butylphenyl))pentaerythritol diphosphite, tristearyl sorbitol triphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, and mixtures thereof.

[0158] In the context of the present invention, organic polyphosphates are salts or esters of polymeric oxyanions formed from tetrahedral PO4 (phosphate) structural units linked together by shared oxygen atoms. The cations are organic cations. Preferred organic polyphosphates are melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, dimelamine phosphate, and dimelamine pyrophosphate. These compounds are also referred to below as melamine-based flame retardants.

[0159] Phosphonites are organophosphorus compounds having the formula P(OR)2R, where R is selected from alkyl or aryl.

[0160] In a further preferred embodiment, the flame retardant A) comprises or consists of a dihydrooxaphosphophenanthrene derivative (DOPO) or a derivative thereof. DOPO and DOPO derivatives suitable as flame retardants are described in U.S. Patent Application Publication No. 2012 / 0095140. DOPO is the abbreviation for 6H-dibenz[c,e][1,2]oxaphosphorine-6-oxide (CAS Registry Number 35948-25-5).

[0161] The nitrogen-containing flame retardant A) is preferably selected from melamine-based flame retardants, guanidine-based flame retardants, sterically hindered amine-based flame retardants, isocyanurate-based flame retardants, allantoin, benzoguanamine, glycoluril, urea cyanurate and mixtures thereof.

[0162] The melamine-based flame retardant A) is preferably selected from melamine, melamine cyanurate, melamine borate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, dimelamine phosphate and dimelamine pyrophosphate, melamine phenylphosphonate, condensation products of melamine and mixtures thereof.

[0163] The term "melamine cyanurate" refers to a 1:1 complex of 1,3,5-triazinane-2,4,6-trione-1,3,5-triazine-2,4,6-triamine.

[0164] Preferred condensation products of melamine are melam (M1), melem (M2), melon (M3) and mixtures thereof.

[0165] [ka]

[0166] The guanidine-based flame retardant A) is preferably selected from guanidine phenylphosphonates. Guanidine phenylphosphonates and melamine phenylphosphonates are described, for example, in US Patent Application Publication No. 2012 / 0108712. Preferred are compounds of formula (M4) and (M5): [ka] [In formulas (M4) and (M5), R 1 ~R 5 are independently selected from hydrogen, C1-C4 alkyl, hydroxyl, hydroxy-C1-C4 alkyl, and C1-C4 alkoxy; x is 1 or 2, In formula (M4), R 6 ~R 9 are independently selected from hydrogen, C1-C4 alkyl, phenyl, phenyl-C1-C4 alkyl, wherein phenyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from C1-C4 alkyl and hydroxyl.

[0167] Suitable melamine phenylphosphonate salts are described in US Pat. No. 4,061,605, and suitable guanidine phenylphosphonate salts are described in US Pat. No. 4,308,197.

[0168] Preferred sterically hindered amine flame retardants A) are, for example, U.S. Patent No. 5,004,770, U.S. Patent No. 5,204,473, U.S. Patent No. 5,096,950, U.S. Patent No. 5,300,544, U.S. Patent No. 5,112,890, U.S. Patent No. 5,124,378, U.S. Patent No. 5,145,893, U.S. Patent No. 5,216,156, U.S. Patent No. 5,844,026, U.S. Patent No. 6,117,995 and U.S. Patent No. 6,271,377, sterically hindered N-alkoxyamines (NOR HALS) disclosed in. Flame retardant compositions based on sterically hindered amine flame retardants are, for example, described in WO 2009 / 080554 and U.S. Patent Application Publication No. 2012 / 0108712.

[0169] The isocyanurate flame retardant A) is preferably selected from polyisocyanurates, esters of isocyanuric acid or isocyanurates. Typical examples are hydroxyalkyl isocyanurates, such as tris-(2-hydroxyethyl)isocyanurate, tris(hydroxymethyl)isocyanurate, tris(3-hydroxy-n-propyl)isocyanurate or triglycidyl isocyanurate.

[0170] Further suitable nitrogen-containing flame retardants A) are allantoin (=(2,5-dioxo-4-imidazolidinyl)urea), benzoguanamine, glycoluril (=tetrahydroimidazo[4,5-d]imidazole-2,5-dione) and urea cyanurate.

[0171] The aforementioned flame retardant A) can be used as the sole flame retardant component of the molded article, or any combination of two or more flame retardants. For the purposes of the present invention, a combination of two or more (e.g., three, four, or five or more) flame retardants A) is also referred to as a flame retardant composition. The flame retardants included in the flame retardant composition can all be selected from the same class of flame retardants or from different classes of flame retardants.

[0172] A particular embodiment is a flame retardant composition comprising at least one flame retardant A) and at least one synergist. The synergist may be the flame retardant itself. In this case, synergistic effect means that the overall flame retardant effect is greater than the sum of the effects of the individual components. The synergist may also be at least one component different from the flame retardant A). In this case, the synergist allows for a reduced concentration of the flame retardant A) in the molded article or curable polymer composition according to the invention and / or has an additional beneficial effect on the properties of the final product. The synergist may, for example, act as an anti-dripping agent, improve performance, for example in UL94 tests, improve char formation during fire, or reduce smoke density.

[0173] A preferred embodiment is a flame retardant composition containing magnesium hydroxide and an inorganic synergist, preferably selected from borates, especially zinc borates, silicates, and nanocomposites based on aluminosilicate clay minerals, especially montmorillonite.

[0174] A further preferred embodiment is a flame retardant composition containing magnesium hydroxide and a further component, preferably selected from phosphorus-containing flame retardants, Sb2O3, zinc borate and mixtures thereof.

[0175] In a further preferred embodiment, at least one phosphorus-containing flame retardant A) can be combined with at least one synergist different from the phosphorus-containing flame retardant. In a particular embodiment, the flame retardant (A) is selected from phosphorus-containing flame retardants selected from phosphates, phosphites, phosphinates, phosphonites, phosphoric and phosphonic esters, phosphazenes, and the synergist is selected from melamine.

[0176] In particular, phosphorus-containing flame retardants selected from phosphates, phosphites, phosphinates, phosphonites, phosphoric acid esters, phosphonic acid esters, phosphazenes.

[0177] A further particular embodiment is a flame retardant composition A) comprising A1) at least one salt of an alkylphosphonic acid or an arylphosphonic acid and A2) at least one nitrogen-containing flame retardant. Preferred is a flame retardant composition A) comprising A1) at least one salt of an alkylphosphonic acid or an arylphosphonic acid and A2) at least one melamine or a condensation product thereof.

[0178] A further particular embodiment is a composition comprising A) at least one phosphinate salt of formula (P1) and / or P2) as defined above, such as aluminum dimethylphosphinate, alumina methylethylphosphinate, and aluminum methylpropylphosphinate, and B) a nitrogen compound, such as allantoin (=(2,5-dioxo-4-imidazolidinyl)urea), benzoguanamine, glycoluril (=tetrahydroimidazo[4,5-d]imidazole-2,5-dione), urea cyanurate, melamine cyanurate, and melamine phosphate. Also suitable are synergistic flame retardant combinations comprising A) a phosphinate of formula (II) above, such as diethylphosphinate, where M is calcium, magnesium, aluminum, and / or zinc, and B) a condensation or reaction product of melamine, such as melamine polyphosphate, melam polyphosphate, and melem polyphosphate.

[0179] A further particular embodiment is a composition comprising as a synergist a zinc compound selected from zinc stannates (ZnSnO3 and Zn2SnO4) and zinc hydroxystannate (ZnSn(OH)6). In particular, zinc hydroxystannate is an environmentally friendly flame retardant with good smoke suppression properties and also acts as a flame retardant itself.

[0180] Preferably, the flame retardant (A) is halogen-free.

[0181] 10. A molded article according to any one of the preceding claims, wherein the molded article preferably comprises said flame retardant (A) in an amount of 5 to 30% by weight, based on the total weight of the polymer matrix, in particular 7 to 15% by weight, based on the total weight of the polymer matrix.

[0182] <Fillers, reinforcing materials and additives> The curable / curable polymer compositions and molded parts may optionally contain fillers and reinforcing materials and / or other additives. The flame-retardant crosslinked PK forms a matrix in which the fillers and reinforcing materials and / or additives are uniformly dispersed.

[0183] The term "fillers and reinforcing materials" is broadly interpreted in the context of the present invention and includes particulate fillers, fibrous materials, and any transitional forms. Particulate fillers can have a wide range of particle sizes, from dust-like to coarse particles. Filler materials can be organic or inorganic fillers and reinforcing materials.

[0184] Suitable inorganic reinforcing materials include, for example, ceramic fillers such as aluminum nitride, silicon nitride, and boron, or mineral fillers such as asbestos, talc, wollastonite, microvite, silicates, basalt, serpentine, chalk, calcined kaolin, mica, vermiculite, illite, smectite, montmorillonite, hectorite, metasilicic acid double hydroxide, feldspar and quartz powder, amorphous silica, kaolin, calcium carbonate, magnesium carbonate, calcium silicate, silicates, titanium dioxide, zinc oxide, glass particles, nanoscale layered silicates, nanoscale aluminum oxide (Al2O3), nanoscale titanium dioxide (TiO2), layered silicates, and nanoscale silicon dioxide (SiO2), and mixtures thereof. The fillers can also be surface-treated.

[0185] Additionally, one or more fibrous materials may be used, preferably selected from known inorganic reinforcing fibers such as carbon fibers, boron fibers, glass fibers, silica fibers, ceramic fibers, and basalt fibers; organic reinforcing fibers such as aramid fibers, polyester fibers, nylon fibers, and polyethylene fibers; and natural fibers such as wood fibers, flax fibers, hemp fibers, cellulosic fibers, cotton fibers, kenaf fibers, and sisal fibers.

[0186] Suitable glass fibers are, for example, short glass fibers (SGF), long glass fibers (LGF), continuous glass fibers, glass fabrics, mats, nonwovens, rovings, yarns, cut or crushed glass fibers, glass silk rovings and crushed glass silk.

[0187] Glass fibers having a length of 5 mm or less are typically referred to as short glass fibers, and glass fibers having a length of more than 5 mm are typically referred to as long glass fibers.

[0188] Suitable glass fibers are conventional glass fibers, for example E, S, C, AR, ECR.

[0189] The glass fibers may be substantially cylindrical with a circular cross section, although other cross-sectional shapes, such as oval or (rounded) square, are also suitable. In a preferred embodiment, the glass fibers have a substantially circular cross section. In this case, the thickness is the same as the average diameter.

[0190] The glass fibers used in the present invention typically have a diameter in the range of 3 to 50 micrometers, preferably 5 to 30 micrometers.

[0191] Single glass filaments are generally bundled together to form fibers, which may be bundled into yarns, ropes, or rovings, or woven into mats. In a particular embodiment, the glass fibers are derived from multifiber glass strands, also known as glass rovings. Multifiber glass strands or rovings preferably contain 500 to 10,000 glass filaments per strand. Examples of suitable rovings are Advantex products available as 1200 or 2400 tex, e.g., designated SE4220, SE4230, or SE4535, available from Binani 3B Fiber Glass company, or TUFRov 4575, TUFRov 4588, available from PPG Fiber Glass.

[0192] In preparing the molding compositions of the present invention, it may be convenient to use filamentous glass in the form of chopped strands.

[0193] Preferably, the filler is short glass fiber, which can be added to the polymer matrix during the extrusion process, or long glass fiber, which can be added to the polymer matrix during extrusion or injection molding.

[0194] Preferably, fillers and reinforcing agents, if present, are used in an amount of up to 80% by weight, especially 0.1% to 80% by weight, and especially 1% to 50% by weight, based on the total weight of the molded article.

[0195] Suitable additives are selected from carbon black, antioxidants, extenders, lubricants, light stabilizers (UV stabilizers, UV absorbers or UV blockers), heat stabilizers, slip and release agents, dyes and pigments, crosslinking reaction catalysts, thickeners, thixotropic agents, surfactants, viscosity modifiers, nucleating agents, plasticizers, antistatic agents, mold release agents, antifoaming agents, bactericides and mixtures thereof.

[0196] Preferably, additives, when present, are used in an amount of up to 20% by weight, especially from 0.1% to 20% by weight, more especially from 0.1% to 18% by weight, based on the total weight of the shaped article.

[0197] <Method> The method according to the present invention relates to a method for improving the flame retardancy of molded articles for electrical devices, which comprises a crosslinking reaction in which polymer chains of a polyketone are intramolecularly bonded to each other via covalent bonds, and the addition of a flame retardant (A). In particular, the method according to the present invention relates to a method for improving the flame retardancy of molded parts for electric transportation, which comprises a crosslinking reaction in which polymer chains of a polyketone are intramolecularly bonded to each other via covalent bonds, and the addition of a flame retardant (A).

[0198] Step (i) In step (i), a mixture containing a polyketone, a crosslinking agent, and a flame retardant is provided. The mixture provided in step (i) can be prepared by conventional compounding methods.

[0199] In one embodiment according to the present invention, the mixture of step (i) can be obtained by adding the individual components, such as PK, flame retardant (A) and crosslinker, and optionally fillers / reinforcements and additives, to the mixture.

[0200] In a second embodiment according to the invention, the mixture of step (i) can be obtained by adding a premix of one or more components, for example by producing a premix of PK and flame retardant (A), which is then mixed in a subsequent step with the crosslinker and, optionally, with fillers / reinforcements and additives.

[0201] In a third embodiment according to the invention, the mixture of step (i) can be obtained by adding a premix of one or more components, for example by producing a premix of the crosslinking agent and the flame retardant (A), which is then mixed in a subsequent step with the PK and, optionally, with fillers / reinforcements and additives.

[0202] In a fourth embodiment according to the invention, the mixture of step (i) can be obtained by adding a premix of one or more components, for example, by preparing a premix of PK, flame retardant (A), fillers / reinforcements and additives, which is then mixed with the crosslinker in a subsequent step.

[0203] The order of addition of the PK, crosslinker and flame retardant components is not important, as long as the crosslinking reaction between the PK and crosslinker occurs after the flame retardant is added to the mixture obtained in step (i).

[0204] In step (i), a mixture of at least one polyketone and at least one flame retardant is preferably provided as a premix, and the premix of flame retardant and polyketone is then blended with at least one crosslinking agent, and optionally with fillers and reinforcing agents, and optionally with other additives.

[0205] In step (i), preferably, at least one polyketone, at least one crosslinking agent, at least one flame retardant, optionally fillers and reinforcing agents, and optionally further additives different therefrom, are melt-mixed (variant 1) or dry-mixed (variant 2).

[0206] In the melt mixing (also referred to as melt blending) according to variant 1, the polymers are heated to a temperature above their melting temperature and intensively mixed by rolling, kneading, or extrusion. In this process, the temperature in step (i) is preferably adjusted so that the mixture is easily processable and has a viscosity suitable for compounding. Furthermore, the temperature in step (i) is preferably adjusted so that significant reaction between the polyketone and the crosslinker does not yet occur. Furthermore, at temperatures where the reaction between the PK and the crosslinker has already occurred, the residence time should be kept as short as possible. In contrast to PAEK, where the reactivity of the reacting carbonyl groups is reduced by the resonance effect of neighboring phenylene groups, the amino crosslinking of the PK with the crosslinker described according to the present invention preferably begins already in the molten state. According to the present invention, it is not necessary for the covalent bonding of the crosslinker to the PK via an amine bond to occur early, as in the methods described in the prior art. This is advantageous because the present invention allows for the elimination of an additional reaction step, which would require precise control to prevent undesired further reaction of the intermediate and the resulting premature crosslinking.

[0207] In one embodiment, in step (i), at least one polyketone, at least one crosslinking agent, at least one flame retardant, optionally fillers and reinforcing materials, and optionally further additives different therefrom, are fed into an extruder and mixed while plasticizing, and optionally granulated.

[0208] The temperature during melt mixing in step (i) is preferably in the range of 220 to 260°C.

[0209] In a further embodiment (variant 2), in step (i), at least one polyketone, at least one crosslinking agent, at least one flame retardant, optionally fillers and reinforcing materials, and optionally other additives are dry mixed. The aforementioned components can be mixed using known dry blending techniques. A dry blend of polyketone, at least one crosslinking agent, at least one flame retardant, optionally fillers and reinforcing materials, and optionally other additives is obtained.

[0210] The term "dry blending" (variant 2) for purposes of this application refers to a blending process at a temperature below the melting point of the polyketone, or below the lowest melting point of the polyketone if the polymer has multiple melting points. However, "dry blending" encompasses the use of each component in liquid form (but not a polymer melt, as previously discussed).

[0211] The temperature in step (i) during dry blending is below the softening range of the polyketone, preferably in the range of 0°C to 100°C.

[0212] During the preparation of the mixture, intensive mixing is carried out by suitable means, such as stirring or kneading equipment, to achieve a uniform distribution of the crosslinking agent and the polymer. This is very important for obtaining uniform material properties in terms of stability. In one embodiment, the crosslinking agent is dispersed in the polymer. In another embodiment, the crosslinking agent is dispersed at least on the surface of the polymer. Preferably, after preparation, the crosslinkable mixture is further processed in step (ii) without undergoing any additional intermediate steps that change the composition.

[0213] During mixing, intermediate products, such as granules, can be obtained, which are stable for long periods at temperatures below 80°C, preferably below 50°C, in particular below ambient temperature, and can, for example, be temporarily stored and / or transported to another location for further processing.

[0214] In a particularly preferred embodiment of the present invention, the mixture is solvent-free. In particular, no external solvent is added to the mixture. It has surprisingly been found that the mixture of polyketone, crosslinker, flame retardant, and filler or reinforcing material can be processed in an intimately mixed state without the use of solvents.

[0215] Preferably, the mixture is heated to a temperature at which it is in a liquid or flowable (plasticized) form, and in order to obtain a homogeneous mixture, it is preferable to select a temperature and residence time such that no significant crosslinking occurs in the process.

[0216] In a preferred embodiment, the crosslinking agent is added continuously to the polyketone to produce the mixture in step (i). In this case, the individual components may be in liquid or solid form. In this way, a particularly homogeneous mixture can be obtained. The crosslinking agent is preferably added under intimate mixing conditions, such as by stirring, kneading, rolling, and / or extrusion. In a preferred embodiment, the crosslinking agent is provided in the form of a concentrate. This has the advantage of allowing for better metering of the crosslinking agent, thereby improving the homogeneity of the mixture. Overall, the continuous addition of the crosslinking agent results in a particularly homogeneous mixture, thereby achieving particularly regular crosslinking. This prevents the formation of regions with different degrees of crosslinking, which could lead to inhomogeneity and damage the product under thermal or mechanical stress. In this way, particularly good properties can be achieved in terms of temperature and mechanical stability.

[0217] Step (ii) In step (ii), a shaped article is produced from the mixture obtained in step (i). Step (ii) of producing the shaped article includes all means for shaping the mixture into a three-dimensional shape that is retained in a cured, crosslinked state. Preferably, the shaped article is produced by a molding process customary for thermoplastics. In this context, it is preferred that the production of the shaped article takes place before and / or during crosslinking. In this context, it is generally not a significant problem if the mixture used in step (ii) already contains small amounts of crosslinked products. Particularly preferably, shaping takes place before step (iii), since the mixture can be advantageously thermoplastically processed and shaped before crosslinking, in particular by hot pressing, extrusion, injection molding and / or 3D printing.

[0218] When the components are mixed by dry blending in step (i), the dry blend is melted in step (ii) and subjected to the above-mentioned molding step.

[0219] In one embodiment, steps (i) and (ii) proceed separately and sequentially.

[0220] In a preferred embodiment, the shaped article is produced by thermoplastic molding in step (ii). This means that the compound can be molded from the melt in an uncrosslinked and / or at least not very crosslinked state, because otherwise thermoplastic processing would no longer be possible. If there are too many crosslinking sites, the PK intermediate loses fluidity and cannot be easily thermoplastically molded. The compound should be exposed to a high processing temperature for only a short time before molding. Therefore, the thermoplastic processing is preferably carried out so that the residence time of the mixture in the equipment is as short as possible. In this context, in one embodiment, it is preferred that the processing be carried out so that the majority of the crosslinking reaction, i.e., more than 80%, more than 90%, or more than 95% of the crosslinking, occurs only after molding, i.e., in step (iii). In another embodiment, it is also preferred that some or all of the crosslinking reaction, i.e., more than 80%, more preferably more than 90%, particularly more than 95%, and especially more than 99% of the crosslinking, occurs during molding, i.e., in step (ii). This embodiment can be implemented in particular when the crosslinking agent is at least one saturated alicyclic or aliphatic compound having at least two primary amino groups and / or an oligomer / polymer that incorporates these, in other words, a shaped article with crosslinked PK is already obtained in step ii).

[0221] In a preferred embodiment, the mixture in step (ii) is processed and thereby shaped by extrusion, hot pressing, injection molding and / or 3D printing. These processes are particularly suitable for easy and efficient processing of thermoplastic polymer compositions. "Shaping" means that the shape initially given is later changed again. Typical shaping processes include bending, stamping, stretching, deep drawing, etc.

[0222] Extrusion can be carried out according to known methods. During extrusion, a solid or viscous, hardenable mass is continuously forced under pressure through a forming orifice (also called a die, dies, or spinneret). This produces an object of theoretically any length and cross-section of the opening, called an extrudate. Preferably, extrusion is carried out at a temperature of at least 220°C, preferably 220°C to 265°C, especially 230°C to 250°C.

[0223] Hot-press molding is a process in which a molding compound is introduced into a preheated cavity, which is then closed using a pressure piston. This pressure causes the molding compound to assume the shape defined by the mold. Preferably, hot-press molding is carried out at a temperature of at least 220°C, preferably between 220°C and 265°C, in particular between 230°C and 250°C.

[0224] Injection molding (often referred to as injection molding or injection molding) is a molding method used in plastics processing. In this process, plastic is plasticized in an injection molding machine and then injected under pressure into a mold, an injection molding tool. Inside the mold, the material cools and returns to a solid state, and after the mold is opened, the molded part is removed. The mold cavity determines the shape and surface structure of the product.

[0225] In 3D printing, for example, a method known as fused deposition modeling (FDM) can be used to mold the molding compound of the present invention. FDM is essentially based on three elements: a print bed (which prints the desired object), a filament spool (which supplies the printing material), and a print head (also called an extruder). During the process, a filament made of thermoplastic molding compound is unwound and fed into the extruder, where it is melted and deposited layer by layer onto the printing plate.

[0226] Particularly preferably, the processing is carried out by extrusion molding followed by injection molding. If the mixture of PK, crosslinker and flame retardant is not already in a liquid state, the mixture is melted in these processes. In step (ii), the mixture is preferably introduced into an extruder, injection molding machine or hot press, melted at an elevated temperature, for example, in the range of 220°C to 250°C, and molded into the desired shape.

[0227] Step (iii) In the above-described embodiments, in which a shaped article comprising a partially or fully crosslinked polyketone has already been obtained in step ii), the heating step iii) can be omitted.

[0228] Step (iii) involves heat-treating the molded article at a temperature at which the PK crosslinks, thereby obtaining a crosslinked molded article. This allows the PK to be intermolecularly crosslinked with a crosslinker. The polyamide is hydrolyzed and decomposed into diamine components. During crosslinking, two imine bonds are formed between the two keto groups of the PK chain and the two amino groups of the released diamine of the crosslinker. Because the imine nitrogen is linked to the organic molecule without a hydrogen atom, the resulting imine-form crosslink is also known as a Schiff base. The crosslinking is as complete as possible, so that as many amino groups of the crosslinker used as possible react with the carbonyl groups of the PK as possible. The advantages of complete crosslinking are improved heat resistance and increased stiffness (elastic modulus). However, only partial crosslinking should also be included in the term "crosslinking." Partial crosslinking can occur when insufficient crosslinker is used to fully incorporate all of the PK chains into the network structure. In this case, the material typically exhibits a higher elongation at break than a fully crosslinked material. The imine bonds impart high stability to the molded article. According to the present invention, the molded article is preferably a PK-based molded article. Here, "PK-based" means that PK is the essential structure-imparting polymer component of the molded article. In one embodiment, it is preferred that PK is the only polymer component of the molded article.

[0229] The crosslinking agents that can be used according to the present invention have relatively high melting and boiling points, so that the temperature in step (iii) can be set relatively high. This is advantageous because such crosslinking reactions are generally favored at high temperatures. However, the temperature is preferably below the melting range of the flame-retardant polyketone and below the softening point of the molded article that has not yet been fully crosslinked.

[0230] Surprisingly, it has been found that in the system according to the invention, the crosslinking reaction occurs already at temperatures below the melting range of the polymer and the molded article, which was unexpected since it is generally believed that the crosslinking reaction occurs preferentially at temperatures above the melting range of the polymer and the molded article.

[0231] Furthermore, the prior art assumes that such crosslinking reactions occur relatively rapidly, within minutes to hours. This depends on the chemical structure of the crosslinker and the post-crosslinking temperature. While aromatic diamines crosslink PK-based materials within a few hours, aliphatic or cycloaliphatic diamines exhibit a much faster crosslinking reaction, which is completed within a few minutes. It has been discovered that the crosslinked PK can exhibit particularly advantageous properties if the heating of the molded article in step (iii) is carried out for a period of preferably at least one hour, e.g., one hour to two days, depending on the crosslinking temperature. It has been discovered that such heat treatment significantly improves thermal stability, modulus, and tensile strength.

[0232] In particular, it has been found that heat treatment can improve the stiffness of samples at high temperatures. It has been observed that heat treatment for a certain period of time can significantly improve stiffness, but then saturation may occur, so that further heat post-treatment does not improve stiffness or only slightly. However, further heat post-treatment usually shows an improvement in heat distortion temperature. It has also been found that the heat distortion temperature can be increased by performing a longer heat post-treatment.

[0233] In a preferred embodiment, the molded article obtained in step (ii) is subjected to a short-term heat treatment. Preferably, the heat treatment of the molded article in step (iii) is carried out for at most 6 hours, for example, 5 minutes to 6 hours, more preferably 0.5 minutes to 5 hours, and especially 1 hour to 4 hours. The advantage here is that the concurrent self-crosslinking reaction of the aliphatic polyketone can be reduced.

[0234] However, it may also be advantageous to subject the shaped article to the heat treatment of step (iii) for a longer period, preferably at least 6 hours, in particular more than 2 days. In a further embodiment of the invention, the heat treatment is carried out for 2 to 10 days, in particular 2 to 6 days. Preferably, the heat treatment is carried out in the absence of oxygen.

[0235] In a preferred embodiment, the heat treatment in step (iii) is carried out at a temperature of at least 160° C., preferably at least 180° C. Preferably, the temperature in step (iii) is between 160° C. and 240° C., more preferably between 190° C. and 230° C., especially between 190° C. and 210° C. At such temperatures, efficient three-dimensional cross-linking can proceed sufficiently rapidly without damaging the thermoplastically produced article, for example by undesired deformation of the molded article.

[0236] After crosslinking, the molded article is cooled and ready for use or further processing.

[0237] As mentioned above, both the mixture of step (i) and the molded article may contain fillers and reinforcing materials and / or additives other than those, if appropriate. The crosslinked PK forms a matrix in which the flame retardant, fillers and reinforcing materials and / or additives are homogeneously dispersed. Such fillers, reinforcing materials and / or additives are as defined above.

[0238] In particular, molded articles can be obtained by the method according to the invention described within the scope of the present invention. The molded articles preferably exhibit the advantageous properties described in the context of the present invention for the flame-retardant crosslinked PK. In the context of the present invention, the term molded article refers to a product composed of the flame-retardant crosslinked PK having a defined three-dimensional shape. In this context, the molded body does not necessarily have to be a defined object, but can also be, for example, a coating. The molded article can consist of the flame-retardant crosslinked PK or can contain the flame-retardant crosslinked PK, for example, as a composite or laminate.

[0239] In a preferred embodiment, the molded article according to the invention is post-cured. In a first variant, the molded article according to the invention is post-cured for 5 minutes to 6 hours. In a second variant, the molded article according to the invention is post-cured for a period of more than 6 hours up to several days. Different advantageous properties can be achieved in each case by different variants.

[0240] Preferably, when the molded article is post-cured for 5 minutes to 6 hours, the molded article exhibits advantageous improvements in mechanical properties compared to molded articles made from flame-retardant uncrosslinked PK, characterized by an increase in tensile modulus, an increase in yield stress, and an increase in elongation at yield. Preferably, molded articles according to the invention that have been post-cured for 5 minutes to 6 hours have a tensile modulus of at least 1800 MPa, in particular at least 1900 MPa, and particularly preferably at least 2000 MPa. Preferably, molded articles according to the invention that have been post-annealed for 5 minutes to 6 hours have a yield strength of at least 65 MPa, in particular at least 68 MPa, and particularly preferably at least 70 MPa. Preferably, molded articles according to the invention that have been post-annealed for 5 minutes to 6 hours exhibit an improvement in elongation at yield of at least 20%, and particularly preferably at least 23%.

[0241] Preferably, when the molded article is post-cured for more than 6 hours and up to several days, the molded article exhibits an advantageous increase in stiffness compared to molded articles made from flame-retardant uncrosslinked PK, characterized by a high tensile modulus and increased tensile strength. However, if the crosslinking is too strong, the elongation at yield point decreases significantly. Preferably, the molded article post-cured for more than 6 hours and up to several days has a tensile modulus of at least 2000 MPa, particularly at least 2250 MPa, and particularly preferably at least 2500 MPa. In particular, the tensile modulus is 2000 MPa to 3000 MPa, or 2250 MPa to 3000 MPa. In contrast, the tensile modulus of uncrosslinked PC is 1400 MPa to 1800 MPa. The tensile modulus is measured in accordance with DIN EN ISO 527-2.

[0242] It may be desirable not to fully crosslink the PK in the molded part, as a high degree of crosslinking can reduce the elongation at break of the material. Therefore, it is preferable to set the degree of crosslinking, for example, by the proportion of crosslinker and the type and time of heat treatment, taking into account the desired application.

[0243] The degree of crosslinking is preferably not measured directly, but rather the molded article is tested for its desired properties by a suitable test method, such as a high temperature tensile test. At very high temperatures, the dynamic modulus can be measured.

[0244] The present invention will now be described with reference to the following examples, but the invention is not limited to the specifically described embodiments. [Brief explanation of the drawings]

[0245] [Figure 1] FIG. 1 shows a simple cylindrical bearing obtained from the material of Example 2 by injection molding and thermal post-curing. [Figure 2] FIG. 1 shows a cylindrical bearing with a collar obtained from the material of Example 2 by injection molding and thermal post-curing. [Figure 3]FIG. 1 shows a cooling tube for a lithium-ion battery obtained from the material of Example 2 by injection molding and thermal post-curing.

[0246] <Example> Abbreviation: DAPI: 1-(4-aminophenyl)-1,3,3-trimethylindan-6-amine and its isomers

[0247] Example 1 Using a twin-screw extruder, 0.6 wt % of a DAPI isomer mixture (crosslinker of formula VII) with CAS number 68170-20-7 was extruded at a melting point of about 220°C and a melt volume rate of 30 cm 3 The mixture was mixed with a commercially available flame-retardant reinforced PK compound RIAMAXX HR GF orange K 2-103 99.4% by weight at 230°C / 10kg / 10min (compliant with ISO 1133) and the polymer strands were cut into granules.

[0248] These granules are injection molded into test plates with dimensions of 80 mm x 80 mm x 2 mm and 80 mm x 80 mm x 1 mm, which are then subjected to a thermal post-cure in a vacuum oven for 2 hours.

[0249] In the UL94V flame test, this material achieves a result of V0 at 0.75 mm.

[0250] In a flame test setup where a propane / oxygen flame was applied directly to the oxidizing flame zone (temperature: 1200°C) on the plate surface, the material neither burned nor melted over a 10 minute test period.

[0251] Example 2 Using a twin-screw extruder, 0.6% by weight of a diamine crosslinker, Priamine 1075 (aminated saturated alicyclic fatty acid dimer, available from Cargill), was extruded into a 1000-kJ / kg copolymer having a melting point of approximately 220°C and a melt volume rate of 30 cm3. 3 / 10 min (according to ISO 1133 / 230 °C / 10 kg) of a commercially available flame-retardant reinforced aliphatic PK compound RIAMAXX® HR GF orange K 2-103 (available from RIA-Polymers GmbH, Germany) 99.4 wt. % was metered in, and the polymer strands were chopped into granules.

[0252] These granules were injection molded into test plates with dimensions 80 mm x 80 mm x 2 mm and 80 mm x 80 mm x 1 mm. Rheological tests showed that Priamine 1075 already crosslinked the PK base material during injection molding, and therefore post-curing step iii) was not necessary.

[0253] In the UL94V flame test, this material achieves a result of V0 at 0.75 mm.

[0254] In a flame test setup where a propane / oxygen flame was applied directly to the oxidizing flame zone (temperature: 1200°C) on the plate surface, the material neither burned nor melted over a 10 minute test period.

[0255] Application example 1 A simple cylindrical bearing was injection molded from the material produced in Example 2 (Figure 1), which was then subjected to a 2 hour thermal post-cure in a vacuum oven.

[0256] Application example 2 Cylindrical bearings with collars were injection molded from the material produced in Example 2 (FIG. 2), which were then subjected to a thermal post-cure in a vacuum oven for 2 hours.

[0257] Application example 3 The material produced in Example 2 was injection molded into cooling tubes for lithium ion batteries (FIG. 3), which were then subjected to thermal post-curing in a vacuum oven for 2 hours.

[0258] Application example 4 The material produced in Example 2 was used to fabricate shaped tubes to protect wire bus bars and other sensitive components from high voltage lithium batteries.

[0259] Application example 5 The material produced in Example 2 was used to produce a molded part for forming a partition plate between modules of a high-voltage lithium battery.

[0260] Application example 6 A molded part was manufactured from the material of Example 2, with the purpose of directing thermal runaway gas to the outside of the housing of a lithium battery.

Claims

1. below: a) a polymer matrix in which an aliphatic polyketone is crosslinked with at least one diamine source as a crosslinking agent to form imine groups, said diamine source being selected from the group consisting of: di(aminophenyl) compounds in which two aminophenyl rings are linked to each other by an aliphatic group containing a carbocyclic ring; Formulae (I), (II) and (III) 【Chemistry 1】 [In the formula, R 1 , R 2 , R 3 and R 4 are independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 6 ~C 14 aryl, wherein the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 6 ~C 14 aryl, wherein the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 6 ~C 14 aryl, wherein the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by X is a bond, oxygen, sulfur, carbonyl, sulfonyl, sulfoxide, C 1 ~C 6 Alkylene, C 2 ~C 6 selected from alkenylene and phenylene; R a is halogen, nitro, cyano, hydroxy, carboxyl, amino, C 6 ~C 12 aryl, wherein the aryl group is unsubstituted or selected from R c is replaced by R b is halogen, nitro, cyano, amino, C 1 ~C 4 Alkyl and C 1 ~C 4 haloalkyl; R c is halogen, nitro, cyano, C 1 ~C 4 Alkyl and C 1 ~C 4 a diamine compound selected from the group consisting of: saturated alicyclic compounds having at least two primary amino groups, and oligomers / polymers containing said compounds in an incorporated form, and - their mixtures shall be selected from the group consisting of: b) Mg(OH) in an amount of 5 to 30 wt. % based on the total weight of the polymer matrix 2 at least one flame retardant (A) selected from the group consisting of phosphates, polyphosphates, phosphites, phosphinates, phosphonites, phosphoric acid esters, phosphonic acid esters, phosphazenes, and mixtures thereof; A device used for one or more selected from the storage, generation, transmission, distribution and use of electrical energy, comprising a flame-retardant molded article comprising:

2. The device of claim 1 , wherein the device comprises at least one filler and reinforcing material and / or additives different therefrom.

3. 3. The device of claim 2, wherein the at least one filler and reinforcing material is selected from glass fiber, wollastonite, calcium carbonate, glass spheres, quartz powder, silicon nitride and boron nitride, amorphous silica, asbestos, magnesium carbonate, calcium silicate, calcium metasilicate, kaolin, mica, feldspar, talc, and mixtures thereof.

4. 2. The device of claim 1, wherein the cross-linking agent is a di(aminophenyl) compound in which two aminophenyl rings are linked to each other by an aliphatic group having a carbon ring, one of the two phenyl rings being fused to the carbon ring.

5. 2. The device according to claim 1, wherein the cross-linking agent is a 4,4' diaminodiphenyl compound and / or a compound represented by formula (V). 【Chemistry 2】 In formula (V), R 19 and R 20 are independently selected from H, substituted or unsubstituted alkyl having 1 to 20 C atoms, substituted or unsubstituted aryl having 5 to 12 C atoms, F and Cl, R 21 is a carbocyclic ring having 2 to 3 C ring atoms, which C ring atoms may be substituted with at least one alkyl group having 1 to 4 C atoms.

6. The crosslinking agent is a saturated alicyclic compound having at least two primary amino groups selected from aminated dimer fatty acids, polymers containing aminated dimer fatty acids in polymerized form therein, and mixtures thereof, in particular the compound 【Transformation 3】 or an oligomer / polymer containing said compound in polymerized form.

7. 10. The device of claim 1, wherein the flame retardant molded article is selected from a powered transportation component, a battery energy storage system component, a power tool component, and a power generation device component.

8. 8. The device according to claim 7, for use in applications selected from batteries, thermal systems, DC-DC converters, electric motors, power inverters, charge ports, on-board chargers, control devices, transmissions, in particular batteries and power electronics.

9. The device of claim 7 , wherein the device is selected from a powered transportation device, a battery energy storage system, a power tool, or a power generation device.

10. 10. The apparatus of claim 9, wherein the electric vehicle is selected from a road electric vehicle, an orbital electric vehicle, a marine electric vehicle, an electric aircraft, and an electric spacecraft, preferably a battery electric vehicle (BEV).

11. 1. A method for improving the flame retardancy of a molded article for electrical equipment, comprising: The molded article for an electrical device comprises: The polymer matrix includes an aliphatic polyketone crosslinked with a crosslinking agent to form an imine group; The method comprises steps i) and ii), or steps i), ii) and iii), Step i) is a step of providing a mixture comprising at least one aliphatic polyketone, at least one crosslinking agent, and at least one flame retardant (A); Step ii) is a step of producing a shaped article from the mixture obtained in step i), Step iii) is a step of post-curing the molded article at a temperature at which the aliphatic polyketone crosslinks; The crosslinking agent may be: di(aminophenyl) compounds in which two aminophenyl rings are linked to each other by an aliphatic group containing a carbocyclic ring; Formulae (I), (II) and (III) 【Chemistry 4】 [In the formula, R 1 , R 2 , R 3 and R 4 are independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 6 ~C 14 aryl, wherein the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 6 ~C 14 aryl, wherein the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently hydrogen, halogen, nitro, cyano, hydroxy, amino, C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 6 ~C 14 aryl, wherein the alkyl, alkenyl, and alkynyl groups are unsubstituted or selected from R a and the aryl group is unsubstituted or substituted with R b is replaced by X is a bond, oxygen, sulfur, carbonyl, sulfonyl, sulfoxide, C 1 ~C 6 Alkylene, C 2 ~C 6 selected from alkenylene and phenylene; R a is halogen, nitro, cyano, hydroxy, carboxyl, amino, C 6 ~C 12 aryl, wherein the aryl group is unsubstituted or selected from R c is replaced by R b is halogen, nitro, cyano, amino, C 1 ~C 4 Alkyl and C 1 ~C 4 haloalkyl; R c is halogen, nitro, cyano, C 1 ~C 4 Alkyl and C 1 ~C 4 a diamine compound selected from the group consisting of: saturated alicyclic compounds having at least two primary amino groups, and oligomers / polymers containing said compounds in an incorporated form, and - their mixtures is selected from The flame retardant (A) is Mg(OH) 2 , phosphates, polyphosphates, phosphites, phosphinates, phosphonites, phosphoric acid esters, phosphonic acid esters, phosphazenes or mixtures thereof; The method of claim 1, wherein the flame retardant (A) is used in an amount of 5 to 30% by weight based on the total weight of the polymer matrix in which the aliphatic polyketone is crosslinked with the crosslinking agent to form imine groups.

12. 12. The method according to claim 11, wherein in step i) the at least one aliphatic polyketone, the at least one crosslinking agent, optionally fillers and reinforcing agents, and optionally further additives different therefrom, are subjected to melt mixing or dry mixing / blending.

13. 12. The method according to claim 11, wherein in step i), the at least one aliphatic polyketone, the at least one crosslinking agent, and the at least one flame retardant (A), optionally a filler and a reinforcing agent, and optionally further additives different therefrom, are fed into an extruder, mixed while plasticizing, and optionally granulated.

14. 12. The method according to claim 11, wherein in step i) the at least one aliphatic polyketone, the at least one crosslinking agent, and the at least one flame retardant (A), optionally fillers and reinforcing agents, and optionally further additives different therefrom, are dry mixed.

15. The aliphatic polyketone has a cross-sectional area of ​​2 cm measured in accordance with DIN ISO 1130 3 / 10min~200cm 3 12. The method of claim 11, wherein the composition has a melt viscosity at 240°C in the range of 1 / 10 min.

16. 12. The method of claim 11, wherein the mixture of step i) does not contain added solvent.

17. 12. The method of claim 11, wherein the temperature of step iii) is at least 220°C.

18. 12. The method of claim 11, wherein the mixture of step i) is processed by extrusion, hot pressing, injection molding and / or 3D printing.

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