• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    processes for producing fiber-reinforced smooth semifinished products and a component made of a fiber-reinforced smooth semifinished product the invention relates to a method for producing fiber-reinforced smooth semifinished products (3) in a polyamide matrix, comprising the following steps: (a) saturation of the textile structures (15) with a mixture containing melted lactam, catalyst and optionally activator, (b) cooling of the saturated textile structures (25), (c) manufacture of the fiber-reinforced smooth semifinished product (3) from of cooled textile structures. the invention further relates to a method for producing a component from the smooth, fiber-reinforced semi-finished product.
    公开号:BR112013022533B1
    申请号:R112013022533-5
    申请日:2012-02-27
    公开日:2020-03-24
    发明作者:Dietrich Scherzer；Stephan Schäfer；Andreas Radtke；Andreas Wollny；Max Ehleben；Olaf Täger；Jörg Hain；Manfred Kramer；Christoph Hermes
    申请人:Basf Se；
    IPC主号:
    专利说明:

    PROCESSES TO PRODUCE FIBER STRENGTHENED FLAT SEMI-FINISHED PRODUCTS AND A COMPONENT MADE OF A FIBER STRENGTHENED FLAT SEMI-FINISHED PRODUCT Description [1] The invention relates to a process for producing smooth fiber-reinforced semi-finished products with a polyamide matrix.
    [2] Smooth, fiber-reinforced semi-finished products are used to produce components made of reinforced thermoplastic polymers, preferably polyamides and after the hardening process they are also called organopanels or pre-impregnated thermoplastics. The modeling process used here is thermoforming or other pressing processes.
    [3] Fiber-reinforced composite materials are usually produced by inserting the fibers into a suitable mold and then using the fused polymers for encapsulation. In another possible method, a monomer solution is used to encapsulate the fibers and polymerize to finish in the mold. However, a disadvantage here, particularly in the case of a dense fiber bundle, is that the high viscosity of the molten polymer leads to incomplete wetting of the fibers and this weakens the material. Monomers are normally used for encapsulation in the case of thermosetting polymers, but this has the disadvantage that continuous processing is not possible, since each of the components produced from the fiber-reinforced composite material has been hardened in the mold. Once the encapsulation process and the hardening process have been completed, the modeling process has already taken place. Semi-finished products capable of further processing cannot be easily produced by this method. There are known prepregs based on partially hardened epoxy resins, but these have to be stored in cooled conditions in order to avoid unwanted hardening during
    Petition 870190121119, of 11/21/2019, p. 10/31 / 17 storage. The mold hardening process also limits the possible result and this is disadvantageous, in particular for mass production of the components. The wetting of fibers with a monomer to a fiber-reinforced thermoplastic polymer is known from DE-A 196 02 638. Here, a fiber-reinforced structure, for example, a braided or individual fold made of continuous fibers, is saturated with a mass in melt made of lactam which comprises activator, catalyst and optionally additional additives. After saturation with the lactam melting mass, the material is heated to the reaction temperature and the lactam is polymerized to result in a corresponding polyamide. In order to avoid dripping from the melted lactam outside the fiber-reinforced structure, it is necessary to carry out the polymerization step immediately after the saturation process. This has the disadvantage that the processing rate is limited by the polymerization step. Production of a relatively large number of parts always requires the provision of systems in which the fiber-reinforced structures are first saturated with the lactam melt and these are then molded to result in molding. DE-A 196 02 638 further describes that, for the production of moldings of the elements reinforced with straight fiber, the elements reinforced with straight fiber are first produced by saturation of textile structures with lactam; this is followed by completion of the polymerization process and the resulting fully polymerized fiber-reinforced elements are then subjected to forming in a heated mold to result in molding.
    [4] DE-A 10 2007 031 467 also describes a process in which fibers used for reinforcement are saturated with a melt made from lactam and, in a step that immediately follows, the lactam is completely polymerized to result in polyamide. . In the process described in this document, a granulated material reinforced only with short fibers is produced and can then be processed by molding by
    Petition 870190121119, of 11/21/2019, p. 11/31 / 17 injection or extrusion. This does not allow the production of organopanels that comprise continuous fibers as reinforcement.
    [5] WO-A 2011/003900 describes another process for producing fiber-reinforced composite materials made of nylon-6 and nylon-6 and nylon-12 copolyamides. Here again, the polymerization of the used monomers takes place immediately after the saturation of the fibers and, thus, there is no possible rational use of the process for mass production of components made from organopanels.
    [6] It is an objective of the present invention to provide a process that can produce smooth, semi-finished products reinforced with fiber and that can be operated continuously and can result in sufficient productivity for mass production.
    [7] The objective is achieved through a process to produce smooth semi-finished products reinforced with fiber, comprising the following steps:
    (a) saturation of textile structures with a mixture comprising melted lactam, catalyst and optionally at least one activator, (b) cooling of the saturated textile structures, and (c) finishing of the cooled saturated textile structures to result in a smooth semi-finished product.
    [8] Saturation of the textile structures and then cooling below the melting point of the lactams allows continuous operation of the process. In addition, there is no need to pass the smooth semi-finished products resulting in a polymerization process immediately and the production of the semi-finished products and the manufacture of the components to be produced from the semi-finished product, in this way, can happen independently of each other.
    [9] The temperature of the melted lactam is preferably in the range of 70 to 100 ° C. It is important that the temperature of the melted lactam is
    Petition 870190121119, of 11/21/2019, p. 12/31 / 17 kept below the starting temperature at which the lactam starts to polymerize to result in polyamide.
    [10] For the purposes of this invention, laurolactam or caprolactam can be used as a lactam. A preferred lactam is caprolactam, in particular, ε-caprolactam, which polymerizes to result in nylon-6.
    [11] Up to 20% by weight, preferably from 0 to 17% by weight, particularly preferably from 0 to 15% by weight, of the caprolactam can be substituted by lactam group comonomers having at least 4 carbon atoms. ω-Laurolactam is particularly preferred.
    [12] In a preferred embodiment, mixtures made of εcaprolactam and ω-laurolactam can be used. The mixing ratio is generally 1000: 1, preferably 100: 1, particularly preferably 10: 1, in particular 2: 1.
    [13] The fused lactam may comprise activators for nylon-6. Suitable activators can, for example, be produced by reacting isocyanates, such as hexamethylene diisocyanate (HDI) with lactams, such as ε-caprolactam. Other suitable activators are capped isocyanates, isophthaloyliscaprolactam, terephthaloylbiscaprolactam, esters, such as dimethyl phthalate-polyethylene glycol, polyols or polydienes in combination with acyl chlorides, carbonylbiscaprolactam, hexamethylene diisocyanate or actamate lactam, hexamethylene diisocyanate or lactamate particularly preferably hexamethylene diisocyanate or acyl lactamate.
    [14] Activators that can be used are any of the activators that are used for the activated anionic polymerization process, examples being N-acylactams, such as N-acetylcaprolactam, substituted triazines, carbodiimides, cyanamides, mono- and polyisocyanates and the compounds of corresponding masked isocyanates. Concentrations
    Petition 870190121119, of 11/21/2019, p. 13/31 / 17 used of the activators are preferably 0.1 to 1 mol%, based on the amount of lactam. With the catalysts used it is possible to polymerize lactams having at least 5 members in the ring, for example, caprolactam, laurolactam, caprylolactam, enantolactam, the corresponding C-substituted lactams or a mixture of the mentioned lactams.
    [15] As an alternative or in addition to mixing the activator with the lactam, it is also possible to start by coating the fibers of the textile structure with the activator and then saturating the textile structure coated with the activator with the lactam. For example, it is possible here to mix the activator with a sieve to treat the fibers.
    [16] Suitable alkaline catalysts can be produced by reacting a lactam or lactone with the corresponding alkali metal compound or alkaline earth metal compound, for example, the alkolate, amide, hydride, Grignard compounds or with the alkali metals or alkaline earth metals. The added amounts of the catalysts are generally from 0.1 to 40% by weight, preferably from 0.2 to 15% by weight, based on the melt weight of lactam.
    [17] Catalysts with good suitability for the polymerization process are alkaline catalysts, such as magnesium and halogen lactates, alkali metal caprolactates, aluminum lactam or magnesium lactam, sodium caprolactate or magnesium bromide lactam, preferably caprolactam of alkali metal, aluminum lactam or magnesium lactam, sodium caprolactate or magnesium bromide lactate, particularly preferably sodium caprolactate or magnesium bromide lactate. Sodium caprolactate is particularly suitable and can be easily produced from sodium and ε-caprolactam.
    [18] The mixing ratio of lactam, preferably caprolactam, activator and alkaline catalyst can vary widely. The molar ratio of
    Petition 870190121119, of 11/21/2019, p. 14/31 / 17 caprolactam for activator for alkaline catalyst is generally 1000: 1: 1 to 1000: 200: 50.
    [19] The lactam can also comprise other additives together with the catalyst and the activator. The other additives are added in order to adjust the properties of the polyamide produced from the lactam. Examples of conventional additives are plasticizers, impact modifiers, cross-linking agents, dyes or flame retardants.
    [20] For the purposes of the present invention a textile structure means braids made of at least one fold, preferably more than one fold, knits made of one or more folds, braids made of one or more folds, fabrics laid out, at least one fold, preferably a plurality of folds, made of fibers, yarns, lines or rigging oriented in parallel, where the individual folds of fibers, yarns, lines or rigging oriented in parallel can be mutually non-parallel or non-twisted. It is preferable that the textile structures have the form of braids or folds of fibers, threads, lines or rigging oriented in parallel.
    [21] If in the case of screens arranged the folds of fibers, yarns, lines or rigging oriented in parallel are used in mutually non-parallel form, it is particularly preferable that the angle of rotation between the individual folds is respectively 90 ° (bidirectional structure) . If the number of folds used is three or a multiple of three, it is also possible to arrange the angle of rotation between the individual folds as 60 ° and If the number of folds is four or a multiple of four it is also possible to arrange the angle of rotation between individual folds like 45 °. In addition, it is also possible to provide more than one fiber fold with identical orientation. It is also possible here that the folds are mutually non-parallel, where the number of folds with identical orientation fibers in each fiber orientation can differ, an example being four folds in one
    Petition 870190121119, of 11/21/2019, p. 15/31 / 17 first direction and a bend in a direction where the angle of rotation between these directions is, for example, 90 ° (bidirectional structure with preferred direction). There is also a known quasi-isotropic structure in which the arrangement has the fibers of a second fold at a 90 ° rotation angle between them and fibers of a first fold and, in addition, has fibers of a third fold with an angle of 45 ° rotation between these and the fibers of the second fold.
    [22] It is particularly preferable to use, for the production of smooth semi-finished products reinforced with fiber, textile structures with 2 to 10 folds, in particular 2 to folds.
    [23] The textile structures used preferably comprise, as fibers, fibers made from inorganic minerals, such as carbon, for example, in the form of low modulus carbon fibers or high modulus carbon fibers, silicic and non-silicic glass from one wide variety of types, boron, silicon carbide, potassium titanate, metals, metal alloys, metal oxides, metal nitrites, metal carbides and silicates and also organic materials, such as natural and synthetic polymers, for example, polyacrylonitriles , polyesters, ultra high withdrawal polyolefin fibers, polyamides, polyimides, aramides, liquid crystal polymers, polyphenylene sulfites, polyether ketones, polyether ether ketones, polyetherimides, cotton, cellulose and other natural fibers such as linen, sisal, kenaf , hemp and abaca. Preference is given to high melting point materials such as glass, carbon, aramides, potassium titanate, liquid crystal polymers, polyphenylene sulfites, polyether ketones, polyether ether ketones and polyetherimides and glass fibers are particularly preferred, carbon fibers, aramid fibers, fibers and steel, potassium titanate fibers, ceramic fibers and / or other polymeric fibers or filaments sufficiently resistant to heat.
    [24] In such a way that textile structures can be uniformly saturated, they are preferably placed continuously in a
    Petition 870190121119, of 11/21/2019, p. 16/31 / 17 conveyor belt and passed through the saturation equipment. An example of suitable saturation equipment is a bath through which the textile structures are passed. Another possible alternative is that the textile structures are coated or saturated by jet application, spreader application or dye coating processes, preferably using a notch press or by means of rotating cylinders or by means of scraper systems. Particular preference is given to application by jet or coating with dye on the textile structures or on a portion of the textile structures using stoichiometric amounts of lactam or lactams that already comprise the additives necessary for the polymerization process. Unlike the saturation processes described, this way there is no need to press to remove excess lactam. Coating of two low pressure components commercially available with dye machinery, such as those marketed by Tartler, Michelstadt is suitable for the process of jet application or dye coating. It is particularly preferable to use a notch press for saturation or coating the fibers.
    [25] In a preferred embodiment, the textile structures are applied to a sheet, preferably a sheet of polyamide, before the saturation process. The blade has a favorable effect on the surface of the smooth, fiber-reinforced semi-finished product produced. The use of the blade in this way can result in high quality surfaces that, for example, can be used as a visible surface. In addition, it is also possible to use the blade as a conveyor belt.
    [26] In order to obtain uniform wetting of the fibers of the textile structure and thus avoid defects, additional preference is given to heating the textile structures to a temperature above the melting point of the lactam, before the saturation process. This has the advantage of preventing the lactam from crystallizing out of the material in contact with the fibers; this may, some
    Petition 870190121119, of 11/21/2019, p. 17/31 / 17 times, block paths through which the lactam flows during the saturation process, with possible cavities resulting in the smooth, semi-finished product reinforced with fiber.
    [27] In a preferred embodiment, a sheet, preferably a polyamide sheet, is applied to the saturated textile structures, after saturation of the lactam textile structures. This also gives a high quality surface that can be used as a visible surface. It is particularly preferable that the blade is applied to the saturated textile structures if the textile structures were placed on a slide before the saturation process. The smooth, semi-finished product reinforced with fiber, in this way, has a polyamide sheet applied not only on the bottom side, but also on the upper side and the smooth semi-finished product reinforced with fiber, in this way, not only has the bottom side, but also on the top side, a high quality surface that can be used as a visible surface.
    [28] In order to obtain uniform distribution of the melted lactam in the textile structures, the textile structures are preferably pressed, after the saturation process. During the pressing process it is also possible to remove excess lactam from textile structures, thus achieving uniform and complete saturation with lactam.
    [29] In order to allow continuous manufacture of the smooth semi-finished product reinforced with fiber, the saturated textile structures are preferably passed through rollers for the pressing process. In a possible alternative, textile structures can also be pressed with a single roller against the used conveyor belt, if the conveyor belt does not yield under pressure.
    [30] The saturated textile structures are cooled in order to allow them to dry. If the saturated textile structures are pressed, cooling occurs after the pressing process. THE
    Petition 870190121119, of 11/21/2019, p. 18/31 / 17 cooling solidifies the used lactam and the textile structures, in this way, comprise the lactam in solid condition, after the drying process.
    [31] In a preferred embodiment, after the saturation process and before the pressing process for the textile structures, in each case at least one fold of the fiber is applied, for example, in the form of a braid, fabric, canvas or not fabric, the upper side and the lower side of saturated textile structures. Due to the pressing process, the lactam comprised in the textile structures is also introduced in the folds of the fiber applied after the saturation process. The amount of excess lactam is reduced by the textile structures applied after the saturation process, as they absorb lactam during the pressing process and become saturated with the lactam.
    [32] After pressing and cooling, which solidifies the lactam, the semi-finished product is submitted to finishing. For this purpose, the smooth, fiber-reinforced semi-finished product produced in the form of continuous strip is cut to size.
    [33] In addition or as an alternative, the application of the blade, preferably the polyamide blade, on the upper side and on the lower side of saturated textile structures, it is possible to weld the smooth, fiber-reinforced semi-finished product to the blades. This first allows protection of the resulting smooth, semi-finished product reinforced with the finished fiber and, secondly, can result in further surface improvement.
    [34] An additional disadvantage of applying the blade to the upper and lower sides of saturated textile structures is that water, which deactivates the catalyst, cannot diffuse into the saturated textile structure. Welding on the blade further amplifies this effect and also, in addition, seals the edges of saturated textile structures, thus also preventing the ingress of water here. The result is an improvement in the half-life of the semi-finished product.
    [35] The blade on which the semi-finished product is welded can be
    Petition 870190121119, of 11/21/2019, p. 19/31 / 17 any desired blade that is impermeable to water. It is preferable to use polyamide sheets or polyester sheets. If blades made of a material other than polyamide or polyester are used, it is generally necessary to remove the semi-finished product from the blade before further processing. If a polyamide blade is used and also sometimes if a polyester blade is used, the semi-finished product can be further processed together with the blade and does not have to be removed. This can result in easy handling of semi-finished products and this is particularly desirable when they are used for large-scale industrial purposes.
    [36] Because the catalyst is sensitive to water, it is necessary that the production and further processing of the semi-finished product takes place with the exclusion of water, that is, in dry air or in an anhydrous inert gas. Insofar as the semi-finished product has not been welded on a sheet or at least has been coated by a sheet on the top and bottom, additional processing is required over a period of 5 minutes in order to avoid unwanted water absorption that deactivates the catalyst and then avoid complete polymerization of the lactam.
    [37] The invention provides not only the process for producing a smooth fiber-reinforced semi-finished product, but also a process for producing a component made of the straight fiber-reinforced semi-finished product.
    [38] The process for producing a component made of a smooth, fiber-reinforced semi-finished product comprises the following steps:
    [39] (i) production of the fiber-reinforced smooth semi-finished product in the manner described above, [40] (ii) insertion of the fiber-reinforced smooth semi-finished product in a mold, and [41] (iii) submission of the reinforced smooth semi-finished product with
    Petition 870190121119, of 11/21/2019, p. 20/31 / 17 fiber to a molding process to result in the component with simultaneous heating of the mold, in such a way that the lactam polymerizes to result in polyamide.
    [42] Production of the smooth semi-finished product reinforced with finished fiber allows separation of component production from the production of the semi-finished product. In this way it is possible to produce the semi-finished product in a continuous process and, after the production process, keep it available to produce the component. This allows for use in mass production, where the production of the semi-finished product is independent of the production of the component. For example, in this way, it is possible to use an apparatus to produce semi-finished products and to use a plurality of apparatus to mold the resulting semi-finished products to result in the components. There is no need for a unit allocated for the production of semi-finished products for each appliance to produce components and thus it is possible to save not only capital spent, but also operating costs.
    [43] For the production process, the smooth, fiber-reinforced semi-finished product produced by the process described above is inserted into a mold in which the smooth, fiber-reinforced semi-finished product is molded to result in a component. An example of a suitable forming process is a thermoforming process or a press process.
    [44] The molding in which the semi-finished product is molded to result in the component is heated in the invention to a temperature at which the lactam polymerizes anionically to result in polyamide. The temperature of the mold here is preferably in the range of 100 to 200 ° C, more preferably in the range of 120 to 180 ° C and in particular in the range of 140 to 170 ° C. The catalyst included in the lactam catalyzes the anionic polymerization reaction and the resulting polyamide still comprises the
    Petition 870190121119, of 11/21/2019, p. 21/31 / 17 catalyst after the polymerization reaction.
    [45] The figure shows one embodiment of the invention and this is explained in more detail in the description below.
    [46] The only figure is a diagram of the process of the invention to produce a smooth, fiber-reinforced semi-finished product.
    [47] A first blade 5 is introduced into an apparatus 1 to produce smooth, semi-finished products reinforced with fiber 3. The first blade 5 is applied to a conveyor belt 7. A suitable conveyor belt 7 is simply any desired conveyor belt that is capable of carry the blade 5 and which is known to those skilled in the technology. The surface of the conveyor belt 7 has been designed here in such a way that the blade 5 is not damaged by the movement of the conveyor belt 7 or in the application on the conveyor belt 7. In such a way that the process can be operated continuously, the blade 5 has been supplied on a roll 9 from which the blade is unrolled and inserted into the device 1.
    [48] In the modality presented here, two folds of fibers 11 are placed on the lamina 5. The fibers 11 here can be in the form of fabric, braid, canvas or non-woven or they can be in the form of oriented fibers, threads, lines or rigging in parallel. If fibers oriented in parallel are used, it is preferable to orient the fibers in the individual folds, in such a way that they are mutually non-parallel, preferably with a 90 ° rotation angle between them. The addition of fibers 11 also happens continuously and the fibers 11 were supplied here on a roll 13. The fibers 11 placed on the blade 5 form the textile structure 15 to be saturated.
    [49] In order to obtain uniform wetting of the fibers of the textile structure 15 with lactam, it is preferable to heat the textile structure. The arrows 17 in the figure show the heat source. After heating, the textile structure 15 is saturated with melted lactam. The fused lactam comprises at least one catalyst that catalyzes the anionic polymerization reaction to
    Petition 870190121119, of 11/21/2019, p. 22/31 / 17 result in polyamide and also optionally comprises at least one activator. The material can also further comprise additives which can influence the properties of a polyamide produced from the lactam. The temperature at which the textile structure 15 is heated is preferably the melting temperature of the lactam used. It is preferable that the temperature is in the range of 70 to 90 ° C. During the heating process, care must be taken that the temperature of the melted lactam and the temperature at which the textile structure 15 is heated are below the starting temperature for the anionic polymerization of the lactam.
    [50] In the modality shown here, lactam fused with activator is added as a first feed 19 and lactam fused with catalyst is added as a second feed 21 to a mixing unit 23. The mixing unit can, at by way of example, it was designed in the form of an extruder or in the form of a static mixer. A homogeneous mixture of the lactam with activator and catalyst is produced in the mixing unit. The fused lactam comprising activator and comprising catalyst is applied to the textile structure 15. Any desired apparatus known to those skilled in the art can be used here to saturate the textile structures 15. As an example, in this way, it is possible to use curtain lining or other dye coating processes to saturate textile structures with the melted lactam. In an alternative possibility, the lactam can be applied by spraying on the textile structures 15. In addition, it is also possible to pass the textile structures through a bath with molten lactam or saturate them using wetted rollers. It is preferable to use jet application processes to saturate textile structures.
    [51] In the modality presented here, a second blade 27 is applied to the saturated textile structure 25, after the saturation process. It is preferable here that the second blade 27, like the first blade 5, is not
    Petition 870190121119, of 11/21/2019, p. 23/31 / 17 woven from a roll 29 on which it was supplied.
    [52] In a next step, the saturated textile structure 25 is pressed. For this purpose, the saturated textile structure 25 is, by way of example, forced by a roller 31 against the conveyor belt 7. In an alternative possibility, the saturated textile structure 25 is, by way of example, passed through two rollers which they rotate oppositely, where the distance between the rollers that rotate oppositely is less than the thickness of the saturated textile structure 25 before passing through the rollers. The distance between the rollers or the distance of the roller 31 of the conveyor belt 7 is used to adjust the force with which the saturated textile structure 25 is pressed.
    [53] In a mode not shown here, at least one fold of the additional fiber is applied to the upper side and / or the lower side of the saturated textile structure, after the saturation process. The fibers additionally applied here are preferably of the same type as the fibers 11 forming the textile structure 15. However, in an alternative possibility, the fibers forming the textile structure 15 are, for example, individual folds of the fibers, yarns, threads or parallel oriented ropes or a nonwoven form the textile structure 15 and the additional folds are woven or braided.
    [54] The pressing of the saturated textile structure 25 forces the lactam into the additionally applied fiber folds and the additionally applied fiber folds are thus also saturated with lactam.
    [55] The saturated textile structure 25 is cooled after the pressing process. An arrow 33 shows this. The cooling process solidifies the lactam and a textile structure comprising solid lactam is produced. This is done using a cutter 35, for example, a shovel, a drill or a saw, to result in the smooth, semi-finished product reinforced with fiber
    3.
    [56] For the production of the components, the smooth, fiber-reinforced semi-finished product is inserted into a mold that has been heated to a
    Petition 870190121119, of 11/21/2019, p. 24/31 / 17 temperature at which the lactam undergoes complete anionic polymerization to result in polyamide. Heating to a temperature above the starting temperature for the anionic polymerization reaction polymerizes the lactam with which the textile structures have been saturated to result in a corresponding polyamide. Due to the simultaneous pressing process, the smooth, semi-finished product reinforced with fiber is converted into the desired shape of the component to be produced.
    [57] Examples of components that can be produced in this way are vehicle body work parts, structural components for vehicles, for example, floors or roofs and constituent components for vehicles, for example, mounting brackets, seat structures, coverings door or interior linings and also components for wind power systems or rail vehicles.
    Key
    I Apparatus for producing fiber-reinforced smooth semifinished products
    Smooth fiber-reinforced semi-finished product
    Polyamide blade
    Conveyor belt
    Roll with polyamide blade
    II Fiber
    Fiber providing roll
    Textile structure
    Heat source
    First feeding
    Second feeding
    Mixing unit
    Saturated textile structure
    Second polyamide blade
    Roll with second polyamide blade
    Petition 870190121119, of 11/21/2019, p. 25/31 / 17
    Roller
    Cooling
    Cutter
    权利要求:
    Claims (18)
    [1]
    1. Process for producing smooth semi-finished products reinforced with fiber (3) based on a polyamide matrix, characterized by the fact that it comprises the following steps:
    (a) saturation of the textile structures (15) with a mixture comprising fused lactam, catalyst and optionally activator, in which the temperature of the fused lactam is maintained below the starting temperature at which the lactam begins to polymerize to result in polyamide;
    (b) drying of the saturated textile structures (25) by cooling; and (c) finishing the cooled textile structures to result in the smooth, semi-finished product reinforced with fiber (3).
    [2]
    2. Process according to claim 1, characterized by the fact that the textile structures (15) are applied on a slide (5) before the saturation process.
    [3]
    Process according to claim 1 or 2, characterized by the fact that the textile structures (15) are heated to a temperature above the melting point of the lactam, before the saturation process.
    [4]
    Process according to any one of claims 1 to 3, characterized by the fact that a sheet (27) is applied to the saturated textile structures (25), after the saturation process in step (a).
    [5]
    Process according to any one of claims 2 to 4, characterized in that the blade (5) on which the textile structures are applied and / or the blade (27) which is applied to the saturated textile structures is a polyamide.
    [6]
    Process according to any one of claims 1 to 5, characterized in that the saturated textile structures (25) are
    Petition 870190121119, of 11/21/2019, p. 27/31
    2/3 pressed.
    [7]
    Process according to any one of claims 1 to 6, characterized in that the saturated textile structures (25) are passed between rollers (31) for the pressing process.
    [8]
    Process according to claim 6 or 7, characterized in that the saturated textile structures (25) are cooled after the pressing process.
    [9]
    Process according to any one of claims 6 to 8, characterized by the fact that, after the saturation process and before the pressing process, in each case at least one fold of the fiber is applied on the upper side and on the lower side saturated textile structures (25).
    [10]
    Process according to any one of claims 1 to 9, characterized by the fact that the textile structures (15) are fabrics, braids, fabrics or non-fabrics made of continuous fibers.
    [11]
    Process according to any one of claims 1 to 9, characterized in that the textile structures (15) were manufactured from individual folds made of continuous fibers, where the individual folds comprise fibers arranged in parallel and the fibers folded together superimposed were arranged so as to be mutually non-parallel.
    [12]
    Process according to any one of claims 1 to 11, characterized in that the material used for the fibers comprises inorganic minerals, such as carbon, silicate and non-silicate glasses of a wide variety of types, boron, silicon carbide, potassium titanate, metals, metal alloys, metal oxides, metal nitrites, metal carbides and silicates or organic materials, such as natural and synthetic polymers.
    [13]
    Process according to any one of claims 1 to 12, characterized in that the textile structures (15) comprise three to ten folds of fibers.
    Petition 870190121119, of 11/21/2019, p. 28/31
    3/3
    [14]
    Process according to any one of claims 1 to 13, characterized in that the smooth, fiber-reinforced semi-finished product (3) is welded to sheets after the finishing process.
    [15]
    Process according to claim 14, characterized in that the blades in which the smooth fiber-reinforced semi-finished product (3) is welded are polyamide sheets or polyester sheets.
    [16]
    16. Process according to any one of claims 1 to 15, characterized in that the fibers of the textile structure are first coated with an activator.
    [17]
    17. Process for producing a component made of a smooth semi-finished product reinforced with continuous fiber, characterized by the fact that it comprises the following steps:
    (i) production of the semi-finished product as defined in any one of claims 1 to 16, (ii) insertion of the semi-finished product into a mold, and (iii) pressing the semi-finished product to result in the component and heating of the mold, in such a way that the lactam polymerizes to result in polyamide and the component is thus molded.
    [18]
    18. Process according to claim 17, characterized in that the mold is heated to a temperature in the range of 100 to 190 ° C.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP2858896B2|1989-07-07|1999-02-17|宇部日東化成株式会社|Method for producing fiber-reinforced polyamide resin composition|
    EP0544049B1|1991-11-28|1998-09-09|Solutia Europe N.V./S.A.|Nylon pultrusion process|
    DE19510237A1|1995-03-21|1996-09-26|Strunz Heinrich Gmbh & Co Kg|Laminates used e.g. for walls or furniture, not requiring grinding or priming before painting|
    DE19527154C2|1995-07-25|2001-06-07|Inventa Ag|Thermoplastic deformable composite materials|
    DE19602638A1|1996-01-25|1997-08-07|Inventa Ag|Process for the production of thermally deformable composite materials with polylactam matrix|
    CN1615215A|2001-12-20|2005-05-11|埃姆斯化学品有限公司|Method for producing composite materials using a thermoplastic matrix|
    JP2008030411A|2006-07-31|2008-02-14|Mitsuboshi Belting Ltd|Manufacturing method for polyamide resin molding|
    DE102007031467A1|2007-07-05|2009-01-08|Polymer-Chemie Gmbh|Producing composite material, comprises passing continuous threads through a bath containing caprolactam and moistening threads with the materials, introducing the threads into an oven, polymerizing the caprolactam and cutting the threads|
    CA2639276A1|2007-09-05|2009-03-05|Tecton Products, Llc|Pultrusion with abrasion resistant finish|
    EP2271703A1|2008-03-30|2011-01-12|IQ Tec Switzerland Gmbh|Apparatus and method for making reactive polymer pre-pregs|
    US7790284B2|2008-09-24|2010-09-07|Davies Robert M|Flexible composite prepreg materials|
    WO2011003900A2|2009-07-08|2011-01-13|Basf Se|Method for producing fiber-reinforced composite materials from polyamide 6 and copolyamides made of polyamide 6 and polyamide 12|
    CN101693418B|2009-10-19|2012-07-25|杭州电子科技大学|Production method of glass fiber mesh and paste resin compound enhanced film|
    CN101786330B|2010-02-04|2011-11-16|合肥圆融材料有限公司|Device and method for production of long-fiber-reinforced thermoplastic resin|EP2666805B1|2012-05-25|2014-10-22|LANXESS Deutschland GmbH|Method for manufacturing a fibre compound material|
    CN105283286B|2012-12-04|2018-02-02|巴斯夫欧洲公司|The method for preparing fibre reinforced composites|
    US9834885B2|2012-12-04|2017-12-05|Basf Se|Process for the production of a fiber-reinforced composite material|
    US9186852B2|2013-11-22|2015-11-17|Johns Manville|Fiber-containing prepregs and methods and systems of making|
    EP2980132A1|2014-08-01|2016-02-03|Basf Se|Method for producing impregnated fibrous structures|
    DE102014223982B3|2014-11-25|2016-04-28|Volkswagen Aktiengesellschaft|Process arrangement for producing a fiber-reinforced plastic component|
    DE102015002107A1|2015-02-23|2016-08-25|Basf Se|Process arrangement and method for producing a fiber-reinforced plastic component|
    DE102015002106A1|2015-02-23|2016-08-25|Basf Se|Process arrangement and method for producing a fiber-reinforced plastic component|
    BR112017017573A2|2015-02-23|2018-05-08|Basf Se|? method for manufacturing fiber reinforced components or semi-finished products?|
    WO2016150716A1|2015-03-24|2016-09-29|Basf Se|Method for producing a thermoplastic, fibre-reinforced semi-finished product|
    US10717245B2|2018-04-03|2020-07-21|Johns Manville|System for producing a fully impregnated thermoplastic prepreg|
    US10857744B2|2018-04-03|2020-12-08|Johns Manville|System for producing a fully impregnated thermoplastic prepreg|
    DE102015217088B4|2015-09-07|2021-01-21|Volkswagen Aktiengesellschaft|Process for producing a semi-finished product from a polyamide-containing composite material and a semi-finished product obtained therefrom|
    DK3390038T3|2015-12-18|2021-02-01|Lanxess Deutschland Gmbh|MANUFACTURE OF FIBER COMPOSITE MATERIALS|
    DE102016202053B4|2016-02-11|2021-02-11|Volkswagen Aktiengesellschaft|Process for the production of thermoplastic preforms|
    JP2019522709A|2016-06-30|2019-08-15|ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ|Method for producing a functionalized three-dimensional shaped body|
    DE102016009907A1|2016-08-18|2018-02-22|Basf Se|Process for producing a fiber-reinforced plastic component|
    DE102016222550B4|2016-11-16|2020-03-05|Volkswagen Aktiengesellschaft|Floor arrangement for a temperature-controlled battery housing|
    DE102017200114A1|2017-01-05|2018-07-05|Volkswagen Aktiengesellschaft|Process for the production of thermoplastic preforms in the tape laying process|
    US10493698B2|2017-07-20|2019-12-03|GM Global Technology Operations LLC|Method of manufacturing a workpiece|
    DE102018203360B4|2018-03-07|2021-12-30|Volkswagen Aktiengesellschaft|Temperature control device for and an organic strip material plant for the production of flat fiber composite semi-finished products, as well as a corresponding production process|
    CN108948345A|2018-06-25|2018-12-07|长沙五犇新材料科技有限公司|Fibre reinforced successive reaction forms nylon composite materials and its preparation method and application|
    KR102339294B1|2020-10-30|2021-12-14|재단법인 한국탄소산업진흥원|Carbon fiber UD tape manufacturing apparatus and manufacturing method using reaction polymerization|
    法律状态:
    2018-05-02| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-05-08| B25A| Requested transfer of rights approved|Owner name: BASF SE (DE) |
    2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-01-14| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-03-24| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/02/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11156759.0|2011-03-03|
    EP11156759|2011-03-03|
    PCT/EP2012/053246|WO2012116947A1|2011-03-03|2012-02-27|Method for producing fiber-reinforced, flat semi-finished products containing a polyamide matrix|
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